WO2020130272A1

WO2020130272A1 - Glass bonding film and manufacturing method thereof

Info

Publication number: WO2020130272A1
Application number: PCT/KR2019/010299
Authority: WO
Inventors: 김혜진
Original assignee: 에스케이씨 주식회사
Priority date: 2018-12-20
Filing date: 2019-08-13
Publication date: 2020-06-25
Also published as: KR20200084390A; KR102156985B1

Abstract

A method for manufacturing a glass bonding film according to one embodiment of the present invention comprises: a melting step of manufacturing a molten resin by melting a composition comprising a polyvinyl acetal resin and an additive; and a molding step of forming a glass bonding film by discharging the molten resin through a molding part and molding the resin into a film shape, wherein the additive contains a metal salt, and an electric force is applied through the molding part to the molten resin in the molding step so as to prepare a glass bonding film that satisfies equation 1 described in the detailed description.

Description

Glass bonding film and manufacturing method thereof

The present invention relates to a film for glass bonding and a method for manufacturing the same.

In general, laminated glass (tempered glass, safety glass) composed of a pair of glass panels and a synthetic resin film interposed between the panels is excellent in safety because the fragments do not scatter even when damaged, and the Widely used in windowpanes and building windowpanes. In many cases, a polyvinyl acetal resin having high affinity for inorganic materials is applied to the film applied to the laminated glass.

Laminate glass, which places a film between a pair of glass panels, has the basic properties required for laminated glass, such as penetration resistance or difficulty in shattering glass, but may have poor moisture resistance, in which case laminated glass in a high humidity atmosphere On the periphery of the film, the interlayer film directly contacts the air and whitening occurs in the periphery. And, for the purpose of preventing such a whitening phenomenon, an additive for adjusting the bonding force between the film and glass is used.

Japanese Unexamined Patent Publication No. 1998-139496 (Application No. 1996-290261) discloses a film that does not undergo whitening as an interlayer film for laminated glass containing polyvinyl butyral, plasticizer, carboxyl metal salt and modified silicone oil. However, the film has reduced compatibility with polyvinyl butyral resins due to the use of modified silicone oils with low polarity, resulting in increased haze in the final film, and functional groups of the glass to react with hydroxyl groups of the polyvinyl butyral resin. As the bonding strength is significantly reduced due to interference with the modified silicone oil, penetration resistance and impact resistance are deteriorated.

In addition, if an excessive amount of additive is applied for the effect of controlling the bonding force, moisture resistance is lowered, and yellowness may be increased in long-term durability evaluation.

An object of the present invention is to provide a method for manufacturing a glass bonding film and a glass bonding film having improved durability and moisture resistance.

In order to achieve the above object, an aspect of the present invention is a melting step of manufacturing a molten resin by melting a composition comprising a polyvinyl acetal resin and an additive; And, it provides a method for manufacturing a film for glass bonding, including a molding step of discharging the molten resin through a molding unit and molding in a film form to form a film for glass bonding.

The additive contains a metal salt.

The forming unit applies electric force to the molten resin.

The glass bonding film satisfies Equation 1 below.

[Equation 1]

M1> M2

In Equation 1, M1 is an average metal ion content from a first depth (D1) to a second depth (D2) based on the surface of the glass bonding film, and the M2 is the surface of the glass bonding film. With reference to, the average content of metal ions from the third depth (D3) to the fourth depth (D4), D1 and D2 are respectively values of 60 nm or less, and D3 and D4 are values of 80 nm or more, respectively.

The molded part may include a tee die located at one end.

The forming unit may apply a voltage of 10 kV or less.

In the forming step, a voltage of 10 kV or less may be applied to the forming part.

The electric force may apply an attraction force to the forming portion to the metal ion.

By the electric force in the forming step, an attraction force to the forming part may be applied to the metal ion.

The D1 may belong to 0.1 nm to 15 nm. The D2 may belong to 40 nm to 55 nm. The D3 may belong to 80 nm to 95 nm. The D4 may belong to 135 nm to 150 nm.

The difference between D2 and D1 may correspond to the difference between D4 and D3.

The D1 may be 5 nm. The D2 may be 55 nm. The D3 may be 90 nm. The D4 may be 140 nm.

The M1 may be three or more times the M2.

In order to achieve the above object, another aspect of the present invention includes a polyvinyl acetal resin, a metal salt or a metal ion together with a plasticizer, and satisfies Equation 1 below, to provide a film for glass bonding.

[Equation 1]

M1> M2

The first depth and the second depth may be the same value or different values. The first depth and the second depth may be a value having a difference of 3 or more, and a value having a difference of 5 or more.

The third depth and the fourth depth may be the same value or different values. The third depth and the fourth depth may be a value having a difference of 3 or more, and a value having a difference of 5 or more.

The M1 may be three or more times the M2.

The metal ion may include a divalent metal ion.

An average whitening distance value of the glass laminate laminated with the glass bonding film therebetween may be 5 mm or less.

The glass bonding film may have 3 to 4 stages of the level of the strength of the laminated glass to form a film.

In order to achieve the above object, another aspect of the present invention is a first glass substrate; A second glass substrate facing the first glass substrate; And a glass bonding film interposed between the first glass substrate and the second glass substrate and bonded to the first glass substrate and the second glass substrate, wherein the film for glass bonding is a polyvinyl acetal resin, It contains a metal salt or a metal ion together with a plasticizer, and satisfies Equation 1 below.

[Equation 1]

M1> M2

In Equation 1 above,

The M1 is the average content of metal ions from the first depth (D1) to the second depth (D2) based on the surface of the film for glass bonding, and the M2 is based on the surface of the film for glass bonding. The average content of metal ions from 3 depths (D3) to 4th depths (D4), D1 and D2 are respectively 60 nm or less, and D3 and D4 are 80 nm or more, respectively.

The film for glass bonding of the present invention can provide a film for glass bonding or the like, which has excellent bonding force control effect even if a relatively small amount of metal salt is applied, and which does not substantially exhibit reduced moisture resistance or long-term durability.

The method for manufacturing a glass bonding film of the present invention can control the concentration of metal salts (or metal ions) depending on the depth of the film by applying an electric force, so that the glass bonding film is controlled with properties such as glass bonding strength and moisture resistance. Can be produced.

1 is a schematic diagram illustrating a device structure of a die lip for adjusting the ion concentration of a film surface applied in an embodiment of the present invention.

2 is a view for explaining a method of measuring a whitening distance measured in an embodiment of the present invention.

3 is a conceptual diagram (a) for explaining a cross section of a laminated glass according to an embodiment of the present invention, and a conceptual diagram (b) for explaining the first to fourth depths of the equation.

Figure 4 is a graph showing the average value in the range of 5 to 105 nm in the results of evaluating the surface ion concentration of the film in the embodiment of the present invention in 10 nm units, the horizontal axis represents the depth (depth, nm) and the vertical axis It means intensity (counts), and #1 and #2 represent Example 1 and Example 2, respectively.

* Cross-referencing with associated applications

This application has the benefit of priority under Korean Patent Application No. 10-2018-0166257 filed on December 20, 2018, and all of the basic applications of the priority are included as content of this application.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains may easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. The same reference numerals are used for similar parts throughout the specification.

Throughout the present specification, the term “combination of these” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the marki form, the component. It means to include one or more selected from the group consisting of.

Throughout this specification, terms such as “first”, “second” or “A” and “B” are used to distinguish the same terms from each other. In addition, a singular expression includes a plural expression unless the context clearly indicates otherwise.

In the present specification, the “~” system may mean that a compound corresponding to “~” or a derivative of “~” is included in the compound.

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

In the present specification, a singular expression is interpreted to include a singular or plural number that is interpreted in context unless otherwise specified.

The inventors of the present invention, when applying a relatively large amount of the metal salt compound, the effect of controlling the bonding force can be sufficiently obtained, but the finding that the yellowing phenomenon is likely to occur, while researching a solution to this, the bonding force is more effective even in a small amount The present invention was completed by developing a film for controlling glass.

The present invention is to produce a film having a concentration gradient so that the metal salt ions are more arranged toward the surface by a method such as applying a voltage during the manufacturing process of the film, while reducing the applied amount of the metal salt compound to less than or equal to obtain a sufficient bonding force control effect, , It is also possible to manufacture a film for glass bonding, etc. with substantially improved moisture resistance and/or durability.

1 is a schematic diagram illustrating a device structure of a die lip for adjusting the ion concentration of a film surface applied in an embodiment of the present invention, and FIG. 2 is a diagram illustrating a method of measuring the whitening distance measured in an embodiment of the present invention 3 is a conceptual diagram (a) for explaining a cross section of a laminated glass according to an embodiment of the present invention, and a conceptual diagram (b) for explaining the first to fourth formulas. The present invention will be described in more detail with reference to FIGS. 1 to 3.

In order to achieve the above object, a method of manufacturing a film for glass bonding according to an embodiment of the present invention, including a melting step and a molding step, in the molding step, the molten resin is applied with electric force through the molding part, A glass bonding film 110 satisfying Equation 1 below is prepared.

[Equation 1]

M1> M2

The melting step is a step of manufacturing a molten resin by melting a composition comprising a polyvinyl acetal resin and an additive.

The additive may contain a metal salt.

The melting step may be applied to a resin melting method applied to a conventional film production, for example, a twin-screw extruder may be applied.

The composition comprising the polyvinyl acetal resin and the additive and the metal salt contained in the additive will be described later.

The forming step is a step of discharging the molten resin through a molding part and forming a film 110 for glass bonding by molding in a film form.

The molding part may be applied as long as it can be manufactured in a film form while controlling the thickness, and in the case of manufacturing a single-layer film, it is put into an extruder (for example, a twin-screw extruder) and melt-discharged to control the thickness through a T-die to be produced in a film form. In the case of a multi-layer film, it may be melt-extruded in an extruder, and then laminated through a laminating device such as a feed block and a multi-manifold, and molded into a film form in a T-die (coextrusion method).

The molding unit may include a T-die 200 positioned at one end.

In the forming step, electric power may be applied to the molten resin 1 through the forming part.

By the electric force in the forming step, the attraction force to the forming part may be applied to the metal ion.

The molding step will be described by way of example where the T-die is located in the molding part. The T-die 200 is located at one end of the molding part, and the T-die 200 has an inlet (not shown) through which the molten resin composition 1 is introduced and an outlet through which the molten resin composition is discharged. Die

ribs

210 and 230 are located on both sides of the portion where the molten resin composition is discharged. In the present invention, the

voltage applying parts

220 and 240 are located on the

die lips

210 and 230 on both sides. The

voltage applying units

220 and 240 are voltage applying devices such as, for example, tungsten wire, and are devices capable of applying the applied voltage to the die

lips

210 and 230. The

voltage applying units

220 and 240 are electrically connected to an external power supply (not shown).

The

voltage application parts

220 and 240 adjust the voltage of the die lip so that the molten resin 1 becomes a charged molten resin 2.

The charged molten resin 2 includes a high concentration region 3 formed by moving metal ions contained in the molten resin 1 to the surface. The high concentration region 3 refers to a region in which the surface ion concentration described below is higher than the film average ion concentration.

Both surfaces of the film for glass bonding may contain the metal salt or the metal ion more distributed compared to the center of the film for glass bonding.

The charged molten resin 2 having the high concentration region 3 on the surface side may then form a glass bonding film having a U-type metal ion concentration gradient in the thickness direction.

Specifically, a voltage applied to the forming unit may be applied with a voltage of 10 kV or less, and a voltage of 1 to 10 kV may be applied. A voltage of 1.5 to 8 kV may be applied to a voltage applied to the molding part, and a voltage of 2.5 to 6 kV may be applied.

If the voltage is too low, the force pulling the metal ion, which is a cation, toward the surface of the film is weak, so that a sufficient concentration gradient may not be induced, and if a too strong voltage is applied, deterioration may occur in the polymer film, and the film for glass bonding It may affect the film properties such as the optical properties and long-term durability of the film, which may degrade the properties of the film.

When the molten resin contains 0.1 to 0.3 wt% of the metal salt, a voltage applied by the voltage application part may be applied at 4 to 6 kV.

When the molten resin contains more than 0.3 wt% and 0.8 wt% or less of the metal salt, a voltage of 3 to 4 kV may be applied.

The voltage may be applied to pull the metal ion, which is a cation, and specifically, may be applied to have a negative charge.

Alternatively, an electric force may be applied to the molten resin by static electricity. For example, when the molten resin is extruded, static electricity generated by friction remains in the molding unit, and an electric force may be applied to the molten resin through the molding unit. For example, the molded part may not be grounded so that static electricity remaining in the molded part is not easily discharged. In addition, even if the molding part is grounded, the resistance of the ground wire connected to the molding part is high, so that some static electricity remains, the amount of static electricity discharged may be adjusted.

The molten resin 2 charged in the forming step may be discharged at a rate of 5 to 15 m per minute to form a film. The speed may be 5 to 15 m per minute, or 7 to 13 m.

After the forming step, a process commonly applied to manufacturing a film for glass bonding can be applied in the same way, and detailed description is omitted.

The polyvinyl acetal resin and additives applied to the molten resin formation will be described.

The polyvinyl acetal may be polyvinyl acetal obtained by acetalizing polyvinyl alcohol having a polymerization degree of 1,600 to 3,000, and may be polyvinyl acetal obtained by acetalizing polyvinyl alcohol having a polymerization degree of 1,700 to 2,500. . When such a polyvinyl acetal is applied, it is possible to sufficiently improve mechanical properties such as penetration resistance.

The polyvinyl acetal may be a synthesis of polyvinyl alcohol and 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 to the aldehyde, the prepared polyvinyl acetal resin may have a refractive index characteristic with a small difference in refractive index of glass and excellent bonding strength with glass.

The additives include plasticizers.

The plasticizer is triethylene glycol bis 2-ethylhexanoate (3G8), tetraethylene glycol diheptanoate (4G7), triethylene glycol bis 2-ethylbutyrate (3GH), triethylene glycol bis 2-heptanoate (3G7) ), dibutoxyethoxyethyl adipate (DBEA), butyl carbitol adipate (DBEEA), dibutyl sebacate (DBS), bis 2-hexyl adipate (DHA) and mixtures thereof. More specifically, triethylene glycol bis 2-ethylhexanoate (3G8) may be applied as the plasticizer.

The additive includes a metal salt compound.

The metal salt compound is applied to obtain the effect of controlling the bonding force, specifically, a metal salt of a carboxylic acid having 2 to 16 carbon atoms may be applied, and more specifically, a metal salt of a divalent metal having 2 to 12 carbon atoms, or 1 to 2 carbon atoms. Metal salts of temporary metals may be applied.

The metal ion contained in the metal salt compound may be any one selected from the group consisting of sodium monovalent cation, magnesium divalent cation, and potassium monovalent cation.

The metal salt compound may be applied to the composition in the form of a metal salt compound or in an ionized state dissolved in a solvent, and serves as a bonding power regulator. Specifically, the bonding force between the film and the glass surface can be adjusted. When the metal salt compound is applied to the composition in a solution state, dispersion and movement of ions derived from the metal salt compound or the metal salt compound may be more easily performed in a film or a bonding layer prepared.

The metal salt compound may be included in less than 1.0% by weight, less than 0.5% by weight, and may be included in 0.35% by weight or less based on the entire molten resin. In addition, the metal salt compound may be included in an amount of 0.01 to 0.5% by weight, 0.01 to 0.35% by weight, 0.01 to 0.25% by weight, and 0.01 to 0.2% by weight based on the entire molten resin. Can. The molten resin may constitute a single-layer film or a surface layer of a multilayer film.

The metal salt compound may be included so that the content of metal ions derived from the metal salt compound is 150 ppm or less, and 100 ppm or less based on the entire molten resin. In addition, the content of the metal ion may be included to be 1 to 70 ppm based on the entire molten resin, may be included to be 1 to 50 ppm, may be included to be 1 to 35 ppm. Even if the metal salt compound or the metal salt ion is contained in such a very low content, the metal ion is positioned on a surface requiring a bonding power control effect by the method applied in the present invention, so that a sufficient bonding power control effect can be obtained. At this time, ppm is calculated based on the weight.

The metal salt compound is included in the amount described above based on the entire composition, to prepare a single layer glass bonding film, and when preparing a multilayer glass bonding film, the surface layer of the composition containing the metal salt compound ( Bonding layer).

In the polyvinyl acetal resin composition applied to the production of laminated glass, an ultraviolet stabilizer (ultraviolet absorber) may be applied together to enhance the UV blocking effect, and a benzotriazole-based compound may also be applied as such an ultraviolet stabilizer.

The benzotriazole-based compound may cause a change in the binding structure of the benzotriazole-based compound due to the interaction between the hydroxyl group in the molecule and the nitrogen contained in the triazole ring located close to the hydroxyl group for energy of ultraviolet rays, At this time, if metal ions are involved, the effect as an ultraviolet stabilizer may be reduced. In addition, the benzotriazole-based compound is coordinated with polyvalent metal ions to form a chelate ring. The benzotriazole-based compound formed with the chelate ring does not sufficiently function as an ultraviolet stabilizer and may weaken the durability of the entire film. .

The ultraviolet stabilizer may be applied without limitation as long as it is applied as an ultraviolet stabilizer, and it is also possible to apply an ultraviolet stabilizer containing a benzotriazole-based compound. Specifically, Chemisorb 12, Chemisolve 79, Chemisolve 74, Chemisolve 102, BASF's Tinuvin 328, Tinuvin 329, Tinuvin 326, etc. may be used.

In the present invention, in order to sufficiently function as a UV stabilizer of the benzotriazole-based compound applied to the production of a film for glass bonding and to improve the durability of the film itself, even if a small amount is applied, it has an excellent bonding strength control effect.

Based on 100 parts by weight of the benzotriazole-based compound, the metal salt compound may include 16 parts by weight or less, 12 parts by weight or less, and 1 to 10 parts by weight. When the metal salt compound is contained in an amount of less than 1 part by weight based on 100 parts by weight of the benzotriazole-based compound, the effect of adjusting the bonding strength obtained by adding the metal salt compound may not be sufficient, and when it is included in more than 16 parts by weight, water resistance is rather Can fall.

The composition may further contain an additive selected from the group consisting of an antioxidant, a heat stabilizer, an IR absorber, and a combination thereof, as necessary. The additive may be included in at least one of the layers above, or may be included in the entire film.

By including the additive in the composition, it is possible to further improve long-term durability and scattering prevention performance, such as thermal stability and light stability of the film.

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

The thermal stabilizer may be a phosphite-based thermal stabilizer when considering compatibility with an antioxidant. For example, BASF's IRGAFOS 168 can be used. ITO, ATO, AZO, etc. may be used as the IR absorber, but the present invention is not limited thereto.

The glass bonding film has the characteristics described below, and the detailed description thereof will be omitted because it overlaps with the description below.

The film 110 for glass bonding according to another embodiment of the present invention is a film for glass bonding containing a metal salt, wherein the average content of metal ions within a depth of 50 nm from the surface is the metal ion of the entire film for glass bonding. Higher than the average content.

More specifically, the film 110 for glass bonding according to an embodiment of the present invention includes a metal salt or a metal ion together with a polyvinyl acetal resin and a plasticizer, and satisfies Equation 1 below.

[Equation 1]

M1> M2

Here, M1 is the average content of metal ions from the first depth (D1) to the second depth (D2) based on one surface 111 of the film for glass bonding, and the M2 is the film for the glass bonding film. Based on one surface 111, the average content of metal ions from the third depth D3 to the fourth depth D4, D1 and D2 are values of 60 nm or less, and D3 and D4 are 80 nm or more Is the value.

The first depth and the second depth may be the same value or different values.

The third depth and the fourth depth may be the same value or different values.

Referring to Figure 3 in more detail, the first depth (D1), the second depth (D2), the third depth (D3) and the fourth depth (D4) are each of the film for the glass bonding It means a predetermined depth from one surface 111. Here, one surface 111 of the glass bonding film may be a bonding surface of the glass bonding film 110 that is directly contacted with a glass substrate or the like and is bonded to the glass substrate or the like.

In one embodiment, the D1 belongs to 0.1 nm to 15 nm, the D2 belongs to 40 nm to 55 nm, the D3 belongs to 80 nm to 95 nm, and the D4 belongs to 135 nm to 150 nm. Can.

In one embodiment, the difference between D2 and D1 may correspond to the difference between D4 and D3. That is, the difference between the first depth and the second depth may be substantially the same as the difference between the third depth and the fourth depth.

In one embodiment, the D1 is 5 nm, the D2 is 55 nm, the D3 is 90 nm, and the 140 nm.

In addition, in one embodiment, the M1 may be 3 times or more of the M2, 3.5 times or more, 8 times or less, and 6 times or less.

When the concentration of metal ions is differently applied depending on the thickness from the surface of the film for the glass bonding, even if an equal amount of the metal salt compound is applied as a bonding force control agent, the concentration gradient is concentrated so that the distribution of the metal salt compound, especially the metal cation, is concentrated on the surface. It is possible to provide a film for glass bonding.

This means that a small amount of a metal salt compound is applied to the entire surface of the film while the additive having the effect of controlling the bonding force (including the material derived from this additive) works sufficiently on the surface of the glass bonding film that interacts with the glass to be bonded. By doing this, it is also possible to obtain the effect of improving the moisture sensitivity of the film.

The film for glass bonding may have an average content of metal ions within a depth of 50 nm from a surface of at least 1.2 times and 1.5 times higher than the average content of metal ions in the entire film for glass bonding.

The film for glass bonding may have an average content of metal ions within a depth of 50 nm from the surface of the glass bonding film 1.5 to 4 times, more specifically 1.9 to 3 times higher than the average content of metal ions in the entire film.

When the metal ion concentration is distributed according to the depth from the clear surface, an excellent bonding force control effect can be obtained even if a smaller amount of the metal salt is applied.

The metal ion may include a divalent metal ion.

The metal ion may be formed of a divalent metal ion.

The metal ion may be magnesium divalent ion.

The film for glass bonding is to have the laminated glass containing the film for glass bonding in a constant temperature and humidity chamber at 65°C and 95%rh for 2 weeks, and then take it out, and the measured whitening distance is 5 mm or less, and has excellent moisture resistance. Can.

In the glass bonding film, the amount of change in yellowness before and after leaving the laminated glass containing the glass bonding film in a constant temperature and humidity chamber at 65°C and 95%rh for 2 weeks may be 2.5 or less.

The film for bonding the glass may have a grade of 3 to 4 in the degree of a polymer bonding strength of the laminated glass including the film for bonding the glass.

The thickness of the film for glass bonding may be 0.4 mm or more, specifically 0.4 to 1.6 mm, 0.5 to 1.2 mm, and 0.6 to 0.9 mm. In the case of manufacturing the film with such a thickness, it is possible to provide a film having characteristics such as excellent impact resistance and penetration resistance while being thin and light.

The glass bonding film may have a single-layer structure, a structure having two or more layers, a structure having three or more layers, or a structure having five or more layers.

When the film for glass bonding has a structure of three or more layers, a layer positioned therein except for the surface layers on both sides may be a functional layer.

The functional layer may be, for example, a sound insulating layer that imparts sound insulating functionality to the film for glass bonding.

The functional layer may be, for example, a wedge layer capable of imparting the functionality of the head-up display.

When the film for glass bonding has a structure of three or more layers, the characteristic for the metal salt or metal ion described above may be a characteristic applied to the surface layer.

The laminated glass 100 according to another embodiment of the present invention includes a laminate including the glass bonding film 110 described above between two sheets of

glass

120 and 130.

Specifically, the laminated glass 100 includes a first glass substrate 120; A second glass substrate 130 facing the first glass substrate; And a glass bonding film 110 interposed between the first glass substrate 120 and the second glass substrate 130 and bonded to the first glass substrate 120 and the second glass substrate 130. It includes.

The glass bonding film 110 includes a metal salt or metal ion together with a polyvinyl acetal resin and a plasticizer, and satisfies Equation 1 below.

[Equation 1]

M1> M2

The two sheets of glass are the first glass substrate and the second glass substrate, which are described herein as glass, but can be applied to any light-transmitting panel, and materials such as plastic are also applicable.

Details of the specific structure, composition, characteristics, manufacturing method, etc. of the glass bonding film are overlapped with those described above, and thus description thereof is omitted.

The laminated glass may have an average whitening distance of 5 mm or less, and may be 0 to 5 mm, after measuring a specimen of 100 mm*100 mm area for 2 weeks in a constant temperature and humidity chamber at 65° C. and 95% rh. mm. This average whitening distance means that it has excellent water resistance even under high temperature and high humidity conditions.

The amount of change in yellowness before and after the laminated glass is left for 2 weeks in a constant temperature and humidity chamber at 65°C and 95%rh may be 2.5 or less. This is a result showing that it has excellent long-term durability, in particular, it can be evaluated as a better result in a film containing a benzotriazole-based compound and a metal salt at the same time.

The laminated glass may have a grade of 3 to 4 in the bonding strength of the polymer. This means that the bonding force between the glass and the film has a sufficient bonding force to function as a safety glass in an appropriate range.

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

1. 재료의 준비1. Preparation of ingredients

1) Preparation of additive composition

The additive composition 1 was prepared by mixing the antioxidant Irganox1010 with 0.15 wt% based on the total film, the UV absorber TINUVIN P with 0.3wt%, and the metal salt adhesion control agent magnesium acetate with 0.18 wt%.

Magnesium acetate (Mg acetate) was prepared in the same manner as the additive composition 1 except that 1.25 wt% was applied to prepare an additive composition 2.

2) Preparation of polyvinyl butyral resin (A)

A polyvinyl acetal resin having a degree of polymerization of 1700 and a degree of saponification of 99 and n-butanal were introduced into the reactor, and the process of synthesizing a conventional polyvinyl butyral resin was followed by hydroxyl 19.5 wt%, butyral group 79.8 wt%, acetyl 0.7 wt% A polyvinyl butyral resin was obtained.

2. 폴리비닐부티랄 필름의 제조2. Preparation of polyvinyl butyral film

1) Setting for film production of the example

In order to control the ion concentration of the film surface, a special type device in which a tungsten wire (manufactured by VWF Industries) is mounted on a die lip portion was applied.

Both ends of the tungsten wire are connected to an electric generator, and it is possible to apply voltage to the tungsten wire, and depending on the mode of the generator, POSITIVE or NEGATIVE can be selected to impart (+) or (-) characteristics to the wire. . In the present invention, the NEGATIVE mode was selected and used to control the concentration distribution of metal ions in Examples (see FIG. 1 ).

2) Preparation of the film of Example 1

A polyvinyl butyral resin (A) in a twin-screw extruder, 3G8 was added to 72.37wt% as a plasticizer, 27wt% and 0.63wt% of the additive composition was melt-extruded, and then 10M per minute through the T-die, which was the device set above A film shape having an overall thickness of 780 µm was prepared. At this time, the applied current was 5 kV.

3) Preparation of the film of Example 2

A film of Example 2 was prepared in the same manner as the film of Example 1, except that the applied voltage was lowered to 4.5 KV.

3. 폴리비닐부티랄 필름의 물성 평가3. Evaluation of physical properties of polyvinyl butyral film

1) Preparation of laminated glass samples for evaluation of durability/water resistance

Examples 1 and 2 were left at 20°C and 30%RH for 1 week, and then cut to a size of 100mm*100mm horizontally and vertically and placed 2.1T (mm, hereinafter the same) transparent glass on both sides to place 2.1T. As a laminated structure of glass-film-2.1T glass, preliminary bonding was performed for 20 seconds at 120'C in a vacuum laminator and 1 atmosphere.

Thereafter, a laminated body of pre-bonded glass-film-glass was subjected to main bonding in an autoclave to obtain a laminated glass sample. The conditions of the main bonding were applied at room temperature from room temperature to 140'C for 25 minutes, and at 140'C for 25 minutes.

2) Durability evaluation: yellowness change amount (d-YI) evaluation method

The yellowness _initial value (YI _initial ) at the center of the center of the laminated glass sample prepared above was measured using the UltraScan Pro manufactured by Hunter Lab, under the conditions of D65 and 10° C. according to ASTM E313 standards. After the yellowness initial value measurement has been completed, the specimen is left in a constant temperature and humidity chamber at 65°C and 95%rh for 2 weeks, taken out, and the yellowness is measured again in the same manner as above to measure the yellowness completion value (YI _final ) and the yellowness difference. Was calculated by the following equation (5).

Equation (5) d-YI = YI _final -YI _initial

When the value obtained by the above formula was 2.5 or less, it was evaluated as Pass, and when it was more than 2.5, it was evaluated as Fail.

3) Moisture resistance evaluation: Whitening distance measurement

The laminated glass sample 100 prepared above was left in a constant temperature and humidity chamber at 65°C and 95%rh for 2 weeks, and then taken out and visually confirmed the area where haze occurred (the area where whitening occurred, 10) from the center of the four sides. The distance was measured with a ruler (refer to FIG. 2), and the average value of the four sides was calculated according to the following equation (6) and expressed as the whitening distance (mm).

Equation (6) Average whitening distance = (d11+ d12+ d13+ d14)÷ 4

In the formula (6), the distances at which the whitening phenomenon measured in the center of the first to fourth sides appeared are referred to as d11 to d14, respectively (unit is mm).

When the average whitening distance was 5 mm or less, it was evaluated as a pass, and when it exceeded 5 mm, it was evaluated as a fail.

4) Evaluation of Fummel bonding power

The bonding strength between the polyvinyl acetal film and the glass was evaluated through the evaluation of the pummel bonding force. Specifically, the PVB films prepared in Examples 1 and 2 were left at 20° C. and 30% RH for 1 week, and then placed two sheets of 2.1T transparent glass on both sides to produce 2.1T glass with a width*length of 100mm×150mm. A laminated structure of film-2.1T glass was prepared. The laminated structure was pre-bonded at 150'C in a vacuum laminator and 20 seconds at 1 atmosphere. Subsequently, the pre-bonded laminated structure was subjected to main bonding in an autoclave at room temperature from room temperature to 140'C for 25 minutes, and retention time at 140'c for 25 minutes to obtain a specimen of laminated glass.

After cooling the specimen in the form of laminated glass at -20°C for 4 hours, after hitting with a hammer, the degree of the amount of glass remaining in the film was measured. After hitting, it was bonded to the film and dropped out according to the amount of glass remaining, and the grade of 0 was assigned to the case where all the glass remained on the film, and the value from grade 0 to grade 8 was assigned. In the case of between 3 and 4, Pass, 5 or more, or 2 or less, was marked as Fail.

5) Evaluation of surface ion concentration

To check the surface ion concentration of the film, a secondary ion mass spectrometer (TOF SIMS) capable of measuring the strength of the surface ions was used. First, in order to increase the precision of the analysis, a pretreatment process was performed to remove the surface roughness of the manufactured film. The pre-treatment method was performed by heat-treating for 3 minutes under a condition of 1 atm and 150 degrees in a vacuum laminator to flatten the pattern on the surface, and then allowed to stand at 20°C and 30% RH (Relative Humidity) for 1 hour to remove heat. .

The pre-treated film was sampled in a size of 10 mm*10 mm in width*length, mounted on a sample holder, and measured. After sputtering once in TOF-SIMS, the thickness of the surface to be cut was set to 1 nm, and after sputtering and measuring about 160 times, data up to 160 nm in depth were obtained and used to conduct ion concentration analysis according to depth. For a more accurate comparison, data up to 4 or 5 nm from the surface was excluded and evaluated to remove noise caused by foreign matter on the surface.

As a result of evaluating the surface ion concentration of the film, the values in the range of 5 to 105 nm were averaged in 10 nm units and shown in the graph of FIG. 4. In FIG. 4, the horizontal axis represents depth (nm), and the vertical axis represents intensity (counts), and #1 and #2 represent Example 1 and Example 2, respectively.

Among them, values of depths of 5 to 55 nm and 90 to 140 nm that can clearly identify changes are shown in Table 1 below.

깊이에 따른According to depth	실시예 1Example 1	실시예 2Example 2
5-55 nm에서 평균Average at 5-55 nm	50.6950.69	39.2139.21
90-140 nm에서 평균Average at 90-140 nm	11.5111.51	10.8110.81

Referring to Table 1, Example 1 and Example 2 showed a concentration difference of about 4.4 times for Example 1 and about 3.6 times for Example 2. These results show that the average value of metal ions obtained at a depth of approximately 5 to 55 nm differs from the average value of metal ions obtained at 90 to 140 nm, which is thought to be a result showing characteristics obtained in Examples of the present invention. do.

In addition, the values in the range of 5 to 145 nm with a large concentration change according to the depth are averaged in 10 units, and are shown in Table 2 and FIG. 4 below. Other measured values and conditions are shown in Table 3 below.

깊이에 따른 (nm)Depending on the depth (nm)	실시예 1Example 1	실시예 2Example 2
6-156-15	89.9689.96	83.7383.73
16-2516-25	60.0260.02	45.5745.57
26-3526-35	42.8642.86	29.9329.93
36-4536-45	31.3331.33	18.1118.11
46-5546-55	24.5224.52	13.2113.21
56-6556-65	19.4119.41	12.6112.61
66-7566-75	15.1115.11	11.7111.71
76-8576-85	13.2113.21	11.3111.31
86-9586-95	13.6113.61	11.9111.91
96-10596-105	12.2112.21	11.0011.00

		실시예 1Example 1	실시예 2Example 2
금속염 투입량(ppm)Metal salt input (ppm)	Mg AcetateMg Acetate	3333	3333
인가 전압Applied voltage		5kV5 kV	4.5kV4.5kV
평가evaluation	펌멜접합력Fummel bonding power	Pass Pass	Pass Pass
	내습성 Moisture resistance	Pass Pass	Pass Pass
	내구성durability	Pass Pass	Pass Pass

Referring to Tables 2, 4, and 3 above, it can be seen that the films of Examples 1 and 2 prepared by applying a voltage had a high concentration of magnesium ions derived from metal salts on the surface. Particularly, it was confirmed that the concentration gradient of the metal ion appeared to a thickness deeper than that of Example 2 in the case of Example 1 in which the voltage was applied more strongly. These characteristics can be confirmed by looking at the difference between the average surface ion concentration except for the surface ion concentration and the surface ion concentration evaluated based on about 50 nm.

In the case of the Fummel bonding force, Examples 1 and 2 were shown as Pass, and it was found to have an appropriate bonding force control effect. In the case of Examples 1 and 2, it was excellent in moisture resistance and durability, and satisfies all three characteristics conditions that are difficult to obtain at the same time. Confirmed.

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.

*Description of code

1: molten resin 2: charged molten resin

3: High concentration area

100: laminated glass 110: glass bonding film

111: one surface of the film for glass bonding

120: glass, first glass 130: second glass

200: T-die 210: first die lip

220: first voltage application unit 230: second die lip

240: second voltage application part 100: laminated glass

10: area where whitening occurred 20: area where whitening did not appear

d11: whitening distance at the first side d12: whitening distance at the second side

d13: whitening distance at the third side d14: whitening distance at the fourth side

Claims

Melting step of melting a composition comprising a polyvinyl acetal resin and an additive to prepare a molten resin; And a molding step of discharging the molten resin through a molding part and forming a film to form a glass bonding film,

The additive contains a metal salt,

The molding unit applies an electric force to the molten resin,

The film for glass bonding satisfies Equation 1 below, a method for manufacturing a film for glass bonding:

[Equation 1]

M1> M2

In Equation 1, M1 is an average metal ion content from a first depth (D1) to a second depth (D2) based on the surface of the glass bonding film, and the M2 is the surface of the glass bonding film. With reference to, the average content of metal ions from the third depth (D3) to the fourth depth (D4), D1 and D2 are respectively values of 60 nm or less, and D3 and D4 are values of 80 nm or more, respectively.
According to claim 1,

The forming portion includes a tea die located at one end, a method for manufacturing a glass bonding film.
According to claim 1,

The molding unit is a method of manufacturing a film for glass bonding, applying a voltage of 10 kV or less.
According to claim 1,

The electric force is a method of manufacturing a film for glass bonding, applying an attraction force to the molding part to the metal ion.
According to claim 1,

The D1 belongs to 0.1 nm to 15 nm, the D2 belongs to 40 nm to 55 nm, the D3 belongs to 80 nm to 95 nm, and the D4 belongs to 135 nm to 150 nm. Method of manufacturing.
The method of claim 5,

The difference between the D2 and the D1 corresponds to the difference between the D4 and the D3, a method for manufacturing a glass bonding film.
According to claim 1,

The D1 is 5 nm, the D2 is 55 nm, the D3 is 90 nm, the D4 is 140 nm, and the M1 is three or more times the M2, a method for manufacturing a glass bonding film.
Contains polyvinyl acetal resin and a plasticizer together with a metal salt or metal ion,

Film for glass bonding, which satisfies the following Equation 1:

[Equation 1]

M1> M2

In Equation 1 above,

The M1 is the average content of metal ions from the first depth (D1) to the second depth (D2) based on the surface of the film for glass bonding, and the M2 is based on the surface of the film for glass bonding. The average content of metal ions from 3 depths (D3) to 4th depths (D4), D1 and D2 are respectively 60 nm or less, and D3 and D4 are 80 nm or more, respectively.
The method of claim 8,

The D1 belongs to 0.1 nm to 15 nm, the D2 belongs to 40 nm to 55 nm, the D3 belongs to 80 nm to 95 nm, and the D4 belongs to 135 nm to 150 nm. .
The method of claim 9,

The difference between D2 and D1 corresponds to the difference between D4 and D3, the film for glass bonding.
The method of claim 8,

The D1 is 5 nm, the D2 is 55 nm, the D3 is 90 nm, and the D4 is 140 nm, the film for glass bonding.
The method according to any one of claims 8 to 11,

The M1 is a film for glass bonding three times or more of the M2.
The method of claim 8,

The metal ion comprises a divalent metal ion, the glass bonding film.
The method of claim 13,

The glass bonding film having an average whitening distance value of 5 mm or less of the glass laminate laminated with the glass bonding film therebetween.
The method of claim 13,

A film for glass bonding, wherein the glass bonding film has 3 to 4 stages of the degree of the polymer bonding strength of the laminated glass.
A first glass substrate;

A second glass substrate facing the first glass substrate; And

And a film for glass bonding interposed between the first glass substrate and the second glass substrate, and bonded to the first glass substrate and the second glass substrate.

The glass bonding film includes a polyvinyl acetal resin and a plasticizer together with a metal salt or metal ion, and satisfies the following formula 1, laminated glass;

[Equation 1]

M1> M2

In Equation 1, M1 is an average metal ion content from a first depth (D1) to a second depth (D2) based on the surface of the glass bonding film, and the M2 is the surface of the glass bonding film. With reference to, the average content of metal ions from the third depth (D3) to the fourth depth (D4), D1 and D2 are respectively values of 60 nm or less, and D3 and D4 are values of 80 nm or more, respectively.