KR20190138618A - Film for laminating glasses, composition for glass laminating film and laminating glasses comprising the film - Google Patents

Abstract

The present invention relates to a glass bonding film, a composition for the same, and a bonding glass including the same. The glass bonding film comprises: a first surface layer; a second surface layer facing the first surface layer; and an intermediate layer placed between the first surface layer and the second surface layer, wherein the intermediate layer includes a trioxane compound. The film is excellent in optical characteristics since melt fracture does not occur or hardly occurs in the intermediate layer, and the optical characteristics can be maintained at almost the same level even after moisture resistance evaluation.

Description

Glass Bonding Film, Composition for Glass Bonding Film, and Laminated Glass Comprising the Same {FILM FOR LAMINATING GLASSES, COMPOSITION FOR GLASS LAMINATING FILM AND LAMINATING GLASSES COMPRISING THE FILM}

The present invention relates to a film for glass bonding, a composition for glass bonding film, a laminated glass including the same, and the like, having improved optical properties and moisture resistance.

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

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

The primary function of laminated glass is to minimize the damage or injury to objects or people in the transparent barrier by absorbing the energy caused by the blow, while not allowing penetration through the laminated glass (penetration resistance) (impact resistance). . In addition, it should have an optically excellent property to be applied to transparent glass, and should also have a strong property against the environment such as moisture (optical properties, moisture resistance). In addition, the interlayer sheet applied to the laminated glass may impart additional functionality to the laminated glass such as to attenuate acoustic noise and reduce UV and / or IR light transmission.

Korean Patent Registration No. 10-1558835, 2015.10.08 notification Korean Patent Publication No. 10-2017-0084220, 2017.07.19 published

An object of the present invention is to provide a film for multilayer glass bonding and the like with improved moisture resistance and optical properties.

In order to achieve the above object, the glass bonding film according to an embodiment of the present invention, the first surface layer, the second surface layer facing the first surface layer, and positioned between the first surface layer and the second surface layer. An intermediate layer, wherein the intermediate layer comprises a trioxane compound.

The trioxane-based compound may be included in an amount of 0.001 to 4 wt% based on the entire intermediate layer.

In the glass bonding film, after the moisture resistance evaluation evaluated by immersion in deionized water at 50 ° C. for 3 hours, the haze value of the glass bonding film is less than 15% of the difference between the haze value of the glass bonding film before the evaluation. It may be visible.

The first surface layer may include a plasticized first polyvinyl acetal.

The second surface layer may include a plasticized second polyvinyl acetal.

The first surface layer may include a plasticized first polyvinyl acetal, and the second surface layer may include a plasticized second polyvinyl acetal.

The intermediate layer may include a first intermediate layer including a plasticized third polyvinyl acetal and the trioxane compound; A second intermediate layer positioned between the first intermediate layer and the first surface layer and comprising a plasticized fourth polyvinyl acetal; And a third intermediate layer disposed between the first intermediate layer and the second surface layer and comprising a plasticized fifth polyvinyl acetal.

The intermediate layer may be a layer having a single layer structure including a plasticized third polyvinyl acetal and the trioxane compound.

The content of the plasticizer contained in the first surface layer may be smaller than the content of the plasticizer contained in the intermediate layer or the first intermediate layer.

The difference between the content of the plasticizer contained in the first surface layer and the content of the plasticizer contained in the intermediate layer or the first intermediate layer may be 5 to 18% by weight.

The amount of hydroxyl groups of the fourth polyvinyl acetal may have a value between the amount of hydroxyl groups of the first polyvinyl acetal and the amount of hydroxyl groups of the third polyvinyl acetal.

The amount of hydroxyl groups of the fifth polyvinyl acetal may have a value between the amount of hydroxyl groups of the second polyvinyl acetal and the amount of hydroxyl groups of the third polyvinyl acetal.

The trioxane-based compound may be included in an amount of 1 wt% or less based on the entire glass bonding film.

The trioxane-based compound may have a 1,3,5-trioxane skeleton and 1 to 3 carbon atoms of the three carbon atoms included in the skeleton may each independently have a hydrogen, an alkyl group having 1 to 5 carbon atoms.

According to another aspect of the present invention, there is provided a method of manufacturing a glass bonded film, which comprises: i) a composition for a surface layer comprising first polyvinyl acetal, and ii) a plasticizer, a third polyvinyl acetal, and 0.001 to 4 wt% of a trioxane-based compound. An extrusion step of kneading and extruding the composition for an intermediate layer, respectively; A lamination step of laminating a surface layer melt resin containing the extruded surface layer composition and an intermediate layer melt resin containing the composition for the intermediate layer so that the surface layer composition is positioned above and below the composition for the intermediate layer; And a molding step of forming the laminated molten resin into a sheet shape and manufacturing a glass bonding film; To prepare a film for glass bonding described above.

Laminated glass according to another embodiment of the present invention includes a laminate in which the above-described glass bonding film is positioned between two sheets of glass.

Moving means according to another embodiment of the present invention includes the laminated glass described above.

The glass bonding film of the present invention, a manufacturing method thereof, laminated glass including the same has excellent or low optical properties of the entire film due to the absence or insignificant melt fracture traces of the intermediate layer that can be formed during the manufacturing process, the optical properties are evaluated moisture resistance It is maintained at about the same level afterwards and has excellent moisture resistance.

Figure 1 (a) and (b) is a view showing an example of the cross-section of the film for glass bonding according to an embodiment of the present invention, respectively.
Figure 2 illustratively showing a cross section of the laminated glass according to an embodiment of the present invention.
3 is a view showing an example in which laminated glass is applied as a windshield to an automobile as an example of a moving means according to an embodiment of the present invention.
Figure 4 is a photograph showing the results of visual observation of the optical distortion (distortion) occurring sample (left) and the non-occurring sample (right) of the film prepared in the embodiment of the present invention.

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

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

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

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

As used herein, B on A means that B is positioned on A while B is directly in contact with A or another layer is in between, while B is on a surface of A It is limited to what does and is not interpreted.

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

In the present specification, the weight average molecular weight or the number average molecular weight is expressed by omitting the Dalton Da. The measurement of the weight average molecular weight, etc. has been described based on values measured using gel permeation chromatography (GPC) -evaporative light scattering detector (ELSD), but the measuring method is not limited thereto.

The glass bonding film having the functionality may be configured in the form of a laminate in which a multi-layered film of three or more layers is laminated, and such a multilayered film may have a melt fracture in the intermediate layer during extrusion, In some cases, the traces do not disappear after glass bonding and the traces are observed as optical defects. The inventors of the present invention, while studying a method for recognizing and solving these problems, confirmed that the problem can be solved by applying a trioxane-based compound to the intermediate layer and completed the present invention.

1 is a view showing a cross-section of the glass bonding film according to an embodiment of the present invention by way of example. 1, the glass bonding film 900 according to an embodiment of the present invention has a first surface layer 100 and a second surface layer facing the first surface layer. And an intermediate layer 300 positioned between the first surface layer and the second surface layer, wherein the intermediate layer 300 includes a trioxane compound.

The trioxane-based compound serves as a fluidity improver of the molten resin in the film manufacturing process.

Specifically, the trioxane compound is a trioxane compound having a 1,3,5-trioxane skeleton, a trioxane compound having a 1,2,4-trioxane skeleton or a 1,2,3-trioxane At least one trioxane-based compound having a skeleton may be applied.

Specifically, the trioxane-based compound has the 1,3,5-trioxane skeleton and one to three carbon atoms of the three carbon atoms included in the skeleton independently have hydrogen or an alkyl group having 1 to 5 carbon atoms It may be one having a structure of the formula (1) below.

[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

Specifically, R ₁ , R ₂ and R ₃ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, wherein R ₁ , R ₂ and R ₃ are not all hydrogen at the same time.

The trioxane compound may be trialkyl trioxane, specifically 2,4,6-trimethyl-1,3,5-trioxane, 2,4,6-triethyl-1,3,5-trioxane , 2,4,6-tri (n-propyl) -1,3,5-trioxane, 2,4,6-tri (iso-propyl) -1,3,5-trioxane, 2,4,6 -Tri (n-butyl) -1,3,5-trioxane, 2,4,6-tri (sec-butyl) -1,3,5-trioxane, 2,4,6-tri (isobutyl) -1,3,5-trioxane, 2,4,6-tri (tert-butyl) -1,3,5-trioxane, 2,4,6-tripentyl-1,3,5-trioxane and It may be any one selected from the group consisting of a combination of these.

The trialkyl trioxane is excellent in improving the flowability of the molten resin in the manufacturing process of the glass bonding film.

The trialkyl trioxane may be tripropyl trioxane, specifically 2,4,6-tri (n-propyl) -1,3,5-trioxane, 2,4,6-tri (iso-propyl) It may be any one selected from the group consisting of -1,3,5-trioxane and combinations thereof.

The tripropyl trioxane has excellent compatibility with each of polyvinyl acetal and plasticizers having different polarities, and thus shows excellent activity as a flow improver in the process of manufacturing a glass bonding film. Significantly reduce the occurrence.

The trioxane-based compound may be included in an amount of 0.001 to 4% by weight, 0.01 to 3% by weight, and 0.1 to 1.6% by weight based on the entire intermediate layer. As such, when the intermediate layer contains more than 4% by weight of trioxane-based compound, the effect of improving fluidity and reducing optical defects may be obtained, but moisture resistance may be lowered, and when the amount of the interlayer is less than 0.001% by weight, the trioxane-based compound may be applied. The effect of improving the fluidity of the molten resin may be insignificant. When the trioxane compound is applied to the intermediate layer in the above-described range, the effect of improving the optical properties and the effect of improving moisture resistance can be obtained.

The trioxane compound may be included in an amount of 1 wt% or less based on the entire glass bonding film, may be included in an amount of 0.001 to 0.75 wt%, and may be included in an amount of 0.01 to 0.65 wt%, and 0.04 to 0.3. It may be included in weight percent. When the trioxane-based compound is included in such a content, the optical properties of the film may be improved while there is no or a slight drop in moisture resistance.

The trioxane compound may be specifically 2,4,6-tripropyl 1,3,5-trioxane. The trioxane-based compound is more effective in improving the optical properties and moisture resistance of the glass bonding film by applying it as a fluidity improver in the manufacturing of the interlayer, particularly in the glass bonding film.

The first surface layer 100 and the second surface layer 200 may each contain polyvinyl acetal, ionomer, polyethylene terephthalate or polyimide.

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

The polyvinyl acetal may be a synthesized polyvinyl alcohol and aldehyde, the aldehyde is not limited in kind. 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 aldehyde n-butyl aldehyde is applied, the manufactured polyvinyl acetal resin may have a refractive index characteristic of which the refractive index is less than that of the glass, and may have excellent bonding strength with glass or the like.

The ionomer may include the olefinic repeating unit in an amount of 20 to 95% by weight, may include 20 to 90% by weight, may include 40 to 95% by weight, and include 40 to 75% by weight. can do. The carboxylic acid repeating unit may include 5 to 80% by weight, may include 10 to 80% by weight, may include 5 to 60% by weight, and may include 25 to 60% by weight. .

As the metal ion, monovalent, divalent or trivalent metal ions may be applied, and specifically, Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Ag ⁺ , Hg ⁺ , Cu ⁺ , Be ²⁺ , Mg ^{2 +} , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Cu ²⁺ , Cd ²⁺ , Hg ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Al ²⁺ , Sc ³⁺ , Fe ³⁺ , Al ³⁺ and Yt ³⁺ can be applied. Specifically, Mg ²⁺ , Na ⁺ and Zn ²⁺ may be applied as the metal ion.

The ionomer may be a copolymer of an ethylenic repeating unit having 2 to 4 carbon atoms and an ethylenically unsaturated carboxylic acid repeating unit having 3 to 6 carbon atoms, and includes 5 mole% or more of an acidic side chain, and the acidic side chain is the metal. It may be an ionic compound capable of binding to ions.

The polyethylene terephthalate resin may have a crystallinity of 0% to 80%, 10% to 70%, and more specifically 40% to 60%. The polyethylene terephthalate resin may be a copolymer resin, but the copolymerized polyethylene terephthalate may be a copolymer of ethylene glycol and neopentyl glycol as a glycol component.

The polyimide resin is a resin prepared by imidizing a polyamic acid derivative by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate, and specifically, an aromatic acid dianhydride including biphenyltetracarboxylic dianhydride. It may be obtained by imidizing a polyamic acid resin synthesized from an aromatic diamine containing water and para-phenylene diamine, but is not limited thereto.

The first surface layer 100 may include plasticized first polyvinyl acetal.

The first polyvinyl acetal may have a hydroxyl group content of 30 mol% or more and an acetyl group content of 5 mol% or less. Specifically, the amount of hydroxyl groups may be 30 to 50 mol%, and the amount of acetyl groups may be 2 mol% or less. The first polyvinyl acetal resin may have a weight average molecular weight value of 200,000 to 300,000. When the polyvinyl acetal having such characteristics is applied to the first polyvinyl acetal, it is possible to produce a glass bonding film having excellent bonding strength with glass and excellent mechanical strength.

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. In more detail, the plasticizer may be triethylene glycol bis 2-ethylhexanoate (3G8).

The first surface layer 100 may include a plasticizer and a first polyvinyl acetal, and may be formed by melting and extruding a composition for a first surface layer further including other additives to be described later in a required range.

The second surface layer 200 may include plasticized second polyvinyl acetal.

The second polyvinyl acetal may have a hydroxyl group content of 30 mol% or more and an acetyl group content of 5 mol% or less. Specifically, the amount of hydroxyl groups may be 30 to 50 mol%, the acetyl group content may be 2 mol% or less. The first polyvinyl acetal resin may have a weight average molecular weight value of 200,000 to 300,000. When the polyvinyl acetal having such characteristics is applied as the second polyvinyl acetal, it is possible to produce a glass bonding film having excellent bonding strength with glass and excellent mechanical strength.

The second polyvinyl acetal may be applied to the same as the first polyvinyl acetal, and the other may be applied.

The plasticizer of the first surface layer may be the same as the plasticizer applied to the first surface layer, and the other may be applied. The detailed description of the kind of the plasticizer is omitted because the description thereof overlaps with the above description.

The intermediate layer 300 may include a plasticized third polyvinyl acetal and the trioxane compound.

The intermediate layer 300 may have a single layer structure including a plasticized third polyvinyl acetal and the trioxane compound.

The intermediate layer 300 may include a first intermediate layer 310 including a plasticized third polyvinyl acetal and the trioxane compound; A second intermediate layer 400 disposed between the first intermediate layer and the first surface layer and including a plasticized fourth polyvinyl acetal; And a third intermediate layer 500 positioned between the first intermediate layer and the second surface layer and including a plasticized fifth polyvinyl acetal.

The intermediate layer 300 or the first intermediate layer 310 may contain a trioxane-based compound to improve fluidity in the molten resin state and to reduce optical defects such as melt defects that may occur in the manufacturing process.

The third polyvinyl acetal has a hydroxyl amount of 40 mol% or less, the acetyl group may be 8 mol% or more, and the third polyvinyl acetal has a hydroxyl amount of 1 to 30 mol% and an acetyl group of 1 to 15 mol% Can be. By applying polyvinyl acetal having such characteristics, it is possible to produce a polyvinyl acetal film having sound insulation properties.

The weight average molecular weight value of the third polyvinyl acetal may be 490,000 to 850,000, 610,000 to 820,000, and 690,000 to 790,000. The weight average molecular weight value of the third polyvinyl acetal resin may be 700,000 to 760,000, may be 720,000 to 750,000. In this case, co-extrusion workability may be improved and mechanical properties of the manufactured film may be simultaneously improved.

A difference between the weight average molecular weight values of the third polyvinyl acetal resin and the first polyvinyl acetal resin may be 250,000 to 500,000, 300,000 to 500,000, and 450,000 to 500,000. In the case of having a difference in the weight average molecular weight value, it has better properties in terms of extrusion temperature control during the process, and can further improve the mechanical properties of the produced film.

The polydispersity index (PDI) value of the third polyvinyl acetal resin may be 3.5 or less, 1.2 to 2.5, and 1.9 to 2.3.

The third polyvinyl acetal resin may have a melt index of 5 to 45 g / 10 min according to ASTM D1238 (150 ° C., 21.6 kg, 37% Kneader). Specifically, the melt index of the 3 polyvinyl acetal resin may be 6 to 35 g / 10min, 7 to 25 g / 10min, 8 to 15 g / 10min, 8.5 to 12.5 g / 10min have. When the twenty-third polyvinyl acetal resin having such a melt index is applied, process stability can be further improved.

The third polyvinyl acetal resin may have a viscosity (Viscosity, 5% BuOH Sol.) Value according to JIS K6728 may be 250 to 900 cP, 500 to 750 cP. When the viscosity conditions are satisfied, the mechanical properties of the film may be further improved, and process efficiency may be further improved during melt extrusion.

The plasticizer of the intermediate layer 300 or the first intermediate layer 310 may be the same as the plasticizer applied to the first surface layer 100 or may be applied to the other. The detailed description of the kind of the plasticizer is omitted because it overlaps with the above description.

The fourth polyvinyl acetal has a value between the amount of hydroxyl groups of the first polyvinyl acetal and the amount of hydroxyl groups of the third polyvinyl acetal. Specifically, the fourth polyvinyl acetal may have a hydroxyl group amount of 20 to 45 mol%, and may be 30 to 45 mol%. When the polyvinyl acetal having such a hydroxyl group is applied as the fourth polyvinyl acetal, the film for glass bonding with less defects is alleviated by alleviating interlayer heterogeneity that may occur at the interface between the first polyvinyl acetal and the third polyvinyl acetal. Can be prepared.

The fifth polyvinyl acetal may be applied to have the characteristics of the fourth polyvinyl acetal. The same as the fourth polyvinyl acetal may be applied, and another having the above characteristics may be applied.

The plasticizer of the second intermediate layer 400 and the third intermediate layer 500 may be the same as the plasticizer applied to the first surface layer 100, or may be different. The detailed description of the kind of the plasticizer is omitted because it overlaps with the above description.

The content of the plasticizer contained in each of the first surface layer 100 or the second surface layer 200 may be smaller than the content of the plasticizer contained in the intermediate layer 300 or the first intermediate layer 310.

The difference between the content of the plasticizer contained in each of the first surface layer 100 or the second surface layer 200 and the content of the plasticizer contained in the intermediate layer 300 or the first intermediate layer 310 is 5 to 18% by weight. May be 5 to 15% by weight, may be 5 to 10% by weight. When applied to the first surface layer 100 or the second surface layer 200 and the intermediate layer 300 or the first intermediate layer 310 so as to have a difference in content in the plasticizer, it contains the trioxane-based compound more optical The film for glass bonding which is excellent in a characteristic and has a sound insulation characteristic can be manufactured.

The first surface layer 100 or the second surface layer 200 may include 21 to 29% by weight of the plasticizer, respectively, based on the entirety of each layer, in which case the mechanical strength of the film may be further improved.

The plasticizer may be included in the intermediate layer 300 or the first intermediate layer 310 in an amount of 29 to 42% by weight, based on the entirety of each layer. .

The second intermediate layer 400 or the third intermediate layer 500 may include 29 to 42 wt% of the plasticizer, respectively, based on the entirety of each layer. In this case, the first surface layer 100 and the second intermediate layer 400 ), Or the interlayer heterogeneity between the second surface layer 200 and the third intermediate layer 500 may be alleviated, thereby manufacturing a film having reduced defects such as bubble generation.

The glass bonding film 900 has a haze value of the film for glass bonding after evaluation by immersion in deionized water at 50 ° C. for 3 hours to within 15% of the haze value of the glass bonding film before the evaluation. It may show a difference of 0 to 15% may show a difference, may show a difference of 0.1 to 15%. This difference means that the excellent optical properties including the trioxane-based compound and the like are maintained above a certain level even after the harsh humidity test.

The glass bonding film 900 may have a haze value of 3% or less, 2.5% or less, and 0.1 to 2%.

The glass bonding film 900 may further contain an additive selected from the group consisting of an antioxidant, a heat stabilizer, a UV absorber, a UV stabilizer, an IR absorber, a glass bonding force control agent, and combinations thereof as necessary. The additive may be included in at least one of the above layers, and by including the additive, it is possible to improve long-term durability and scattering prevention performance, such as thermal stability and light stability of the film.

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

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

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

The glass bonding film 900 may have a total thickness of 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. The glass bonding film may be applied to manufacture laminated glass, so that the thicker the thickness, the mechanical strength or the sound insulation performance may be improved. However, the thickness range satisfies various conditions in consideration of minimum legal performance, cost, and weight reduction. Film production is possible.

The thicknesses of the first surface layer 100 and the second surface layer 200 may be each independently 0.01 to 0.05 mm, and may be 0.02 to 0.04 mm.

The intermediate layer 300 may have a thickness of 0.04 to 0.20 mm, 0.07 to 0.18 mm, and 0.09 to 0.15 mm.

The thicknesses of the second intermediate layer 400 and the third interlayer 500 included in the glass bonding film 900 may be each independently 0.1 mm or less, 0.09 mm or less, and 0.001 to 0.1 mm. , 0.001 to 0.08 mm, and 0.001 to 0.3 mm. In the case where the second intermediate layer 400 and the third intermediate layer 500 are applied in the thickness range, optical defects that may occur at an interface between layers may be minimized.

The composition for a glass bonding film according to another embodiment of the present invention is a composition for an intermediate layer comprising a plasticizer, a third polyvinyl acetal and a trioxane compound, wherein the trioxane compound is 0.001 based on the entire composition for the intermediate layer. To 4% by weight.

The composition for a glass bonding film is applied to manufacture of the film 900 for glass bonding.

The glass bonding film 900 may include a first surface layer 100, a second surface layer 200 facing the first surface layer, and an intermediate layer 300 or a second layer disposed between the first surface layer and the second surface layer. By including the intermediate layer 310, the composition for the intermediate layer is applied to the production of the intermediate layer 300 or the first intermediate layer 310.

The intermediate layer composition may include an intermediate layer composition including 57 to 69 wt% of the third polyvinyl acetal, 30 to 42 wt% of the plasticizer, and 0.001 to 4 wt% of the trioxane compound. Specifically, the intermediate layer composition may include 63 to 68% by weight of the third polyvinyl acetal, 31 to 36% by weight of the plasticizer and 0.001 to 4% by weight of the trioxane-based compound. The intermediate layer composition may further include the additional additives described above as needed. The additional additive may be applied at 0.01 to 1% by weight.

The first surface layer composition and the second surface layer composition applied to the first surface layer 100 and the second surface layer 200 are each independently 66 to 74 wt% of the first polyvinyl acetal or the second polyvinyl acetal; It may comprise 25 to 33% by weight of the plasticizer. In addition, if necessary, the additives described above may be included in an amount of 0.01 to 1% by weight. In this case, it is possible to form a surface layer having glass bonding strength with excellent strength and excellent mechanical strength.

The second intermediate layer composition applied to the second intermediate layer 400 and the third intermediate layer composition applied to the third intermediate layer 500 are each independently the fourth polyvinyl acetal or the fifth polyvinyl acetal 57 to 72. It may include weight percent and 27 to 42 weight percent of the plasticizer. In addition, when the fluidity needs to be improved, the trioxane-based compound may be included in an amount of 0.001 to 0.4% by weight, and if necessary, the additive described above may be included in an amount of 0.01 to 1% by weight. In this case, the second intermediate layer or the third intermediate layer may be manufactured in which the interlayer heterogeneity is alleviated to improve the optical properties of the film.

The compositions may be manufactured in the form of a film by melt extrusion in an extruder to which each composition is injected, and then laminated through a laminating apparatus such as a feed block and formed into a film in a Ti-die, for example, by co-extrusion. Can be.

Method for producing a glass bonding film according to another embodiment of the present invention includes an extrusion step, a lamination step, and a molding step.

The extruding step comprises kneading and extruding the composition for the intermediate layer comprising i) a surface layer composition comprising first polyvinyl acetal and ii) a plasticizer, a third polyvinyl acetal and 0.001 to 4 wt% of a trioxane compound. to be.

The surface layer composition may be selectively or both of the composition for the first surface layer and the composition for the second surface layer described above. In this case, the glass bonding film of the three-layer structure described above can be prepared.

Detailed descriptions of the first surface layer composition, the second surface layer composition, the intermediate layer composition, and the like are duplicated above, and thus description thereof is omitted.

The extruding step may further include a step of kneading extrusion of the second intermediate layer composition and the third intermediate layer composition selectively or all together in the extrusion step. In this case, it is possible to manufacture the film for glass bonding of the five-layer structure described above.

The laminating step is a step of manufacturing a laminated molten resin by laminating the surface layer melt resin containing the extruded surface layer composition and the intermediate layer melt resin containing the intermediate layer composition such that the surface layer composition is positioned above and below the intermediate layer composition. .

When manufacturing a 5-layered glass bonding film, the laminated molten resin further includes the second intermediate layer melt resin or the third intermediate layer melt resin between the surface layer melt resin and the intermediate layer (first intermediate layer) melt resin. can do.

The lamination may be utilized a conventional lamination means applied to the multilayer film production, specifically, a feed block, multi manifold, etc. may be applied, but is not limited thereto.

The molding step is a step of forming the laminated molten resin into a sheet shape and manufacturing a film for glass bonding. Specifically, the molding may include forming the molten resin in the form of a sheet and forming a film in a T-die.

In the case of manufacturing the glass bonding film by applying the manufacturing method of the glass bonding film of the present invention, in the case of manufacturing a multilayer film by applying two or more compositions having different compositions and fluidity, in particular, the fluidity of the intermediate layer is improved and looks awkward It is possible to manufacture a film for glass bonding with improved optical properties.

2 is a view showing a cross-section of the laminated glass according to an embodiment of the present invention by way of example. Referring to Figure 2 will be described a laminated glass according to another embodiment of the present invention. The laminated glass 950 includes a laminate in which the glass bonding film 900 described above is positioned between two sheets of glass 10 and 20.

The two sheets of glass 10 and 20 are described herein as glass, but may be applied to a light transmissive panel, and materials such as plastic may also be applied.

Details about the specific structure, composition, characteristics, manufacturing method, etc. of the glass bonding film 900 are overlapped with the above description, and thus description thereof is omitted.

3 is a view showing an example in which laminated glass is applied as a windshield to an automobile 800 that is an example of a moving means according to an embodiment of the present invention.

Another embodiment of the present invention, a moving means 800 will be described with reference to the drawings. The moving means 800 includes the laminated glass described above. Specifically, the moving means 800 includes the laminated glass 950 as a windshield.

The windshield blocks the wind from the outside, and the driver of the vehicle is installed to observe the outside with the naked eye, the laminated glass 950 described above may be applied.

The moving means 800 may include a body part forming a main body of the moving means, a driving part (engine, etc.) mounted to the body part, a driving wheel (wheel, etc.) rotatably mounted to the body part, the driving wheel and the driving part. Connecting device for connecting; And a windshield, which is mounted to a part of the body part and is a light transmitting laminate that blocks wind from the outside.

The moving means 800 may be applied to any moving means to which a windshield is applied, and typically, the moving means 800 may be a car, and the body part, the driving part, the driving wheel, the connecting device, etc. are usually a car. If it applies to, it can be applied without limitation.

The vehicle, which is the vehicle 800, may be applied to the laminated glass 950 as a windshield windshield, and has excellent optical properties and impact resistance to the entire area of the laminated glass 950 with excellent optical properties. , Penetration resistance, and the like can be given.

EMBODIMENT OF THE INVENTION Hereinafter, the specific Example of this invention is described in detail.

(Manufacture of film for glass bonding)

1) Preparation of Polyvinyl Acetal Resin

Preparation of polyvinyl butyral resin (A): Polyvinyl butyral resin (A) having 54.5 mol% butyral group and 44.7 mol% hydroxyl group by synthesizing n-butylaldehyde to polyvinyl alcohol resin having an average degree of polymerization of 1700 and saponification degree 99 ) Was prepared.

Preparation of polyvinyl butyral resin (B): polyvinyl butyral resin having 63.1 mol% butyral group and 18.5 mol% hydroxyl group prepared by synthesizing n-butylaldehyde to polyvinyl alcohol resin having an average degree of polymerization of 2400 and saponification degree of 88 (B) was prepared.

2) Preparation of Glass Bonding Film

(Preparation of film of Example 1) Polyvinyl butyral resin (A) 73 g of polyvinyl butyral resin 3G8 27 wt% in a twin screw extruder A was kneaded sufficiently (composition for film A), polyvinyl butyral resin (B ), 64 wt% of 34 wt% of 3G8 as a plasticizer, and 1 wt% of 2,4,6-tripropyl-1,3,5-trioxane as additives were mixed in a twin screw extruder B (for film B). Composition), (Film A) / (Film B) / (Film A) to coextrude to prepare Example 1 film having a total thickness of 780 μm with a thickness of 330 μm / 120 μm / 330 μm of each layer ( 1 (a) structure).

(Production of Comparative Example 1 Film) In 73 wt% of polyvinyl butyral resin (A), 27 wt% of 3G8 was added to a twin screw extruder A as a plasticizer, and sufficiently kneaded (composition for film A), and polyvinyl butyral resin (B) After mixing 3 wt% of 3G8 as a plasticizer and 5 wt% of 2,4,6-tripropyl-1,3,5-trioxane as an additive in a twin screw extruder B at 64 wt%, the mixture was sufficiently kneaded (composition for film B) By co-extrusion in the structure of (Film A) / (Film B) / (Film A) to prepare a Comparative Example 1 film having a total thickness of 780㎛ each layer consisting of 330㎛ / 120㎛ / 330㎛.

(Production of Comparative Example 2 Film) In 73 wt% of polyvinyl butyral resin (A), 3 wt% of GG was added into a twin screw extruder A by adding 27 wt% of 3G8 as a plasticizer (composition for film A), and polyvinyl butyral resin (B) 3G8 36wt% of plasticizer was added to 64wt% in a twin screw extruder B and kneaded sufficiently (composition for film B), and then the thickness of each layer was coextruded in the structure of (film A) / (film B) / (film A). A film of Comparative Example 2 having a total thickness of 780 μm having a thickness of 330 μm / 120 μm / 330 μm was prepared.

(Physical property evaluation of the film for glass bonding)

Optical defect (DISTORTION evaluation)

The films were cut into 10 cm long and 10 cm wide, respectively, and sandwiched between two pieces of transparent glass (10 cm long, 10 cm wide, and 2.1 cm thick) in a laminator of 110 ° C and 1 atm for 30 seconds. After carrying out preliminary crimping | bonding of the laminated glass by carrying out, the laminated glass which was preliminarily crimped | bonded by the temperature of 140 degreeC and the pressure conditions of 1.2 MPa in the autoclave was crimped for 20 minutes, and obtained the laminated glass.

The resulting laminated glass sample was placed at a distance of 10 cm from the wall, and then lit by a led light at a distance of 30 cm at a 20 degree angle, and confirmed that optical defects were observed in the shadows reflected on the wall. If it fails, and if it is not confirmed, it is evaluated as a pass (see FIG. 4). The results are summarized in Table 1 below.

Sound Insulation Performance (L / F) Measurement Method

The prepared films were cut into 30 cm long and 2.5 cm wide, respectively, and sandwiched between two pieces of transparent glass (30 cm wide, 2.5 cm wide and 2.1 cm thick) in a laminator of 110 ° C and 1 atm for 30 seconds. After carrying out preliminary crimping | bonding of laminated glass by carrying out, the laminated glass preliminarily crimped | bonded by autoclave at the temperature of 140 degreeC and the pressure conditions of 1.2 MPa was crimped for 20 minutes, and the laminated glass used for sound insulation measurement was obtained. The prepared glass samples were stored for 2 weeks in a constant temperature and humidity chamber at 20 ° C. and 20 RH%, and then the sound insulation performance was measured.

The sound insulation performance was measured as follows. Vibration is applied to the laminated glass by a vibration generator for testing the DAMP, and the vibration characteristics obtained therefrom are amplified by a mechanical impedance measuring device, the vibration spectrum is analyzed by an FFT spectrum analyzer, and then calculated by the 1 dB method to calculate L / F (loss). factor) values were obtained. When the obtained L / F value is more than 0.34, pass is evaluated and fail is less than 0.34, and it is shown in Table 1 below.

Moisture Resistance Evaluation

The prepared film was cut to a size of 10 cm * 10 cm in width * length, and a specimen was prepared. The specimen was immersed in a thermostatic chamber filled with deionized water at 50 ° C. for 3 hours, and then taken out to observe a haze value.

The change in the haze value before entering the thermostat and the haze value after entering the thermostat was evaluated as pass when the change was less than 15% and fail when exceeded 15%. The haze evaluation was performed by applying the NDH 5000W model of Nippon Denshoku Co., Ltd. to the center of the sample and measuring it according to JIS K 7105 standard.

Bleed Out Evaluation

The prepared film was cut to a size of 5 cm * 5 cm to prepare a specimen, heat-treated in a constant temperature oven heated to 75 ℃ 10 minutes and then taken out, the surface was rubbed with oil paper. Observing with the naked eye, if there is nothing on the oil paper, pass, and if there is any, it is judged to fail and is shown in Table 1 below.

Evaluation of Penetration Resistance

Penetration resistance was evaluated using the specimen prepared above according to KS L 2007.

30 cm * 30 cm, 2.1 cm thick glass and the film prepared above were prepared in a laminated structure of glass-film-glass, and were pre-bonded by vacuum to degas and edge sealing. Thereafter, this bonding was performed at 150 ° C. for 2 hours using an autoclave to prepare a sample for evaluation of physical properties. In the sample for evaluation of physical properties, a steel ball of 2.27 kg was dropped at about 20 ° C., and the height (MBH) through which the specimen penetrated was measured. At this time, when penetrated at a height less than 4 m, fail, and when penetrated at more than 4 m are shown in Table 1.

Evaluation of impact resistance

The specimens were prepared and evaluated for impact resistance according to KS L 2007: 2008.

Specimens were prepared for property evaluation samples in the same manner as the penetration resistance evaluation.

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

Room temperature evaluation is a failure of 227 g of steel ball at about 40 ℃ for 4 hours and then dropping at 10 m height, if the impacted specimen is broken and glass is scattered or the amount of glass falling from the sheet is more than 15 g, When the impacted specimen is not broken or the glass is scattered and the amount of glass falling from the sheet is less than 15 g, it is marked as pass.

Trioxane compound content (wt%) in the interlayer Sound insulation performance Moisture resistance Optical defect
Distortion Bleed out Penetration Tolerance Impact resistance Example 1 One Pass Pass Pass Pass Pass Pass Comparative Example 1 5 Pass Fail Pass Pass Pass Pass Comparative Example 2 0 Pass Fail Fail Pass Pass Pass

Content of 2,4,6tripropyl1,3,5 trioxane in the intermediate layer. Referring to the results of Table 1, the samples of Example 1 and Comparative Example 1, which applied a trioxane compound as a fluidity improver, were applied. It can be seen that the optical properties are superior to the sample of Comparative Example 2 not. This is thought to be a result obtained by not forming the trioxane-based compound or reducing the degree of formation of the melt fracture on the surface of the intermediate layer which may be produced during the production of the relatively sticky intermediate layer. However, when excessively applying the trioxane-based compound as in the case of Comparative Example 1 may be rather poor moisture resistance. In addition, it was confirmed that the optical property improvement effect and the moisture resistance improvement effect by the trioxane-based compound did not adversely affect the mechanical properties. Therefore, it was confirmed that when the appropriate amount of the trioxane-based compound additive of the present invention is applied, a film for glass bonding with improved water resistance can be produced while preventing the optical defect.

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.

100: first surface layer 200: second surface layer
300: intermediate layer 310: first intermediate layer
400: second intermediate layer 500: third intermediate layer
900: film for glass bonding 950: laminated glass
800: means of transportation

Claims (10)

A first surface layer, a second surface layer opposite the first surface layer, and an intermediate layer located between the first surface layer and the second surface layer,
The intermediate layer comprises a trioxane-based compound, the film for glass bonding.
The method of claim 1,
In the glass bonding film, after the moisture resistance evaluation evaluated by immersion in deionized water at 50 ° C. for 3 hours, the haze value of the glass bonding film is less than 15% of the difference between the haze value of the glass bonding film before the evaluation. What is seen, film for glass bonding.
The method of claim 1,
The first surface layer comprises a plasticized first polyvinyl acetal,
The second surface layer comprises a plasticized second polyvinyl acetal,
The intermediate layer is a single layer structure containing a plasticized third polyvinyl acetal and the trioxane compound,
The content of the plasticizer contained in the first surface layer is less than the content of the plasticizer contained in the intermediate layer, the film for glass bonding.
The method of claim 3,
The difference between the content of the plasticizer contained in the first surface layer and the content of the plasticizer contained in the intermediate layer is 5 to 18% by weight, glass bonding film.
The method of claim 1,
The first surface layer comprises a plasticized first polyvinyl acetal, the second surface layer comprises a plasticized second polyvinyl acetal,
The intermediate layer,
A first intermediate layer comprising a plasticized third polyvinyl acetal and the trioxane compound;
A second intermediate layer positioned between the first intermediate layer and the first surface layer and comprising a plasticized fourth polyvinyl acetal; And
A third intermediate layer positioned between the first intermediate layer and the second surface layer and comprising a plasticized fifth polyvinyl acetal;
Is a multilayer structure containing
The content of the plasticizer contained in the first surface layer is less than the content of the plasticizer contained in the first intermediate layer, the film for glass bonding.
The method of claim 5,
The hydroxyl group amount of a said 4th polyvinyl acetal has a value between the hydroxyl group amount of a said 1st polyvinyl acetal, and the hydroxyl group amount of a said 3rd polyvinyl acetal, The film for glass bonding.
The method of claim 1,
The trioxane-based compound is contained in the glass bonding film not more than 1% by weight based on the entire glass bonding film.
The method of claim 1,
The trioxane-based compound has a 1,3,5-trioxane skeleton and 1 to 3 carbon atoms of the three carbon atoms included in the skeleton are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, glass Bonding film.
A laminated glass comprising a laminate in which the film for glass bonding according to claim 1 is located between two sheets of glass.
A moving means comprising the laminated glass according to claim 9.

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