专利摘要:
INTERMEDIATE FILM FOR LAMINATED GLASS AND LAMINATED GLASS. The present invention aims to provide an interlayer film for a laminated glass which includes two or more layers of resin laminated together and which has excellent deaeration properties in the process of manufacturing a laminated glass and prevents ghosting. The present invention also aims to provide a laminated glass comprising the interlayer film for a laminated glass. The present invention relates to an interlayer film for a laminated glass which includes two or more layers of resin laminated together and has many fine undercuts and many fine protrusions on at least one surface thereof. The recesses have a groove shape with a continuous bottom. The recesses are formed in a regular manner, and recesses adjacent to each other being parallel. Recesses adjacent to each other are spaced less than 750 (Mi)m apart.
公开号:BR112015002011B1
申请号:R112015002011-9
申请日:2013-08-02
公开日:2021-06-08
发明作者:Hirofumi Kitano;Taiki Katayama
申请人:Sekisui Chemical Co., Ltd;
IPC主号:
专利说明:

TECHNICAL FIELD
[0001] The present invention relates to an interlayer film for a laminated glass including two or more layers of resin laminated together. The interlayer film has excellent deaeration properties in the laminated glass manufacturing process and prevents ghosting. The present invention also relates to a laminated glass comprising the interlayer film for a laminated glass. BACKGROUND TECHNIQUE
[0002] A laminated glass composed of two sheets of glass with a plasticized polyvinyl butyral interlayer film between them, all bonded together, has been widely used as window glass for automobiles, aircraft, architectures, and others .
[0003] Interlayer films for a laminated glass may include a single resin layer, or may include a laminate of two or more resin layers. If an interlayer film includes, as the two or more resin layers, a first resin layer and a second resin layer having different characteristics, the interlayer film can provide various properties that are difficult to achieve with interlayer films of a single layer.
[0004] For example, Patent Literature 1 discloses an interlayer film for a laminated glass including a sound-insulating layer and two protective layers that intersperse the sound-insulating layer. The sound insulating layer of the interlayer film for a laminated glass of Patent Literature 1 contains a polyvinyl acetal resin highly compatible with the plasticizer and a large amount of plasticizer, thereby providing excellent sound insulating properties. The protective layers that intersperse the sound-insulating layer prevent a large amount of plasticizer in the sound-insulating layer from bleeding out, thereby preventing reduced adhesion between the interlayer film and the glass.
[0005] However, a laminated glass with such an interlayer film including a laminate of two or more resin layers can unfortunately cause ghost images when external light rays are seen through the glass. Such ghosting is especially accentuated in interlayer films for a laminated glass having excellent sound-insulating properties, such as that of Patent Literature 1. QUOTE LIST
[0006] - Patent Literature
[0007] Patent Literature 1: JP 2007-331959 A SUMMARY OF THE INVENTION
[0008] - Technical problem
[0009] The present inventors studied to identify the reason that an interlayer film for a laminated glass including two or more layers of resin laminated together causes ghosting. As a result, they found that ghosting is caused by recesses and protrusions formed in the surface of the interlayer film for a laminated glass.
[00010] In the typical manufacture of laminated glass, a laminate of at least two glass plates with an interlayer film for a laminated glass between them is compressed between the pressure rollers (deaeration by compression) or placed in a bag of rubber and subjected to vacuum suction (vacuum deaeration), so that the laminate is preliminarily pressure-linked while the air that remains between the glass plates and the interlayer film can be removed. The laminate is subsequently completely pressure bound, for example by heating and pressurizing in an autoclave. This produces a laminated glass. The deaeration properties of laminated glass and an interlayer film for laminated glass are important in the manufacturing process of laminated glass. The interlayer film for a laminated glass has minute recesses and protrusions formed in at least one surface thereof to achieve sufficient deaeration properties in the manufacture of a laminated glass.
[00011] Such recesses and protrusions formed in the surface of an interlayer film for a laminated glass are generally crushed during the bonding under preliminary pressure or bonding under full pressure in the process of manufacturing a laminated glass. Therefore, they have barely been a problem for finished laminated glass.
[00012] However, the present inventors have found that in the case of an interlayer film for a laminated glass including two or more layers of resin laminated together, the recesses and protrusions affect laminated glass obtained through a laminated glass manufacturing process, causing ghost formation.
[00013] That is, in the case of forming recesses and protrusions on a surface of such an interlayer film, not only are the recesses and protrusions formed on the surface of the interlayer film, but also the recesses and protrusions are transferred to the interface between the resin layers due to the pressure applied during processing, thereby making the interface uneven. Although undercuts and protrusions in the surface of the interlayer film are crushed during preliminary pressure bonding and full pressure bonding in the laminated glass manufacturing process, this uneven interface presumably causes ghosting. Interlayer films for a laminated glass having excellent sound-insulating properties such as those in Patent Literature 1 which are likely to allow the transfer of recesses and protrusions to the interface between the protective layers and the sound-insulating layer, seem especially prone to cause ghost formation.
[00014] An interlayer film for a laminated glass having no recess or protrusion will not cause ghosting. However, such a film without undercuts or protrusions results in insufficient deaeration in the manufacture of laminated glass. This causes air bubbles between the glass and the interlayer film that detract from the appearance of the laminated glass.
[00015] In view of the situation in the art, an object of the present invention is to provide an interlayer film for a laminated glass that includes two or more resin layers laminated together and that exhibits excellent deaeration properties in the manufacture of laminated glass and prevents ghost formation. Another object of the present invention is to provide a laminated glass including the interlayer film for a laminated glass.
[00016] - Solution to the Problem
[00017] The present invention relates to an interlayer film for a laminated glass including two or more layers of resin laminated together. The interlayer film has many fine undercuts and many fine protrusions on at least one surface thereof. The recesses each have a groove shape with a continuous bottom. The recesses being formed in a regular manner, and the recesses adjacent to each other being parallel. Recesses adjacent to each other being spaced less than 750 µm apart.
[00018] The present invention is described below in detail.
[00019] As a result of in-depth examination, the present inventors found that the invention of the pattern of recesses and protrusions in a surface of an interlayer film for a laminated glass allows an interlayer film to have excellent deaeration properties in the manufacture of a laminated glass and at the same time preventing ghosting, even if the film includes two or more layers of resin laminated together. Such a discovery led to the completion of the present invention.
[00020] The interlayer film for a laminated glass of the present invention has many minute recesses and many minute protrusions on at least one surface thereof.
[00021] The recesses in the interlayer film for a laminated glass of the present invention have a groove shape with a continuous bottom. The recesses are formed in a regular way, and the recesses adjacent to each other are parallel. In preliminary pressure bonding and full pressure bonding of a laminate of two glass plates with an interlayer film to a glass laminated therebetween, the ease of air removal is generally strictly related to the continuity and smoothness of the bottom. of the recesses. When the recesses in the at least one surface of the interlayer film have a groove shape with a continuous bottom and are formed parallel to each other in a regular manner, the bottom of the recesses has better continuity. This significantly improves the deaeration properties in the preliminary pressure bonding and the full pressure bonding.
[00022] The phrase "formed in a regular manner" here means that the recesses are formed parallel and may be formed at equal or unequal intervals.
[00023] Figs. 1 and 2 are schematic views each illustrating an example of an interlayer film for a laminated glass in which the recesses each having a groove shape with a continuous bottom are formed at equal intervals, and the recesses adjacent to each other are parallel.
[00024] In the interlayer film for a laminated glass of the present invention, the gap (hereinafter, also referred to as "undercut gap") between an undercut having a groove shape with a continuous bottom and an adjacent one is less than 750 µm. If the undercut interval is less than 750 µm, ghosting in the obtained laminated glass can be prevented without sacrificing the deaeration properties during bonding under preliminary pressure and bonding under full pressure. This is presumably because the undercut interval of less than 750 µm allows the prevention of transfer of undercuts and protrusions at the interface of the resin layers forming the interlayer film to a laminated glass. The upper limit of the undercut interval is preferably 600 µm, more preferably 500 µm, even more preferably 400 µm, and particularly preferably 200 µm.
[00025] Especially for the further prevention of ghosting, the upper limit of the undercut interval is preferably 400 µm, more preferably 300 µm, and even more preferably 200 µm. The higher the intensity of light incident on the outside of the laminated glass, the more likely it is for ghosting to occur. However, if the recess range is 400 µm or less, the interlayer film can reliably prevent ghosting if light with a very high intensity is incident on the laminated glass.
[00026] The lower limit of the undercut range is not particularly limited. From the standpoint of workability in manufacturing a laminated glass, the lower limit thereof in practice is preferably 10 µm, more preferably 50 µm, and even more preferably 100 µm.
[00027] The recess gap here means the shortest distance between the deeper portions of two adjacent recesses having a groove shape with a continuous bottom. Specifically, the recess range can be determined as follows. A surface (viewing range: 20 mm x 20 mm) of the interlayer film for a laminated glass is observed with a light microscope (eg "BS-8000III" available from SONIC-GROUP), and the shortest distance between the deepest portions of each pair of recesses observed adjacent to each other are measured. This is followed by averaging the shortest measured distances through which the undercut interval is determined. Alternatively, the recess range can be set to the maximum of the shortest measured distances. Thus, the undercut range here can be set to the average of the shortest distances or it can be set to the maximum of the shortest distances. Preferably it is defined as the average of the shortest distances.
[00028] The lower limit of the groove depth (Rzg) of the recesses is preferably 10 µm, and the upper limit thereof is preferably 40 µm. If the recesses have a groove depth (Rzg) of 10 µm or greater, the deaeration properties during preliminary pressure bonding and full pressure bonding are further improved. If the recesses have a groove depth of 40 μm or less, the temperature during bonding under preliminary pressure and bonding under full pressure can be lower. The lower limit of the groove depth (Rzg) of the recesses is more preferably 15 µm, and the upper limit thereof is most preferably 35 µm. The lower limit thereof is even more preferably 18 µm, and the upper limit thereof is even more preferably 30 µm. The lower limit thereof is particularly preferably 20 µm, and the upper limit thereof is particularly preferably 28 µm.
[00029] The groove depth (Rzg) of the recesses here means the average value of the groove depth determined using the groove depth of the observed recesses and the number of the observed recesses. The groove depths of the observed recesses are each calculated based on the mean line (a line that is adjusted so that the sum of squares of deviations from that line to the roughness curve is minimized) of a roughness curve specified in JIS B- 0601 (1994) "Surface Roughness - Definitions and Designation". The groove depth (Rzg) of the recesses can be easily determined by processing the digital signals obtained using the surface roughness tester ("SE1700α" available from Kosaka Laboratory Ltd.).
[00030] The recesses and protrusions can take the form of those commonly formed in a surface of an interlayer film for a laminated glass. The recesses and protrusions can be shaped, for example, as an engraved line, a grid, or a hemisphere. The recesses and protrusions can be in the form of reliefs. The recesses and protrusions preferably have the shape of an etched line.
[00031] The protrusions can have a flat top as illustrated in Fig. 1. Alternatively, the protrusions can have a non-flat top as shown in Fig. 2. For protrusions with a flat top, recesses and minute protrusions can be further formed at the top planar.
[00032] The heights of the protrusions can be the same or different from each other. The depths of the recesses, which correspond to the heights of the protrusions, can also be the same or different from each other, as long as the bottom of the recesses is continuous.
[00033] In the present invention, many fine undercuts and many fine protrusions can be formed in at least one surface of the interlayer film for a laminated glass, for example, by a roll molding method, a roll calendering method, or a profile extrusion. Among these, a casting roll method which can form recesses in a regular manner or at equal intervals so that recesses adjacent to each other can be parallel is preferable. For a significant improvement in deaeration properties during preliminary pressure bonding and full pressure bonding, the interlayer film for a laminated glass preferably has many fine undercuts and many fine protrusions on both surfaces thereof.
[00034] Examples of the casting roll to be used in the casting roll method include: having a minute embossed pattern (textured pattern) on its roll surface formed by etching the surface of a metal roll with abrasive (eg, oxide aluminum, silicon oxide) and then polishing the surface with vertical polish to reduce the number of huge spikes on the surface; one having minutely embossed pattern (textured pattern) on its roll surface formed by transferring an embossed pattern (textured pattern) from an engraving mill (mother mill) to the surface of a metal roll; and one having a minutely embossed pattern engraved (textured pattern) on its roller surface.
[00035] The interlayer film for a laminated glass of the present invention includes two or more layers of resin laminated together. For example, if the interlayer film for a laminated glass includes, as the two or more resin layers, a first resin layer and a second resin layer having different characteristics, the interlayer film may give properties that are difficult to achieve. achieve with the interlayer films of a single resin layer. Furthermore, an interlayer film including such two or more resin layers laminated together has a problem of ghosting.
[00036] Preferably, the resin layers each contain a thermoplastic resin.
[00037] Examples of the thermoplastic resin include polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride-propylene hexafluoride copolymer, polytrifluoroethylene, acrylonitrile-butadiene-styrene copolymer, polyesters, polyethers, polyamides, polycarbonate, polyacrylate, polymethacrylate, poly( vinyl), polyethylene, polypropylene, polystyrene, poly(vinyl acetal), and ethylene-vinyl acetate copolymer. The resin layers preferably contain poly(vinyl acetal) or an ethylene-vinyl acetate copolymer, and more preferably contain poly(vinyl acetal).
[00038] Preferably, the resin layers each contain poly(vinyl acetal) and a plasticizer.
[00039] The plasticizer can be any plasticizer commonly used in interlayer films for a laminated glass. Examples thereof include organic plasticizers such as monobasic organic esters and polybasic organic esters and phosphoric acid plasticizers such as organophosphate compounds and organophosphite compounds.
[00040] Examples of the organic plasticizers include triethylene glycol-di-2-ethyl-hexanoate, triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-n-heptanoate, tetraethylene glycol-di-2-ethyl-hexanoate, tetraethylene glycol-di-2- ethylbutyrate, tetraethyleneglycol-di-n-heptanoate, diethyleneglycol-di-2-ethylhexanoate, diethyleneglycol-di-2-ethylbutyrate, and diethyleneglycol-di-n-heptanoate. The resin layers preferably contain triethyleneglycol-di-2-ethylhexanoate, triethyleneglycol-di-2-ethylbutyrate, or triethyleneglycol-di-n-heptanoate, and more preferably contain triethyleneglycol-di-2-ethylhexanoate.
[00041] Preferably, the resin layers each contain an adhesion control agent. In particular, a resin layer which contacts glass in laminated glass manufacture preferably contains an adhesion control agent.
[00042] Suitable examples of the adhesion control agent include alkali metal salts and alkaline earth metal salts. Specific examples of the adhesion control agent include potassium, sodium, and magnesium salts.
[00043] Examples of the acid forming salts include organic carboxylic acids such as octyl acid, hexyl acid, 2-ethylbutyric acid, butyric acid, acetic acid, and formic acid and inorganic acids such as hydrochloric acid and nitric acid. It is preferred that the resin layer that contacts the glass contains a magnesium salt or a potassium salt because these salts facilitate adhesion control between the glass and the resin layer in the manufacture of laminated glass.
[00044] The resin layers can each contain additives such as an antioxidant, a light stabilizer, a modified silicone oil as the adhesion control agent, a flame retardant, an antistatic agent, a moisture-proofing agent, a heat-reflecting agent, and a heat-absorbing agent, depending on the need.
[00045] The interlayer film for a laminated glass of the present invention at least includes a first resin layer and a second resin layer as the two or more resin layers. Preferably, poly(vinyl acetal) in the first resin layer (hereinafter, referred to as "poly(vinyl acetal) A") and poly(vinyl acetal) in the second resin layer (hereinafter, referred to as "poly(vinyl acetal) A") vinyl) B") have different amounts of hydroxy groups.
[00046] The difference in characteristics between poly(vinyl acetal) A and poly(vinyl acetal) B allows the interlayer film for a laminated glass to have several properties that are difficult to achieve with a single layer. For example, if the first resin layer is interposed between two layers of the second resin layers, and if poly(vinyl acetal) A contains a smaller amount of hydroxy groups than poly(vinyl acetal) B, the first layer resin tends to have a lower glass transition temperature than second resin layers. This allows the first resin layer to be softer than the second resin layers, thereby allowing the interlayer film for a laminated glass to have high sound insulating properties. In contrast, if the first resin layer is interposed between the two layers of the second resin layers, and if poly(vinyl acetal) A contains a greater amount of hydroxy groups than poly(vinyl acetal) B, the first resin layer tends to have a higher glass transition temperature than second resin layers. This allows the first resin layer to be harder than the second resin layers, thereby allowing the interlayer film for a laminated glass to have high penetration resistance.
[00047] If the first resin layer and the second resin layer each additionally contain a plasticizer, the amount of plasticizer in the first resin layer (hereinafter, referred to as "Amount") based on 100 parts by weight of poly( vinyl acetal) is preferably different from the amount of plasticizer in the second resin layer (hereinafter, referred to as "Amount B") based on 100 parts by weight of poly(vinyl acetal). For example, if the first resin layer is interposed between two layers of the second resin layers, and Quantity A is greater than Quantity B, the first resin layer tends to have a lower glass transition temperature than the second layers of resin. This allows the first resin layer to be softer than the second resin layers, thereby allowing the interlayer film for a laminated glass to have high sound insulating properties. In contrast, if the first resin layer is interposed between the two layers of the second resin layers, and if Quantity A is less than Quantity B, the first resin layer tends to have a higher glass transition temperature than the second resin layers. This allows the first resin layer to be harder than the second resin layers, thereby allowing the interlayer film for a laminated glass to have high penetration resistance.
[00048] The two or more resin layers that make up the interlayer film for a laminated glass of the present invention may include, for example, a combination of a sound-insulating layer as the first resin layer and a protective layer as the second resin layer, to improve the sound insulating properties of laminated glass. From the standpoint of improving the sound insulating properties of laminated glass, it is preferred that the sound insulating layer contains poly(vinyl acetal) X and a plasticizer and that the protective layer contains poly(vinyl acetal) Y and a plasticizer. Interposing the sound insulating layer between the two layers of the protective layers results in an interlayer film for laminated glass (hereafter also referred to as a "sound insulating interlayer film") having excellent sound insulating properties. The present invention can provide an interlayer film for a laminated glass that can prevent ghosting while containing a laminate of resin layers of different characteristics, such as the sound-insulating layer and the protective layer. The sound insulating interlayer film is described in more detail below.
[00049] In sound insulating interlayer film, the sound insulating layer gives sound insulating properties.
[00050] The sound-insulating layer preferably contains poly(vinyl acetal) X and a plasticizer.
[00051] Poly(vinyl acetal) X can be prepared by treating poly(vinyl alcohol) with an acetal with an aldehyde. Poly(vinyl alcohol) can typically be prepared by saponifying poly(vinyl acetate).
[00052] The lower limit of the degree of polymerization of poly(vinyl alcohol) is preferably 200, and the upper limit thereof is preferably 5000. If the degree of polymerization of poly(vinyl alcohol) is 200 or greater, the interlayer film resulting sound insulator may have improved penetration resistance. If the degree of polymerization is 5000 or less, the moldability of the sound-insulating layer is ensured. The lower limit of the degree of polymerization of the poly(vinyl alcohol) is more preferably 500, and the upper limit thereof is most preferably 4000.
[00053] The lower limit of the carbon number of the aldehyde to be used in the poly(vinyl alcohol) acetal treatment is preferably 4, and the upper limit thereof is preferably 6. If the aldehyde has a carbon number of 4 or larger, the sound-insulating layer can stably contain enough plasticizer, leading to excellent sound-insulating properties. In addition, bleeding of the plasticizer can be prevented. If the aldehyde has a carbon number of 6 or less, poly(vinyl acetal) X can be easily synthesized, ensuring productivity.
[00054] The aldehyde that has a carbon number from 4 to 6 can be a straight chain aldehyde or a branched aldehyde. Examples thereof include n-butylaldehyde and n-valeraldehyde.
[00055] The upper limit of the amount of hydroxy groups in poly(vinyl acetal) X is preferably 30% mol. If the amount of hydroxy groups in poly(vinyl acetal) X is 30% by mol or less, the sound-insulating layer may contain the plasticizer in an amount required to give sound-insulating properties. In addition, bleeding of the plasticizer can be prevented. The upper limit of the amount of hydroxy groups in polyvinyl acetal X is more preferably 28% by mol, even more preferably 26% by mol, and particularly preferably 24% by mol. The lower limit thereof is preferably 10 mol%, more preferably 15 mol%, and even more preferably 20 mol%.
[00056] The amount of hydroxy groups in poly(vinyl acetal) X here means a molar fraction expressed as a percentage (% in mol), determined by dividing the amount of ethylene groups to which a hydroxy group is attached by the amount of all groups ethylene in the main chain. The amount of ethylene groups to which a hydroxy group is attached can be determined, for example, by determining the amount of ethylene groups to which an hydroxy group is attached in poly(vinyl acetal) X according to JIS K6728 "Testing methods for polyvinyl butyral".
[00057] The lower limit of the amount of acetal groups in poly(vinyl acetal) X is preferably 60% by mol, and the upper limit thereof is preferably 85% by mol. If the amount of acetal groups in poly(vinyl acetal) X is 60% by mol or more, the sound-insulating layer can have significantly improved hydrophobic properties and contain the plasticizer in an amount required to give sound-insulating properties. In addition, plasticizer bleed and whitening of laminated glass can be prevented. If the amount of acetal groups in poly(vinyl acetal) X is 85% by mol or less, poly(vinyl acetal) X can be easily synthesized, ensuring productivity. The amount of acetal groups can be determined by determining the amount of ethylene groups to which an acetal group is attached in poly(vinyl acetal) X according to JIS K6728 "Testing methods for polyvinyl butyral".
[00058] The lower limit of the amount of acetyl groups in poly(vinyl acetal) X is preferably 0.1 mol%, and the upper limit thereof is preferably mol%. If the amount of acetyl groups in poly(vinyl acetal) X is 0.1 mol% or more, the sound-insulating layer may contain the plasticizer in an amount required to give sound-insulating properties. Also, bleeding can be prevented. If the amount of acetyl groups in poly(vinyl acetal) X is 30% by mol or less, the sound-insulating layer may have high hydrophobic properties, thereby preventing whitening of a laminated glass. The lower limit of the amount of acetyl groups is more preferably 1% by mol, even more preferably 5% by mol, particularly preferably 6% by mol, and most preferably 8% by mol. The upper limit thereof is more preferably 25% mol and even more preferably 20% mol. The amount of acetyl groups here means the molar fraction expressed as a percentage (% in mol), determined by subtracting the amount of ethylene groups to which an acetal group is attached and the amount of ethylene groups to which a hydroxy group is attached from the amount of all the ethylene groups in the main chain and dividing the resulting difference by the amount of all ethylene groups in the main chain.
[00059] It is particularly preferred that poly(vinyl acetal) X is poly(vinyl acetal) containing 8% by mol or more of acetyl groups or poly(vinyl acetal) containing less than 8% by mol of acetyl groups and 68 Mol % or more of acetal groups because such a poly(vinyl acetal) facilitates the incorporation of the plasticizer in an amount required to impart sound-insulating properties to the sound-insulating layer.
[00060] The lower limit of the amount of plasticizer in the sound-insulating layer is preferably 45 parts by mass based on 100 parts by mass of polyvinyl acetal X, and the upper limit thereof is preferably 80 parts by mass. If the amount of plasticizer is 45 parts by mass or more, the sound-insulating layer can exhibit high sound-insulating properties. If the amount of plasticizer is 80 parts by mass or less, bleeding of the plasticizer that reduces the transparency or adhesion of the interlayer film to a laminated glass can be prevented. The lower limit of the amount of plasticizer in the sound-insulating layer is more preferably 50 parts by mass, even more preferably 55 parts by mass. The upper limit thereof is more preferably 75 parts by mass and even more preferably 70 parts by mass.
[00061] The lower limit of the thickness of the sound-insulating layer is preferably 0.05 mm. If the thickness of the sound-insulating layer is 0.05 mm or greater, the layer may exhibit sufficient sound-insulating properties. The lower limit of the thickness of the sound-insulating layer is most preferably 0.08 mm. The upper limit thereof is not particularly limited, but preferably 0.3 mm in view of the interlayer film thickness for a laminated glass.
[00062] The protective layer prevents a large amount of plasticizer in the sound-insulating layer from bleeding and thus prevents the reduction of adhesion between the interlayer film for a laminated glass and the glass. The protective layer also gives penetration resistance to the interlayer film for a laminated glass.
[00063] The protective layer preferably contains, for example, poly(vinyl acetal) Y and a plasticizer, and more preferably contains poly(vinyl acetal) Y containing a greater amount of hydroxy groups than poly(vinyl acetal) X and a plasticizer.
[00064] Poly(vinyl acetal) Y can be obtained by treating poly(vinyl alcohol) acetal with an aldehyde.
[00065] Poly(vinyl alcohol) can typically be prepared by saponifying poly(vinyl acetate).
[00066] The lower limit of the degree of polymerization of poly(vinyl alcohol) is preferably 200, and the upper limit thereof is preferably 5000. If the degree of polymerization of poly(vinyl alcohol) is 200 or greater, the interlayer film for a laminated glass it may have improved penetration resistance. If the degree of polymerization is 5000 or less, the moldability of the protective layer is ensured. The lower limit of the degree of polymerization of the poly(vinyl alcohol) is more preferably 500, and the upper limit thereof is most preferably 4000.
[00067] The lower limit of the carbon number of the aldehyde to be used in the acetalization of poly(vinyl alcohol) is preferably 3, and the upper limit thereof is preferably 4. If the aldehyde has a carbon number of 3 or greater, the interlayer film for a laminated glass has improved penetration resistance. If the aldehyde has a carbon number of 4 or less, the productivity of poly(vinyl acetal) Y is improved.
[00068] The aldehyde having a carbon number from 3 to 4 can be a straight chain aldehyde or a branched aldehyde. Examples thereof include n-butylaldehyde.
[00069] The upper limit of the amount of hydroxy groups in poly(vinyl acetal) Y is preferably 33% by mol, and the lower limit thereof is preferably 28% by mol. If the amount of hydroxy groups in poly(vinyl acetal) Y is 33% mol or less, the whitening of the interlayer film for a laminated glass can be prevented. If the amount of hydroxy groups in poly(vinyl acetal) Y is 28 mol% or more, the interlayer film for a laminated glass has high penetration resistance.
[00070] The lower limit of the amount of acetal groups in poly(vinyl acetal) Y is preferably 60% by mol, and the upper limit thereof is preferably 80% by mol. If the amount of acetal groups is 60% by mol or more, the protective layer may contain the plasticizer in an amount required to give sufficient penetration resistance. If the amount of acetal groups is 80% mol or less, the adhesion between the protective layer and the glass can be ensured. The lower limit of the amount of acetal groups is more preferably 65% by mol, and the upper limit thereof is more preferably 69% by mol.
[00071] The upper limit of the amount of acetyl groups in poly(vinyl acetal) Y is preferably 7 mol%. If the amount of acetyl groups in poly(vinyl acetal) Y is 7 mol% or less, the protective layer may have high hydrophobic properties, thereby preventing whitening. The upper limit of the amount of acetyl groups is more preferably 2% by mol, and the lower limit thereof is preferably 0.1% by mol. The amount of hydroxy groups, the amount of acetal groups, and the amount of acetyl groups in poly(vinyl acetals) A, B, and Y can be determined in the same way as those of poly(vinyl acetal) X.
[00072] The lower limit of the amount of plasticizer in the protective layer is preferably 20 parts by mass based on 100 parts by mass of poly(vinyl acetal) Y, and the upper limit thereof is preferably 45 parts by mass. If the amount of plasticizer in the protective layer is 20 parts by mass or more, the penetration resistance of the protective layer is ensured. If the amount of plasticizer in the protective layer is 45 parts by mass or less, bleeding of the plasticizer that reduces the transparency or adhesion of the interlayer film to a laminated glass can be prevented. The lower limit of the amount of plasticizer in the protective layer is more preferably 30 parts by mass, and even more preferably 35 parts by mass. The upper limit thereof is more preferably 43 parts by mass and even more preferably 41 parts by mass.
[00073] For further improvement in the sound insulating properties of a laminated glass, poly(vinyl acetal) Y preferably contains a greater amount of hydroxy groups than poly(vinyl acetal) X. Poly(vinyl acetal) Y more preferably contains at least 1 mol% more hydroxy groups, even more preferably at least 5 mol% more hydroxy groups, and particularly preferably at least 8 mol% more hydroxy groups than poly(vinyl acetal). ) X. Controlling the amount of hydroxy groups in poly(vinyl acetal) X and in poly(vinyl acetal) Y allows control of the amount of plasticizer in the sound-insulating layer and in the protective layer, thereby enabling the sound-insulating layer have a low glass transition temperature. This additionally improves the sound insulating properties of laminated glass.
[00074] For further improvement in the sound insulating properties of a laminated glass, the amount of plasticizer in the sound insulating layer (hereinafter, also referred to as "Quantity X") based on 100 parts by mass of poly(vinyl acetal) X is preferably greater than the amount of plasticizer in the protective layer (hereinafter, also referred to as "Amount Y") based on 100 parts by mass of polyvinyl acetal Y. Amount X is preferably greater by at least 5 parts by mass, more preferably by at least 15 parts by mass, and particularly preferably by at least 20 parts by mass, than Quantity Y. Control of Quantity X and Quantity Y allows the sound-insulating layer to have a low glass transition temperature . This further improves the sound insulating properties of laminated glass.
[00075] The lower limit of the thickness of the protective layer is preferably 0.2 mm, and the upper limit of the same is preferably 3 mm. If the protective layer is 0.2 mm thick or greater, the layer can provide sufficient penetration resistance.
[00076] The lower limit of the thickness of the protective layer is more preferably 0.3 mm. The upper limit thereof is more preferably 1.5 mm, even more preferably 0.5 mm, and particularly preferably 0.4 mm.
[00077] The way to produce the sound insulating interlayer film is not particularly limited. For example, the sound-insulating interlayer film can be produced by forming sheets of the sound-insulating layer and the protective layer by a common film production method, such as an extrusion method, a calendering method, or a compression method. and laminating the sheets together.
[00078] The present invention also provides a laminated glass comprising the interlayer film for a laminated glass of the present invention. The glass plate to be used in the laminated glass of the present invention is not particularly limited, and can be any commonly used clear mirror glass. Examples thereof include inorganic glass such as float mirror glass, polished mirror glass, figured mirror glass, wire mesh glass, wire-lined glass, colored mirror glass, and heat ray absorbing glass.
[00079] The way to produce the laminated glass of the present invention is not particularly limited. A conventionally known production method can be employed.
[00080] - Advantageous Effects of the Invention
[00081] The present invention provides an interlayer film for a laminated glass including two or more layers of resin laminated together. The interlayer film has excellent deaeration properties in the laminated glass manufacturing process and prevents ghosting. The present invention also provides a laminated glass including the interlayer film for a laminated glass. BRIEF DESCRIPTION OF THE DRAWINGS
[00082] Fig. 1 is a schematic view illustrating an example of an interlayer film for a glass laminated on the surface of these recesses each having a groove shape with a continuous bottom are formed at equal intervals, and recesses adjacent to each other are parallel.
[00083] Fig. 2 is a schematic view illustrating an example of an interlayer film for a glass laminated on the surface of these recesses each having a groove shape with a continuous bottom are formed at equal intervals, and recesses adjacent to each other are parallel. DESCRIPTION OF MODALITIES
[00084] Embodiments of the present invention are described in detail below based on the examples, but not limited thereto. EXAMPLE 1 Preparation of resin composition for first resin layer (sound insulating layer)
[00085] Poly(vinyl alcohol) having an average degree of polymerization of 2400 was acetylized with n-butylaldehyde to prepare poly(vinyl butyral) (acetyl group content: 12% by mol, butyral content: 66% by mol, hydroxy group content: 22% by mol). Poly(vinyl butyral) (100 parts by mass) was mixed with triethylene glycol-di-2-ethylhexanoate (3GO) (60 parts by mass) as a plasticizer, and the mixture was sufficiently mixed with a mixing roller. A resin composition for a first resin layer (sound insulating layer) was thereby obtained. Preparation of resin composition for second resin layer (protective layer)
[00086] Poly(vinyl alcohol) having an average degree of polymerization of 1700 was acetylized with n-butylaldehyde to prepare poly(vinyl butyral) (acetyl group content: 1% by mol, butyral content: 69% by mol, hydroxy group content: 30% by mol). Poly(vinyl butyral) (100 parts by mass) was mixed with triethylene glycol-di-2-ethylhexanoate (3GO) (40 parts by mass) as a plasticizer, and the mixture was sufficiently mixed with a mixing roller. A resin composition for a second resin layer (protective layer) was thereby obtained. Preparation of interlayer film for laminated glass
[00087] The resin composition to form a first resin layer (sound insulating layer) and the resin composition to form the second resin layers (protective layers) was coextruded with a coextruder, by means of which an interlayer film (thickness: 0.8 mm) for a laminated glass in which the first resin layer (sound insulating layer) was interposed between the two second resin layers (protective layers) was obtained. The first resin layer had a thickness of 0.1 mm. The second resin layers each had a thickness of 0.35 mm. Formation of undercuts and protrusions
[00088] A pair of rollers including a metal roller having a ground surface with a triangular oblique line type mill (available from YURIROLL Co., Ltd.) and a rubber roller having a JIS hardness of 45 to 75 was used as a device to transfer the pattern of recesses and protrusions. The interlayer film obtained for a laminated glass was passed over these rollers, whereby recesses and protrusions were formed on a surface (a first surface) of the interlayer film. The recesses each had a groove shape with a continuous bottom and formed parallel to each other at equal intervals. The transfer was carried out under the conditions that the temperature of the interlayer film to a laminated glass was room temperature, the roll temperature was 130°C, the linear speed was 10 m/min, and the linear pressure compression was 500 kPa .
[00089] Subsequently, the other surface (a second surface) of the interlayer film for a laminated glass was subjected to the same operation, whereby recesses each having a groove shape with a continuous bottom were formed in the surface.
[00090] As for the recesses and protrusions formed on the first surface, the gap between a recess having a groove shape with a continuous bottom and an adjacent one was 200 µm, and the recesses had a groove depth (Rzg) of 22 µm. As for the recesses and protrusions formed on the second surface, the gap between a recess having a groove shape with a continuous bottom and an adjacent one was 200 µm, and the recesses had a groove depth (Rzg) of 18 µm.
[00091] The above recess range was determined as follows. The first and second surfaces (viewing range: 20 mm x 20 mm) of the interlayer film for a laminated glass were each observed with a light microscope ("BS-8000III" available from SONIC-GROUP), and the range between each pair of recesses adjacent to each other was determined. Based on the values obtained, the mean of the shortest distances between the deepest portions of the recesses adjacent to each other was calculated, whereby the recess interval was determined. The average of the shortest and longest distances was the same.
[00092] The groove depth (Rzg) of the recesses here is the mean value of the groove depth determined using the groove depth of the observed recesses and the number of the observed recesses. The groove depths of the observed recesses are each calculated based on the mean line (a line that is adjusted so that the sum of squares of deviations from that line to the roughness curve is minimized) of a roughness curve according to JIS B -0601 (1994) "Surface roughness - Definitions and designation". The groove depth (Rzg) of the recesses was determined by processing the digital signals obtained using surface roughness tester ("SE1700α" available from Kosaka Laboratory Ltd.). EXAMPLES 2 TO 7, COMPARATIVE EXAMPLE 1
[00093] The interlayer films for a laminated glass having recesses and protrusions on the surfaces were obtained in the same manner as in Example 1 except that the gap between a recess having a groove shape with a continuous and an adjacent bottom and the groove depth (Rzg) of the recesses were as listed in Table 1.
[00094] The mean of the shortest distances and the maximum of the shortest distances, which were determined in the measurement of the undercut interval, were equal to each other in each of Examples 2 to 7 and Comparative Example 1. EXAMPLE 8
[00095] An interlayer film for a laminated glass was obtained in the same manner as in Example 1 except the amount of triethylene glycol-di-2-ethyl-hexanoate (3GO) added in preparing the resin composition for the first resin layer (sound insulating layer) was 70 parts by mass. EXAMPLE 9
[00096] An interlayer film for a laminated glass was obtained in the same manner as in Example 2 except the amount of triethylene glycol-di-2-ethyl-hexanoate (3GO) added in preparing the resin composition for a first resin layer (sound insulating layer) was 70 parts by mass. EXAMPLE 10
[00097] An interlayer film for a laminated glass was obtained in the same manner as in Example 7 except the amount of triethylene glycol-di-2-ethyl-hexanoate (3GO) added in preparing the resin composition for the first resin layer (sound insulating layer) was 70 parts by mass. EXAMPLE 11
[00098] An interlayer film for a laminated glass was obtained in the same manner as in Example 1 except that the poly(vinyl butyral) used in preparing the resin composition for the first resin layer (sound insulating layer) was poly (vinyl butyral) (acetyl group content: 6% by mol, butyral group content: 72% by mol, hydroxy group content: 22% by mol) obtained by acetylating poly(vinyl alcohol) having an average degree of polymerization of 2400 with n-butylaldehyde. EXAMPLE 12
[00099] An interlayer film for a laminated glass was obtained in the same manner as in Example 1 except that the poly(vinyl butyral) used in preparing the resin composition for the first resin layer (sound insulating layer) was poly (vinyl butyral) (acetyl group content: 24% by mol, butyral group content: 56% by mol, hydroxy group content: 20% by mol) obtained by acetylating poly(vinyl alcohol) having an average degree of polymerization of 2400 with n-butylaldehyde. EXAMPLE 13
[000100] An interlayer film for a laminated glass was obtained in the same manner as in Example 5 except that the poly(vinyl butyral) used in preparing the resin composition for the first resin layer (sound insulating layer) was poly (vinyl butyral) (acetyl group content: 1% by mol, butyral group content: 79% by mol, hydroxy group content: 20% by mol) obtained by acetylating poly(vinyl alcohol) having an average degree of polymerization of 2400 with n-butylaldehyde. ASSESSMENT
[000101] The interlayer films for a laminated glass having recesses and protrusions on the surfaces obtained in the examples and the comparative example were evaluated by the following methods.
[000102] The results are shown in Tables 1 and 2. Evaluation of deaeration properties
[000103] A laminated glass was produced using the interlayer film obtained for a laminated glass having recesses and protrusions on the surfaces. Specifically, preliminary pressure bonding by a vacuum deaeration method and full pressure bonding were performed as follows. VACUUM DEAERATION METHOD
[000104] The interlayer film was interposed between two clear glass plates (length 30 cm x width 30 cm x thickness 2.5 mm). Portions of the film protruding from the plates were cut away. A laminated (laminated) glass structure was thus produced. This structure was transported in a rubber bag which was then connected to a vacuum suction device. The rubber bag was kept under a reduced pressure of -60 kPa (absolute pressure 16 kPa) for 10 minutes with heating so that the temperature (bonding temperature under preliminary pressure) of the laminated (laminate) glass structure reached 70°C . Thereafter, the pressure was returned to atmospheric pressure, whereby the preliminary pressure bonding was completed. Here, the principle temperature of deaeration in the connection under preliminary pressure was 40°C, 50°C, or 60°C. CONNECTION UNDER FULL PRESSURE
[000105] The laminated glass structure (laminated) preliminarily bonded under pressure in the above manner was placed in an autoclave and maintained at a temperature of 140°C at a pressure of 1300 kPa for 10 minutes. Thereafter, the temperature was lowered to 50°C and the pressure was returned to atmospheric pressure, whereby binding under full pressure was completed. A laminated glass was thus produced. ROLLED GLASS RASH TEST
[000106] The laminated glass obtained was heated in an oven at 140°C for 2 hours. After that, the laminated glass was taken out of the oven and allowed to cool for 3 hours. The appearance of the cooled laminated glass was visually observed. The twenty sheets of laminated glass were tested, and the number of sheets on which foam (air bubbles) was formed was determined. Deaeration properties were evaluated based on the number. Ghost Formation Assessment
[000107] The laminated glass was evaluated for the presence of ghosting using two light sources having different intensities, a light source 1 and a light source 2. Light source 1 was a 10 W silica bulb (available from Kyokko Electric Co., Ltd., PS55 E26 110V-10W, total flux: 70 lm) to simulate a light source of a typical intensity that may be incident on window glass of automobiles, aircraft, architectures, or others. Light source 2 was a 40 W silica bulb (available from ASAHI ELECTRIC Co., Ltd., LW100V38W-W, total flux: 440 lm) to simulate a light source that particularly had a high intensity between lights that could be incidents on the window glass of automobiles, aircraft, architectures or others.
[000108] The assessment was performed in accordance with JIS R 3212 (2008). A laminated glass was rated "excellent (oo)" if at all, using either light source 1 or light source 2, a single image or a double image with a separation within 15 arc minutes. It was rated "good (O)" if it gave ghost images using light source 2 but gave a single image or a double image with a separation within 15 minutes of arc using light source 1. It was rated "poor (x )" if giving ghost images or using light source 1 or light source 2.
[000109] The mounting angle for the current vehicle was 30°. The double image with a separation of within 15 minutes of arc was due to the glass, not the interlayer film. TABLE 1

INDUSTRIAL APPLICABILITY
[000110] The present invention provides an interlayer film for a laminated glass including two or more layers of resin laminated together. The interlayer film has excellent deaeration properties in the process of making a laminated glass and prevents ghosting. The present invention also provides a laminated glass comprising the interlayer film for a laminated glass.
权利要求:
Claims (6)
[0001]
1. Interlayer film for a laminated glass, characterized in that the interlayer film comprises: two or more resin layers laminated together, the interlayer film having many minute recesses and many minute protrusions on at least one surface thereof, the recesses each having a groove shape with a continuous bottom, the recesses being formed in a regular manner, recesses adjacent to each other being parallel, and recesses adjacent to each other being spaced less than 600 µm apart.
[0002]
2. Interlayer film according to claim 1, characterized in that the recesses have a groove depth (Rzg) determined in accordance with JIS B-0601(1994) from 10 to 40 μm.
[0003]
3. Interlayer film according to claim 1 or 2, characterized in that the recesses are formed at equal intervals, and recesses adjacent to each other are parallel.
[0004]
4. Interlayer film according to claim 1, 2 or 3, characterized in that the resin layers each contain poly(vinyl acetal) and a plasticizer.
[0005]
5. Interlayer film according to claim 4, characterized in that the resin layers comprise at least a first resin layer and a second resin layer, and poly(vinyl acetal) in the first resin layer and poly (vinyl acetal) in the second resin layer contain different amounts of hydroxy groups.
[0006]
6. Interlayer film according to claim 5, characterized in that the amount of plasticizer in the first resin layer based on 100 parts by mass of poly(vinyl acetal) is different from the amount of plasticizer in the second resin layer. resin based on 100 parts by mass of poly(vinyl acetal).
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同族专利:
公开号 | 公开日
CA2878938A1|2014-02-06|
IN2015KN00204A|2015-06-12|
JP5676773B2|2015-02-25|
KR20180131645A|2018-12-10|
ZA201600672B|2017-03-29|
JP2018177638A|2018-11-15|
JP6192633B2|2017-09-06|
EP2881376A4|2016-03-16|
WO2014021459A1|2014-02-06|
EP2881376A1|2015-06-10|
MX338543B|2016-04-20|
ZA201500661B|2016-10-26|
AU2017200859A1|2017-03-02|
US10744744B2|2020-08-18|
JP6370451B2|2018-08-08|
KR101927041B1|2018-12-07|
AU2013297368A1|2015-02-12|
EP2881376B1|2017-08-30|
JPWO2014021459A1|2016-07-21|
KR20150054755A|2015-05-20|
KR101968071B1|2019-04-10|
JP2017218376A|2017-12-14|
CA2878938C|2019-09-10|
US20150174862A1|2015-06-25|
RU2691796C2|2019-06-18|
RU2015106715A|2016-09-27|
KR20180089563A|2018-08-08|
JP2015107915A|2015-06-11|
AU2017200859B2|2017-12-07|
CN104507887A|2015-04-08|
KR20190039612A|2019-04-12|
KR101886913B1|2018-08-08|
EP3205633B1|2018-06-27|
EP3205633A1|2017-08-16|
BR112015002011A2|2017-07-04|
AU2013297368B2|2016-11-10|
MX2015000972A|2015-04-10|
CN107962837A|2018-04-27|
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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
2021-04-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
2021-06-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |
优先权:
申请号 | 申请日 | 专利标题
JP2012-172165|2012-08-02|
JP2012172165|2012-08-02|
PCT/JP2013/071046|WO2014021459A1|2012-08-02|2013-08-02|Intermediate film for laminated glass and laminated glass|
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