CN110114217A - With enhanced propertied multilayer sandwich - Google Patents

With enhanced propertied multilayer sandwich Download PDF

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Publication number
CN110114217A
CN110114217A CN201780081501.9A CN201780081501A CN110114217A CN 110114217 A CN110114217 A CN 110114217A CN 201780081501 A CN201780081501 A CN 201780081501A CN 110114217 A CN110114217 A CN 110114217A
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CN
China
Prior art keywords
resin
poly
interlayer
layer
vinyl acetal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201780081501.9A
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Chinese (zh)
Inventor
吕军
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Solutia Inc
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Solutia Inc
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Filing date
Publication date
Priority claimed from US15/394,747 external-priority patent/US10286638B2/en
Application filed by Solutia Inc filed Critical Solutia Inc
Publication of CN110114217A publication Critical patent/CN110114217A/en
Pending legal-status Critical Current

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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/263—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer having non-uniform thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

The present invention provides include alternate polymeric layer pair multilayer sandwich, and the method for manufacturing and using the multilayer sandwich.The multilayer sandwich of embodiment according to the present invention can comprise more than three polymeric layers, and can show desirable acoustics and optical property, this may make them to be suitable for various types of Multilayer panels, including the safety glass for automobile and Application in Building.

Description

With enhanced propertied multilayer sandwich
The cross reference of related application
The application is the part continuation application for the U.S.Application Serial Number 14/886,469 submitted on October 19th, 2015, whole Disclosure is incorporated herein by this reference.
Background of invention
1. invention field
This disclosure relates to which polymer interlayers, in particular to be suitable for the polymer interlayers of such as Multilayer panel.
2. description of Related Art
Poly- (vinyl butyral) (PVB) is frequently utilized for manufacture polymer sheet, and the polymer sheet may be used as stage construction Interlayer in plate (including such as light-transmitting laminate, such as safety glass).Safety glass typically refers to include that at least one setting exists The translucent laminate of polymer sheet or interlayer between two glass sheets.Safety glass is usually in building and automobile application As transparent barrier part, major function first is that absorb the energy by impacting or hitting generation, without allowing object penetration glass Glass.In the case where the power of application is enough to destroy glass, it is broken that the polymer interlayers being arranged between panel retain sharp glass Piece, this to minimize the injury of people or object and damage in the closed region of glass.Safety glass can also provide it Its benefit such as reduces ultraviolet (UV) and/or infrared (IR) radiation, and it can also be reinforced by increasing color, texture etc. The aesthetic appearance of window opening.In addition, also having manufactured the safety glass with desirable acoustic properties, generate quieter Inner space.
The interlayer for being used to form acoustics glass panel may include single " core " layer being clipped between two outside " skin " layers. In general, sandwich layer is the more soft layer compared with outer skin with more lower glass transition temperatures.Increased using more soft layer The strong interlayer makes the ability of the acoustic energy dissipative of vibrational structure, so that sound be made to minimize by the transmission of panel.In order to abundant Sound transmitting is reduced, the sandwich layer of acoustic interlayer must be sufficiently thick to allow that lateral shear occurs in laminar structure.Sandwich layer is insufficient Three layers of acoustic interlayer enough acoustic attenuation performances cannot be provided.
Those of formed using the Multilayer panel of conventional acoustic interlayer, including with glass substrate, in extreme processing and/or Under environmental condition, it is possible to create be known as the defects of vision of " frost flower " or " snowflake ".The temperature of the defects of these types in raising In the presence of and in laminate retain excess air when formed, more particularly formed in more soft sandwich layer.When to laminate surface When plate imposes the temperature and/or glass strain of raising, remaining any air pocket is likely to form bubble in interlayer, when panel exposure When extreme condition, bubble is nucleated in more soft sandwich layer and is then diffused in entire polymeric layer.It is more when being used to form The substrate of deck panels includes mismatch glass, as tempered glass, thermal reinforced glass, annealed glass panel and with significant curvature When glass panel (such as windshield), the defect of these types be it is especially problematic, forming air pocket can wherein gather So-called " bending gap ".
Thus, it is desirable to resist the multilayer sandwich of defect (including frost flower) formation, while still showing good optical property With suitable acoustical behavior.Such interlayer should can be used for diversified application, including automobile and aviation safety glass, and Building panel and other polymer laminates.
Summary of the invention
One embodiment of the invention is related to a kind of multilayer sandwich comprising: comprising the first poly- (vinyl acetal) resin First polymer layer；The second polymer layer comprising the second poly- (vinyl acetal) resin；It is poly- (vinyl acetal) comprising third The third polymer layer of resin；The 4th polymeric layer comprising the 4th poly- (vinyl acetal) resin；With include the 5th poly- (ethylene Acetal) resin the 5th polymeric layer.The second polymer layer is arranged between first and third polymer layer and with it respectively Contact, and wherein the 4th polymeric layer is arranged between third and the 5th polymeric layer and respectively contacts with it.Second and Four polymeric layers respectively have differed with the glass transition temperature of at least one of first, third and the 5th polymeric layer to Few 3 DEG C of glass transition temperature, and second and the 4th at least one of polymeric layer there is the thickness less than 50 microns.
Another embodiment of the present invention is related to a kind of multilayer sandwich comprising: it is set comprising first poly- (vinyl acetal) The first polymer layer of rouge；The second polymer layer comprising the second poly- (vinyl acetal) resin；Include poly- (the vinyl alcohol contracting of third Aldehyde) resin third polymer layer；The 4th polymeric layer comprising the 4th poly- (vinyl acetal) resin；Gather with comprising the 5th 5th polymeric layer of (vinyl acetal) resin.The second polymer layer be arranged between first and third polymer layer and and its Respectively contact, and wherein the 4th polymeric layer is arranged between third and the 5th polymeric layer and respectively contacts with it.Second Respectively there is the glass transition temperature phase at least one of first, third and the 5th polymeric layer with the 4th polymeric layer At least 3 DEG C of glass transition temperature of difference, and second and the 4th at least one of polymeric layer have greater than 50 microns Thickness, and second and the 4th polymeric layer combination thickness be greater than 75 microns.The interlayer has according to ASTM E90(2009) At least 35 decibels (dB) of the sound transmission loss measured at 20 DEG C of temperature and the frequency of 3150 Hz, wherein test panel has 80 centimetres of length and 50 centimetres of width respectively have the transparent glass panel structure of 2.1 or 2.3 millimeters of thickness by two pieces At.
Another embodiment of the present invention is related to a kind of multilayer sandwich comprising at least three pairs of alternate polymeric layers.Respectively It include: the first polymer comprising the first poly- (vinyl acetal) resin and at least one plasticizer to alternate polymeric layer Layer, and the second polymer layer adjacent with first polymer layer.The second polymer layer is set comprising second poly- (vinyl acetal) Rouge and at least one plasticizer.For it is described at least one of, the first poly- (vinyl acetal) resin have with it is second poly- Residual hydroxyl content the difference at least residual hydroxyl content of 2 weight % and/or the first poly- (vinyl alcohol of (vinyl acetal) resin Acetal) resin has and differs the Residual acetic acid of at least 2 weight % with the residual acetate content of the second poly- (vinyl acetal) resin Ester content.The interlayer have according to ASTM E90(2009) measured at 20 DEG C of temperature and the frequency of 3150 Hz at least 35 The sound transmission loss of decibel (dB), wherein test panel has 80 centimetres of length and 50 centimetres of width, is respectively had by two pieces The transparent glass panel of 2.1 or 2.3 millimeters of thickness is constituted.
Another embodiment of the present invention is related to a kind of multilayer sandwich comprising at least three pairs of alternate polymeric layers.It hands over The polymeric layer replaced to respectively including: the first polymerization comprising the first poly- (vinyl acetal) resin and at least one plasticizer Nitride layer, and the second polymer layer adjacent with first polymer layer.The second polymer layer includes second poly- (vinyl acetal) Resin and at least one plasticizer.For it is described at least one of, the first poly- (vinyl acetal) resin have and second Residual hydroxyl content the difference at least residual hydroxyl content of 2 weight % and/or the first poly- (ethylene of poly- (vinyl acetal) resin Acetal) resin has and differs the remaining second of at least 2 weight % with the residual acetate content of the second poly- (vinyl acetal) resin Acid and esters content.For at least the two of the centering, the combination of the combination thickness and the second polymer layer of first polymer layer is thick Degree is greater than 75 microns.The interlayer has according to ASTM E90(2009) measured at 20 DEG C of temperature and the frequency of 3150 Hz At least 35 decibels (dB) of sound transmission loss, wherein test panel has 80 centimetres of length and 50 centimetres of width, each by two pieces It is constituted from the transparent glass panel of the thickness with 2.1 or 2.3 millimeters.
A further embodiment of the invention is related to a kind of multilayer sandwich comprising: it is set comprising first poly- (vinyl acetal) The first polymer layer of rouge and at least one plasticizer；The second polymer layer that is adjacent with first polymer layer and contacting, wherein The second polymer layer includes the second poly- (vinyl acetal) resin and at least one plasticizer；It is adjacent with the second polymer layer and connect The third polymer layer of touching, wherein third polymer layer includes poly- (vinyl acetal) resin of third and at least one plasticizer； The 4th polymeric layer that is adjacent with third polymer layer and contacting, wherein the 4th polymeric layer includes the 4th poly- (vinyl acetal) Resin and at least one plasticizer；And the 5th polymeric layer that is adjacent with the 4th polymeric layer and contacting, wherein the 5th polymerization Nitride layer includes the 5th poly- (vinyl acetal) resin and at least one plasticizer.Second and the 4th poly- (vinyl acetal) resin it is each At least 2 are differed with the residual hydroxyl content of at least one of first, third and the 5th poly- (vinyl acetal) resin from having The residual hydroxyl content of weight % and/or wherein second and the 4th poly- (vinyl acetal) resin respectively have with first, third and The residual acetate content difference at least residual acetate of 2 weight % of at least one of 5th poly- (vinyl acetal) resin Content.Second and the 4th polymeric layer respectively there is the average thickness less than 50 microns.
A further embodiment of the invention is related to a kind of multilayer sandwich comprising: it is set comprising first poly- (vinyl acetal) The first polymer layer of rouge and at least one plasticizer；The second polymer layer that is adjacent with first polymer layer and contacting, wherein The second polymer layer includes the second poly- (vinyl acetal) resin and at least one plasticizer；It is adjacent with the second polymer layer and connect The third polymer layer of touching, wherein third polymer layer includes poly- (vinyl acetal) resin of third and at least one plasticizer； The 4th polymeric layer that is adjacent with third polymer layer and contacting, wherein the 4th polymeric layer includes the 4th poly- (vinyl acetal) Resin and at least one plasticizer；And the 5th polymeric layer that is adjacent with the 4th polymeric layer and contacting, wherein the 5th polymerization Nitride layer includes the 5th poly- (vinyl acetal) resin and at least one plasticizer.Second and the 4th poly- (vinyl acetal) resin it is each At least 2 are differed with the residual hydroxyl content of at least one of first, third and the 5th poly- (vinyl acetal) resin from having The residual hydroxyl content of weight % and/or wherein second and the 4th poly- (vinyl acetal) resin respectively have with first, third and The residual acetate content difference at least residual acetate of 2 weight % of at least one of 5th poly- (vinyl acetal) resin Content.Second and the 4th at least one of polymeric layer there is the average thickness greater than about 50 microns, and second and the The combination thickness of four polymeric layers is greater than 75 microns.
Brief Description Of Drawings
Various embodiments of the present invention are described in detail hereinafter with reference to attached drawing, in which:
Fig. 1 is the sectional view of the multilayer sandwich 10 of embodiment configuration according to the present invention；
Fig. 2 is the sectional view of multilayer sandwich 10 shown in Fig. 1；
Fig. 3 is the sectional view of the gradual change interlayer of embodiment configuration according to the present invention, wherein marking the gradual change interlayer Various features are in order to referring to；
Fig. 4 is the sectional view of the gradual change interlayer with the gradation zone extended on the entire width of the interlayer, wherein entirely gradually Becoming region has the constant angle of wedge and straight line thickness distribution；
Fig. 5 is to extend with the gradation zone extended on the partial width of the interlayer and on the partial width of the interlayer flat The sectional view of the gradual change interlayer of smooth fringe region, wherein the gradation zone includes constant angular zone and variable angular zone；
Fig. 6 is with the gradation zone extended on the partial width of the interlayer and extend on the partial width of the interlayer two The sectional view of the gradual change interlayer in a planar edge region, wherein the gradation zone includes constant angular zone and two variable angular regions Domain；
Fig. 7 is with the gradation zone extended on the partial width of the interlayer and extend on the partial width of the interlayer two The sectional view of the gradual change interlayer in a planar edge region, wherein the gradation zone is completely by the variable angle with curve thickness distribution Region is constituted；
Fig. 8 is the sectional view of the gradual change interlayer with the gradation zone extended on the entire width of the interlayer, the wherein gradual change Region includes the three constant angular zones separated each other by two variable angular zones；
Fig. 9 is with the gradation zone extended on the partial width of the interlayer and extend on the partial width of the interlayer two The sectional view of the gradual change interlayer in a planar edge region, wherein the gradation zone includes three constant angular zones and four variable angles Region；
Figure 10 a is the plan view for being configured for use in the gradual change interlayer of vehicle windscreen, wherein the thickness distribution class of the interlayer It is similar to the thickness distribution of interlayer described in Fig. 4；With
Figure 10 b is the sectional view of the interlayer of Figure 10 a, it is shown that the thickness distribution of the interlayer.
Detailed description of the invention
There is described herein the polymer interlayers for being suitable for Multilayer panel (including safety glass and building panel).According to some realities Scheme is applied, polymer interlayers described herein can be the multilayer sandwich including one or more pairs of alternate polymeric layers, institute Stating polymeric layer respectively has different property and/or composition.The one or more of the layer may include micro- with such as 75 The relatively thin layer of rice or smaller thickness, but the interlayer can still show desirable optical property and/or acoustics Matter.According to other embodiments, for including the multilayer sandwich of multipair alternate polymeric layer and each pair of all having the first polymerization The one or more of nitride layer and the second polymer layer, first layer or the second layer can have the thickness greater than 50 microns, and The combination thickness of the first layer of the centering of alternate polymeric layer and the combination thickness of the second layer are greater than 75 microns, which can be with Show improved acoustic properties.It will be described in the various embodiments of multilayer sandwich later, and manufacture such interlayer Method.Multilayer sandwich described herein can be used for various types of Multilayer panels, including for example in automobile, aircraft and/or build Build those used in application.In some embodiments, multilayer sandwich can be aobvious in the head-up for automobile and aircraft application Show in device (HUD) panel and uses.
Term " polymer " layer used herein " and " layer " refer to the one or more polymer for being already shaped into sheet material Resin, optionally with one or more plasticizer combinations.Polymeric layer can further include one or more additional additives, and It can combine with one or more of the other layer to form interlayer.Term " interlayer " used herein typically refers to single-layer or multi-layer Polymer sheet can be adapted to be used together at least one rigid substrates to form Multilayer panel.Term " multiple layers " and " multilayer " refers to that the interlayer with two or more polymeric layers to overlie one another, the polymeric layer are coextruded, are laminated Or it is coupled each other in other ways.
Each polymeric layer of multilayer sandwich described herein may include one or more thermoplastic polymers.Suitably The example of thermoplastic polymer can include but is not limited to poly- (vinyl acetal) resin, polyurethane (PU), poly- (ethylene -co- second Vinyl acetate) (EVA), polyvinyl chloride (PVC), poly- (vinyl chloride -co- methacrylate), polyethylene, polyolefin, ethylene propylene Olefin(e) acid ester copolymer, poly- (ethylene-co-butyl acrylate), elastomer silicone, epoxy resin and be derived from any listed earlier Polymer acid copolymer, such as ethylene/carboxylic acid copolymer and its ionomer, with and combinations thereof.In some embodiments, more One or more layers of layer interlayer may include thermoplastic polymer, and the thermoplastic polymer can be selected from poly- (vinyl alcohol contracting Aldehyde) resin, polyvinyl chloride and polyurethane.In certain embodiments, one or more polymeric layers may include at least one Poly- (vinyl acetal) resin.Although having carried out general description to poly- (vinyl acetal) resin herein, it should be understood that root According to various embodiments of the present invention, one of above-mentioned fluoropolymer resin or it is a variety of can with hereafter described in poly- (ethylene Acetal) resin is included together in interior, or poly- (vinyl acetal) resin of substitution.
Polyurethane can have different hardness.Illustrative polyether polyols have according to ASTM D-2240 less than 85 Xiao A hardness.The example of polyether polyols is AG8451 and AG5050, has the glass transition temperature less than 20 DEG C Aliphatic isocyanate polyether based polyurethanes (available commercially from Woburn, the Thermedics Inc. of MA).EVA polymer can contain There are the vinyl acetate groups of various amounts.Desirable vinyl acetate content is typically about 10 to about 90 moles of %.With compared with The EVA of Low vinyl acetate content can be used for sound insulation at low temperature.Ethylene/carboxylic acid copolymer is usually to have 1 to 25 mole of % It is poly- (ethylene co-methacrylic acid) of carboxylic acid content and poly- (ethylene-co-acrylic acid).The ionomer of ethylene/carboxylic acid copolymer It can be by with alkali, (such as such as the hydroxide of alkali metal (such as sodium) and alkaline-earth metal (such as magnesium), ammonia or other transition metal Zinc) hydroxide moiety or the complete neutralization copolymer obtain.The example of suitable ionomer includes Surlyn®Ionomer tree Rouge (available commercially from Wilmington, the DuPont of Delaware).
The example of exemplary multiple layer sandwich structure includes but is not limited to PVB//PVB//PVB, PVB//PVisoB//PVB, Middle PVB and PVisoB(poly- (the different butyral of vinyl alcohol)) layer include single resin or two or more with different remaining hydroxyl The resin of base content or different polymer compositions；PVC//PVB//PVC, PU//PVB//PU, ionomer //PVB//ionomer, from Polymers //PU//ionomer, ionomer //EVA//ionomer, center core layer PVB(includes PVisoB), PU or EVA include single Resin or two or more resins with different glass transition temperature.Alternatively, cortex and sandwich layer can be with all PVB (using identical or different initial resin).Other combinations of resin and polymer are obvious to those skilled in the art 's.
When one or more polymeric layers include at least one poly- (vinyl acetal) resin, poly- (vinyl acetal) Resin can be formed according to any known method.For example, poly- (vinyl acetal) resin can pass through the presence in catalyst It is lower to be formed Polyvinyl acetal with one or more aldehyde.Gained resin then can be special according to known method, such as the U.S. Benefit numbers 2,282,057 and 2,282,026 andEncyclopedia of Polymer Science & TechnologyIn " Vinyl Acetal Polymers ", volume 8, the 381-399 pages, is write in (2003) by B.E. Wade and is retouched by the 3rd edition It those of states method separation, stabilize and dry.Poly- (vinyl acetal) resin of gained can have at least about 35, be at least big Total acetalation hundred of about 50, at least about 60, at least about 70, at least about 75, at least about 80 or at least about 85 weight % Divide ratio, total acetalation percentage is measured according to ASTM D-1396, unless otherwise stated.In poly- (vinyl acetal) resin The total amount of aldehyde residue may be collectively referred to as acetal component, and the surplus of poly- (vinyl acetal) resin can be residual hydroxy groups and remnants Acetate group, they will be discussed in further detail below.
Poly- (vinyl acetal) resin may include the residue of one or more aldehyde, and can wrap in certain embodiments Containing at least one C1To C12Aldehyde or at least one C4To C8The residue of aldehyde.Suitable C4To C8The example of aldehyde may include but unlimited In butyraldehyde (n-butanal or isobutylaldehyde), 2 methyl pentanal, n-hexyl aldehyde, 2- ethyl hexanal, n-octaldehyde and combinations thereof.In other implementations In scheme, poly- (vinyl acetal) resin may include the residue of other aldehyde, other aldehyde include but is not limited to cinnamic acid, oneself Base cinnamic acid, benzaldehyde, hydrocinnamaldehyde, 4- chlorobenzaldehyde, 4- tert-butyl benzene acetaldehyde, propionic aldehyde, 2- hydrocinnamicaldehyde and combinations thereof, It combines individually or with one or more other aldehyde described herein.
In some embodiments, poly- (vinyl acetal) resin being present in one or more layers of the multilayer sandwich May include the aldehyde residue based on the resin total weight at least about 20, at least about 30, at least about 40, at least about 50, at least about 60 or at least about 70 weight % and/or be no more than about 93, be no more than about 90, be no more than about 85, no More than about 80, at least one C no more than about 75, no more than about 70 or no more than about 65 weight %4To C8Aldehyde it is residual Base.In addition, the total weight of the aldehyde residue based on the resin, poly- (vinyl acetal) resin may include 20 to 93 weight %, 30 to At least one C of the 80 weight weight of % or 40 to 70 %4To C8The residue of aldehyde.C4To C8Aldehyde can be selected from group listed above, or It can be selected from n-butanal, isobutylaldehyde, 2- ethyl hexanal and combinations thereof.In certain embodiments, poly- (vinyl acetal) Resin can be poly- (vinyl butyral), and may include the total weight of all aldehyde residues based on the resin for example not More than about 30, no more than about 20, no more than about 10, no more than about 5 or no more than about 2 weight % except butyraldehyde it The residue of outer aldehyde.
When it is present, one or more layers of the multilayer sandwich may include the combination weight based on resins all in this layer Meter at least about 0.5, at least about 1, at least about 2, at least about 3, at least about 5, at least about 10, at least about 15, At least about 20, at least about 30, at least about 40, at least about 45, at least about 50, at least about 60, at least about 75 Or one or more poly- (vinyl acetal) resins of at least about 80 weight %.In some embodiments, the one of the interlayer There may be resins in addition to poly- (vinyl acetal) resin in a or multiple polymeric layers, and when it is present, can be with It is no more than about 20 based on the combination weight of resins all in this layer, is no more than about 15, is no more than about 10, is no more than greatly About 5, the amount no more than about 2 or no more than about 1 weight % exists.
Multilayer sandwich of the invention may include several different poly- (vinyl acetal) resins.For example, multilayer sandwich can To include at least first poly- (vinyl acetal) polymeric layer and adjacent with the first poly- (vinyl acetal) polymeric layer second Poly- (vinyl acetal) polymeric layer.First poly- (vinyl acetal) polymeric layer may include first poly- (vinyl acetal) tree Rouge, the second polymer layer include the second poly- (vinyl acetal) resin.Term " first " used herein, " second ", " Three " etc. for describing the various elements in specification and claims, these elements should not be limited by such term.This A little terms are only used for distinguishing an element and another element, are not necessarily mean that specific order or even specific element.Example Such as, single element can be referred to as " first " element in the description, and be referred to as " the second element " in detail in the claims.? Be consistent in specification and to each independent claims and its dependent claims, but it is such name be not necessarily intended to for It is restrictive.
Poly- (vinyl acetal) resin of first and second be present in the adjacent polymer layers of the multilayer sandwich can have It is made of different.Similarly, when one or more layers of multilayer sandwich are set comprising two or more poly- (vinyl acetals) When the blend of rouge, at least first and second poly- (vinyl acetal) resins also can have different compositions.For example, some In embodiment, the first poly- (vinyl acetal) resin can have to be contained with the residual hydroxy groups of the second poly- (vinyl acetal) resin Amount and/or the different residual hydroxyl content and/or residual acetate content of residual acetate content.Term used herein " residual hydroxyl content " and " residual acetate content " refers respectively to stay in after processing is completed on poly- (vinyl acetal) resin Hydroxyl and acetate group amount.For example, poly- (vinyl butyral) can be by being hydrolyzed into poly- (second for poly- (vinyl acetate) Enol) and Polyvinyl acetal is then formed to poly- (vinyl butyral) to manufacture with butyraldehyde.Hydrolyzing poly- (acetic acid second Enester) during, and not all acetate group is all converted to hydroxyl group, residual acetate groups stay over the resin. Similarly, during by poly- (vinyl alcohol) acetalation, and not all hydroxyl group is all converted to acetal groups, this is also at this Residual hydroxy groups group is left on resin.Therefore, most of poly- (vinyl acetal) resins include residual hydroxy groups group (as ethylene Base hydroxyl group) and a part as polymer chain of residual acetate groups (as vinyl acetate groups).Residual hydroxy groups Content and residual acetate content indicate with weight %, the poidometer based on fluoropolymer resin, and is surveyed according to ASTM D-1396 , unless otherwise stated.
In some embodiments, first and second poly- (vinyl acetals) being present in the adjacent layer of the multilayer sandwich Difference between the residual hydroxyl content of resin can at least about 2, at least about 5, at least about 10, at least about 12, At least about 15, at least about 20 or at least about 30 weight %.Term " weight percent difference " used herein " should Difference is at least ... weight % " refers to by two given weight percent that a number is subtracted to another numerical calculation it Between difference.For example, it is 14 that poly- (vinyl acetal) resin that residual hydroxyl content is 12 weight %, which has than residual hydroxyl content, The residual hydroxyl content (14 weight % -12 weight %=2 weight %) of the low 2 weight % of poly- (vinyl acetal) resin of weight %. Term " difference " used herein can refer to that a value is higher or lower than another value.
In some embodiments, at least one of first and second poly- (vinyl acetal) resins can have at least About 14, at least about 14.5, at least about 15, at least about 15.5, at least about 16, at least about 16.5, at least about 17, at least about 17.5, at least about 18, at least about 18.5, at least about 19 or at least about 19.5 and/or it is no more than big About 45, no more than about 40, no more than about 35, no more than about 33, no more than about 30, no more than about 27, be no more than About 25, it is no more than about 23.5, is no more than about 22.5, is no more than about 21.5, is no more than about 21, is no more than about 20.5 or it is no more than about 20 weight %, or in 14 to 45 weight %, 16 to 30 weight %, 18 to 25 weight %, 18.5 to 23.5 Residual hydroxyl content in the range of the weight weight of % or 19.5 to 22.5 %.
The other of first and second poly- (vinyl acetal) resins can have at least about 8, at least about 9, extremely Few about 10 or at least about 11 weight % and/or no more than about 16, no more than about 15, no more than about 14.5, be no more than About 13, it is no more than about 11.5, is no more than about 11, is no more than about 10.5, is no more than about 10, is no more than about 9.5 Or it is no more than about 9 weight %, or in 8 to 16 weight %, 9 to 15 weight %, 9.5 to the 14.5 weight weight of % or 10 to 13 % Residual hydroxyl content in range.
It can choose the first and/or second poly- (vinyl acetal) resin, so that first and second poly- (vinyl acetals) Difference between the residual hydroxyl content of resin is fallen in the range of one or more is mentioned above.In addition, it is one or more its Its poly- (vinyl acetal) resin can also exist in one or more extra plays of the interlayer, and these other resins Also it can have the residual hydroxyl content in one or more above ranges.Such other poly- (vinyl acetal) resin can It is set with having with first and/or second poly- (vinyl acetal) in the first and second polymeric layers for being present in the multilayer sandwich The identical or different residual hydroxyl content of the residual hydroxyl content of rouge.
In some embodiments, at least one of first and second poly- (vinyl acetal) resins can have difference In the residual acetate content of another one.For example, in some embodiments, the first and second poly- (vinyl acetal) resins Difference between residual acetate content can at least about 2, at least about 3, at least about 4, at least about 5, it is at least big About 8 or at least about 10 weight %.At least one of poly- (vinyl acetal) resin can have not surpassing of measuring as described above Cross about 4, no more than the about 3, residual acetate content no more than about 2 or no more than about 1 weight %.Or or in addition, At least one of first and second poly- (vinyl acetal) resins can have at least about 5, at least about 8, at least about 10, at least about 12, at least about 14, at least about 16, at least about 18, at least about 20 or at least about 30 weight % Residual acetate content.In other embodiments, the first and second poly- (vinyl acetal) resins, which can have, is no more than About 35, no more than about 30, no more than about 20, no more than 18, no more than about 16, no more than about 14, no more than greatly About 12, no more than about 10, no more than the about 8, remnants no more than about 5, no more than about 2 or no more than about 1 weight % Acetate content.
In some embodiments, the remnants between poly- (vinyl acetal) resin of first and second measured as described above The difference of acetate content can for no more than about 8, no more than about 6, no more than about 5, no more than about 4, be no more than About 3, it is no more than about 2, be no more than about 1 or is no more than about 0.5 weight %.It is present in another in other layers of the interlayer Outer poly- (vinyl acetal) resin can have the residual acetate content in one or more aforementioned ranges, and can have The remnants of the first and/or second poly- (vinyl acetal) resin for having and being present in such as first and/or the second polymer layer The similar and different residual acetate content of acetate content.
In addition, at least one polymeric layer of the multilayer sandwich may include at least one plasticizer.Depending on the polymerization The concrete composition of nitride layer, plasticizer can at least about 5, at least about 10, at least about 15, at least about 20, it is at least big About 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55, it is at least big About 60, at least about 65, at least about 67 or at least about 70 parts/100 parts resins (phr) and/or be no more than about 120, no More than about 110, it is no more than about 105, is no more than about 100, is no more than about 95, is no more than about 90, is no more than about 85, no more than about 75, no more than about 70, no more than about 65, no more than about 60, no more than about 55, no more than greatly About 50, the amount no more than about 45 or no more than about 40 phr exists.In addition, one or more polymerizations in the multilayer sandwich Nitride layer can have the plasticizer loading in one or more following ranges: 5 to 120 phr, 10 to 110 phr, 20 to 90 Phr, 25 to 75 phr, 5 to 50 phr, 15 to 45 phr, 25 to 40 phr, 45 to 120 phr, 55 to 90 phr, 60 to 85 The phr of phr or 65 to 75.
Term " number of resin per hundred parts " used herein or " phr " refer to by weight compared with 100 parts of resins The amount of existing plasticizer.For example, plasticizer will be with the amount of 30 phr if 30 grams of plasticizer are added in 100 grams of resins In the presence of.If the polymeric layer includes two or more resins, the weight of plasticizer merges with existing all resins Amount compares to determine the number of resin per hundred parts.In addition, reference is used for when providing the plasticizer loading of layer herein The amount of the mixture or the plasticizer in melt that manufacture this layer or interlayer provides.
The example for the plasticizer being suitably employed in interlayer of the invention can include but is not limited to: (the 2- second of triethylene glycol two Base capronate) (" 3GEH "), triethylene glycol two (2 Ethylbutanoic acid ester), two heptanoate of triethylene glycol, tetraethylene glycol bis-enanthate, Tetraethylene glycol two (2 ethyl hexanoic acid ester) (" 4GEH "), dihexyl adipate, dioctyl adipate, adipic acid hexyl cyclohexyl, Diisononyl adipate, adipic acid heptyl nonyl ester, (butoxyethyl group) ester of adipic acid two and bis- (2- (the 2- butoxy second of adipic acid Oxygroup) ethyl) ester, dibutyl sebacate, dioctyl sebacate, dipropylene glycol dibenzoate, tripropylene glycol dibenzoate, Dibenzonate, isodecyl benzoate, benzoic acid 2- ethylhexyl, diethylene glycol benzoic ether, propylene glycol hexichol Formic acid esters, 2,2,4- trimethyl -1,3- glycol dibenzoate, 2,2,4- trimethyl -1,3- pentanediol benzoic ether isobutyl The adjacent toluene of acid esters, 1,3 butylene glycol dibenzoate, 2,2,4- trimethyl -1,3- glycol dibenzoate, diethylene glycol two Formic acid esters, two ortho-toluic acid ester of triethylene glycol, two ortho-toluic acid ester of dipropylene glycol, dibenzoic acid 1,2- monooctyl ester, inclined benzene three Sour three -2- ethylhexyls, di-2-ethylhexyl terephthalate, bisphenol-A bis- (2 ethyl hexanoic acid esters), ethoxylated nonyl benzene Phenol and its mixture.The plasticizer can be selected from triethylene glycol two (2 ethyl hexanoic acid ester), two (2 ethyl hexanoic acid of tetraethylene glycol Ester) and its mixture or the plasticizer may include triethylene glycol two (2 ethyl hexanoic acid ester).
Include poly- (vinyl acetal) resin of difference with different residual hydroxyl contents and/or residual acetate content Adjacent polymer layers may also finally include different amounts of plasticizer when at least one plasticizer combinations.Therefore, comprising tool There may also be different property by the adjacent polymer layers of different poly- (vinyl acetal) resins formed.Although be not intended to by Theory constraint, it is envisaged that the compatibility of given plasticizer and poly- (vinyl acetal) resin can be at least partially dependent on this The composition of resin is particularly depending on its residual hydroxyl content.In general, with the poly- (ethylene of higher residual hydroxyl content Acetal) resin tends to the lower phase to given plasticizer of the similar resin shown than with lower residual hydroxyl content Capacitive (or capacity).Therefore, poly- (vinyl acetal) resin with higher residual hydroxyl content tends to than with lower residual The similar resin of remaining hydroxy radical content is less plasticized and shows higher rigidity.On the contrary, having lower residual hydroxyl content Poly- (vinyl acetal) resin tend to the plasticizer for being incorporated to higher amount when with given elasticizer plasticizing, this can lead to generation Show the more soft polymeric layer than the lower glass transition temperature of similar resin with higher residual hydroxyl content. Depending on specific resin and plasticizer, these trend can be reversed.
In some embodiments, first polymer layer may include the first poly- (vinyl acetal) resin and at least one Plasticizer, and the second polymer layer adjacent with first polymer layer may include the second poly- (vinyl acetal) resin and extremely A kind of few plasticizer.First and second plasticizer can be the plasticizer of same type or the first and second plasticizer can be with It is different.In some embodiments, at least one of first and second plasticizer are also possible to two or more plasticizer Blend, the plasticizer can be identical as one of other layers for being present in the interlayer or a variety of other plasticizer or not Together.
In some embodiments, the first and second polymeric layers can have different plasticizer loadings.For example, first And the difference of the second plasticizer loading between adjacent polymer layers can at least about 2, at least about 5, at least about 8, At least about 10, at least about 12 or at least about 15 phr.In many embodiments, comprising with lower hydroxy radical content The polymeric layer of resin can have higher plasticizer loading.In order to control or keep other property of the polymeric layer or interlayer Matter, the difference of the plasticizer loading between the first and second adjacent polymeric layers can for no more than about 40, be no more than it is big About 30, it is no more than about 25, be no more than about 20 or is no more than about 17 phr.In other embodiments, first and second The difference of plasticizer loading between polymeric layer can be at least about 40, at least about 50, at least about 60 or at least big About 70 phr.
When poly- (vinyl acetal) resin of two kinds of residual hydroxyl contents with different level is respectively blended with plasticizer And when being configured to adjacent polymeric layer, plasticizer can distribute between the adjacent polymer layers in the interlayer, so that more Plasticizer can reside in the layer with lower residual hydroxyl content, and less plasticizer can reside in higher residual In the layer of remaining hydroxy radical content.Finally, equilibrium state is realized between two polymeric layers.The remnants of poly- (vinyl acetal) resin Relationship between hydroxy radical content and plasticizer compatbility/capacity can be in order to the plasticising of the addition appropriate amount into fluoropolymer resin Agent.Such relationship, which is additionally aided, stably keeps two or more when plasticizer migrates between resin in other ways The difference of plasticizer loading between resin.
In addition to a plasticizer, one or more of polymeric layer can also be comprising assigning the interlayer special properties or spy Other additives of sign.Such additives can include but is not limited to dyestuff, pigment, stabilizer (such as ultra-violet stabilizer), Antioxidant, anti-blocking agent, fire retardant, infrared absorbing agents or blocking agent (such as tin indium oxide, antimony tin, lanthanum hexaboride (LaB6) and cesium tungsten oxide), processing aid, flow enhuancement additive, lubricant, impact modifier, nucleating agent, heat stabilizer, UV absorbent, dispersing agent, surfactant, chelating agent, coupling agent, adhesive, priming paint, reinforced additive, filler and combinations thereof.
In addition, in some embodiments, at least one of described layer may include one or more bond control agents (" ACA ") is to control the bonding of sheet material and glass or other rigid substrates.In various embodiments, it is present in the polymeric layer In ACA amount can at least about 0.003, at least about 0.01, at least about 0.025 and/or be no more than about 0.15, No more than about 0.10 or it is no more than about 0.04 phr, or in 0.003 to 0.15 phr, 0.01 to 0.10 phr, 0.025 To 0.040 phr.Suitable ACA can include but is not limited to sodium acetate, potassium acetate, bis- (2 Ethylbutanoic acid) magnesium, ACA disclosed in bis- (2 ethyl hexanoic acid) magnesium and combinations thereof and, for example, U.S. Patent number 5,728,472.
Since with different compositions, poly- (vinyl acetal) polymeric layer of adjacent first and second can be shown not Same property.For example, in some embodiments, the first and second polymeric layers can have different glass transition temperatures Degree.The glass transition temperature or T of polymer materialgIt is the temperature for marking the transformation from the glassy state of polymer to rubbery state. Glass transition is measured by dynamic mechanical analysis (DMTA), measurement under shear mode in the frequency of oscillation of 1 Hz and Energy storage (elasticity) modulus as unit of Pascal of the sample changed with temperature under the temperature scan rate of 3 DEG C/min (G '), loss (viscosity) modulus (G ") as unit of Pascal and tan δ (G "/G ').Then pass through the peak tan δ on temperature scale Position determines glass transition temperature.
According to some embodiments, the first poly- (vinyl acetal) polymeric layer be can have than the second adjacent poly- (second Enol acetal) polymeric layer glass transition temperature it is high or low at least about 3, at least about 5, at least about 8, at least about 10, at least about 12, at least about 15, at least about 18, at least about 20, at least about 22, at least about 25 DEG C, at least big About 30 DEG C or at least about 35 DEG C of glass transition temperature.One of first and second polymeric layers can have at least big About 26, at least about 28, at least about 30, at least about 33 or at least about 35 DEG C and/or be no more than about 70, be no more than it is big About 65, be no more than about 60, be no more than about 55 or be no more than about 50 DEG C, or 26 to 70 DEG C, 30 to 60 DEG C or 35 to Glass transition temperature in the range of 50 DEG C.The other of first and second poly- (vinyl acetal) resins can have not More than 25, no more than about 20, no more than about 15, no more than about 10, no more than about 5, no more than about 0, be no more than About -5 or the glass transition temperature no more than about -10 DEG C.
Other than the first and second poly- (vinyl acetal) polymeric layers, the other layers being present in the multilayer sandwich can To have the vitrifying similar or different from the glass transition temperature of poly- (vinyl acetal) polymeric layer of the first or second to turn Temperature.For example, in some embodiments, multilayer sandwich may include at least with the second poly- (vinyl acetal) polymeric layer Poly- (vinyl acetal) polymeric layer of adjacent third, and the second poly- (vinyl acetal) polymeric layer can be set first It is respectively contacted between poly- (vinyl acetal) polymeric layer of third and with it.Poly- (vinyl acetal) polymeric layer of third can be with With glass transition temperature similar with the glass transition temperature of the first poly- (vinyl acetal) polymeric layer.In some realities It applies in scheme, third polymer layer can have the glass transition temperature than the second adjacent poly- (vinyl acetal) polymeric layer Spend high or low at least about 3, at least about 5, at least about 8, at least about 10, at least about 12, at least about 15, it is at least big About 18, at least about 20, at least about 22 or at least about 25 DEG C of glass transition temperature.
In certain embodiments, multilayer sandwich of the invention can comprise more than three layers.With more than three layers One example of multilayer sandwich 10 is shown in fig 1 and 2.As shown in embodiment discribed in Fig. 1 and 2, interlayer 10 can To include corresponding first, second, and third poly- (vinyl acetal) polymeric layer 12a, 12b and 12c.In some embodiments In, which can also be poly- including being shown as the 4th and the 5th poly- (vinyl acetal) of layer 12d and 12e in fig 1 and 2 Close nitride layer.In some embodiments, interlayer 10 can have alternate polymeric layer, so that first, third and the 5th poly- (second Enol acetal) polymeric layer 12a, 12c and 12e have similar property and/or composition, and second and the 4th poly- (vinyl alcohol contracting Aldehyde) polymeric layer 12b and 12d have similar property and/or composition.It is provided below with multiple alternate polymer The additional detail of the multilayer sandwich of layer.
Multilayer sandwich described herein may include any appropriate number of polymeric layer.In some embodiments, The interlayer can have totalnA polymeric layer, whereinnIt is the integer of the value at least 5.In some embodiments,nIt can Be at least 6, at least 7, at least 8, at least 9, at least 10, at least 11, at least 15, at least 25, at least 35, at least 55, extremely Few 75, at least 125, at least 175, at least 225, at least 275, at least 325, at least 375, at least 425 or at least 475 and/or not More than 2450, no more than 2050, no more than 1025, no more than 975, no more than 875, no more than 775, no more than 675, be no more than 575 or no more than 525, no more than 425, no more than 325, no more than 225, no more than 125, no more than 75, no more than 55, do not surpass 45 are crossed, is no more than 35, is no more than 30, is no more than 25, is no more than 20, is no more than 17, is no more than 15, is no more than 13, is no more than 11 Or the integer of the value no more than 9.In addition,nIt can have 5 to 55,5 to 35,5 to 25,7 to 25,7 to 17,9 to 15,9 to 13 Or the value in the range of 9 to 11, ornIt can have value in the range of 9 to 75,15 to 55,25 to 45, ornIt can be with With value in the range of 50 to 2450,75 to 1025,125 to 975,325 to 775 or 425 to 575.
It is amounted to when havingnWhen the adjacent polymer layers of the multilayer sandwich of a polymeric layer have different compositions, every one Layer (i.e. alternate layer) can have similar composition and/or property.Therefore, in some embodiments, at least one is poly- Closing nitride layer can have the property similar to polymeric layer one or more of the other in the interlayer.For example, in some embodiments In, glass transition temperature in multilayer sandwich than amounting tonThe glass transition temperature of at least one of a polymeric layer is low At least about 3, at least about 5, at least about 8, at least about 10, at least about 12, at least about 15, at least about 18, extremely The sum for lacking the layer of about 20, at least about 22, at least about 25 DEG C, at least about 30 DEG C or at least about 35 DEG C can be equal to (n- 1) if/2(nIt is odd number) ornIf/2(nIt is even number).It similarly, in some embodiments, include its residual hydroxy groups Content and/or residual acetate content are than amounting tonAt least one of a poly- (vinyl acetal) polymeric layer is low at least about 2, poly- (vinyl acetal) resin of at least about 3, at least about 4, at least about 5, at least about 6 or at least about 8 weight % Poly- (vinyl acetal) polymeric layer quantity can be equal to (n- 1) if/2(nIt is odd number) ornIf/2(nIt is even number). It in certain embodiments, is also likely to be with lower residual hydroxyl content with the polymeric layer compared with lower glass transition temperatures And/or the layer with higher residual acetate content.
Alternate polymeric layer 12a-e, which may be considered that, to be arranged with several Duis, has two adjacent layer structures of alternately composition At each right.Although illustratively comprising two in fig 1 and 2 to (such as 12a, b and 12c, d) alternate polymeric layer, according to this The interlayer of the embodiment of invention may include at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 8, at least about 10, at least about 12 or at least about 15 or more to alternate polymeric layer.Such as Fig. 1 and 2 Shown in, it is each to alternate polymeric layer respectively include one of polymeric layer 12a and 12c (such as " first group " polymeric layer) with One of polymeric layer 12b and 12d (such as " second group " polymeric layer).Each polymer in first group of polymeric layer 12a, c Layer can have similar composition and/or property with each polymeric layer in second group of polymeric layer 12b, d, and adjacent polymeric Nitride layer 12a, b and 12c, the property of d and/or composition can be different from each other, as being hereinbefore discussed in detail.
Also as shown in figs. 1 and 2, multilayer sandwich 10 may include unpaired coating, be shown as polymeric layer 12e, Its position is adjacent with the polymeric layer 12d in alternate polymeric layer 12c, d of end pair.Coating 12e can have similar In the composition of one or more of other polymeric layer 12a-d of interlayer 10, or can have different from the other of interlayer 10 At least one of polymeric layer 12a-d layer or each layer of composition.Although being shown as simple layer in fig 1 and 2, coating 12e itself can be the multiple layer polymer including at least two, at least three, at least four, at least five or more polymeric layer Sheet material.When coating 12e includes multiple layers, at least part in polymeric layer can have first similar to interlayer 10 The composition of group polymeric layer 12a, c, and at least part in polymeric layer can have second group similar to interlayer 10 The composition of polymeric layer 12b, d.According to such embodiment, coating 12e can be configured to keep shown in interlayer 10 The pattern of alternating polymer layers.In other embodiment (not shown)s, at least part of coating 12e or whole polymer The composition of layer can be totally different from the composition of any of polymeric layer 12a-d of interlayer 10.
When coating 12e is single polymers layer and its composition is similar to the composition of first group of polymeric layer 12a, c, The glass transition temperature that polymeric layer 12a, c, e respectively can have the second polymer layer 12b, d than second group is high by least 3 DEG C glass transition temperature so that glass of the glass transition temperature than coating 12e of the layer 12d adjacent with coating 12e Glass transition temperature is at least 3 DEG C low.In some embodiments, coating 12e may include for example and have and adjacent polymer Poly- (vinyl acetal) resin in layer 12d compares poly- (vinyl acetal) resin of higher residual hydroxyl content, and/or covers Cap rock 12e can have and the relatively low plasticizer loading of adjacent polymer layers 12d.When it is present, " hardness " coating 12e Interlayer 10 with improvement property (impact strength including raising) can be provided, and/or easy to process can be post-processed (as pressed Flower) during and/or form operation to interlayer 10 during Multilayer panel.It will discuss later about manufacture according to this hair The additional detail of the method for the multilayer sandwich of bright various embodiments.
In various embodiments, multilayer sandwich of the invention can have at least about 125, at least about 250, at least About 350, at least about 400, at least about 450, at least about 500, at least about 550 or at least about 600 microns and/or No more than about 3360, it is no more than about 2540, is no more than about 2290, being no more than about 1520, being no more than about 890, no More than the integral thickness of the about 850, integral thickness no more than about 760 microns or the multilayer sandwich can 350 to In the range of 2800 microns, 350 to 2540 microns, 400 to 1520 microns, 450 to 890 microns or 600 to 850 microns.This is more The individual polymeric layer of layer interlayer respectively can have at least about 0.05, at least about 0.1, at least about 0.25, at least About 0.5, at least about 1, at least about 2, at least about 3, at least about 4, at least about 5, at least about 10, at least about 15, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40 or at least about 45 microns and/ Or it is less than about 75, is less than about 65, is less than about 60, is less than about 55, is less than about 50, is less than about 49, is less than about 45, it is less than about 40, is less than about 35, is less than about 30, is less than about 25, is less than about 20, is less than about 15, is less than about 10, it is less than about 5, is less than about 4, is less than about 3, is less than about 2, is less than about 1, is less than about 0.5, is less than about 0.1 The thickness of micron.In addition, individually polymeric layer can have at 0.05 to 75 micron, 0.1 to 65 micron or 1 to 49 micron Thickness in range.
In other embodiments, at least one of the individual polymeric layer of the multilayer sandwich, which can have, is greater than 50, it is greater than 55, is greater than 60, is greater than 65, is greater than 70, is greater than 75, is greater than 80, is greater than 85, is greater than 90, is greater than 95, is greater than 100, is big In 105, greater than 110, greater than 115, greater than 120 or greater than 125 microns and/or less than about 1500, less than about 1400, be less than About 1300, less than about 1200, less than about 1100, less than about 1000, less than about 900, less than about 800, be less than About 700, it is less than about 600, is less than about 500, is less than about 400, is less than about 300, being less than about 200 or be less than about 100 microns of thickness.In addition, individually polymeric layer can have be greater than 50 to 1500 microns, be greater than 50 to 1000 microns, Greater than the thickness in the range of 50 to 800 microns, 55 to 500 microns, 60 to 400 microns or 65 to 200 microns.
In some embodiments, multilayer sandwich can have the alternating pair of polymeric layer, so that the alternating centering has The combination thickness or overall thickness of the polymeric layer of similarity or composition can be greater than 75, be greater than 100, be greater than 125, be greater than 150, Greater than 175, it is greater than 200, is greater than 225 or is greater than 250 microns, and is being greater than 75 to 510 microns, 90 to 375 microns, 100 to 260 Micron or 125 to 260 microns in the range of.The combination thickness or overall thickness of the other polymeric layers of alternating centering can be greater than 75, it is greater than about 100, is greater than about 250, is greater than about 300, is greater than about 400, is greater than about 500, is greater than about 600, is big In about 700, it is greater than about 800, is greater than about 900, being greater than about 1000 or be greater than about 1250 microns, and 75 to 2780 In the range of micron, 100 to 2250 microns, 200 to 2000 microns or 500 to 2000 microns.
In some embodiments, two or more being polymerized alone in nitride layer of the multilayer sandwich can have similar Thickness so that the thickness of for example described layer is within about 2 microns of another layer, within about 5 microns, about 10 microns with It is interior, within about 15 microns or within about 20 microns.Several individual layers can have similar thickness, so that some In embodiment, polymeric layer sum at least about 5%, at least about 10%, at least about 30%, at least about 40%, extremely Few about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95% or at least big About 97%, it is rounded up to immediate integer, can have about 20 of the average thickness of all polymeric layers in the interlayer Within micron, within about 15 microns, within about 10 microns, within about 5 microns, within about 2 microns, it is about 1.5 micro- Thickness within rice, within about 1 micron or within about 0.5 micron.
In some embodiments, two or more individual polymeric layers can have and polymer other in interlayer One or more different thickness in layer.It polymerize for example, at least one of polymeric layer can have with other in interlayer The thickness of one or more of nitride layer differs at least about 3, at least about 3.5, at least about 4 or at least about 5 microns Thickness.In addition, in some embodiments, in the multilayer sandwich all polymeric layers at least about 50%, at least about 55%, At least about 60% or at least about 65% can have and differ at least about 3 microns of thickness with the average thickness of all polymeric layers Degree.But according to other embodiments, being no more than about 20%, be no more than about 10% of multilayer sandwich middle polymeric layer sum, It can have no more than about 5% or no more than about 1% and to differ at least about 3 microns with the average thickness of all polymeric layers Thickness.
Multilayer sandwich described herein may include the interlayer of general planar, along the length or longest of the sheet material Size and/or width or the second long size there is essentially identical thickness.But in some embodiments, of the invention Multilayer sandwich can be the gradual change comprising at least one gradation zone with wedge profile or wedge shape interlayer.Gradual change interlayer Along the length of the sheet material and/or the modified thickness distribution of at least part of width, so that for example the interlayer is at least One edge has the thickness greater than other edges.When the interlayer is gradual change interlayer, in individual polymeric layer at least 1 A, at least two, at least three, at least four or more may include at least one gradation zone.Gradual change interlayer is particularly useful for Such as the head up display (HUD) panel in automobile and aircraft application.
Turning now to Fig. 3 to 10, several embodiments of gradual change interlayer according to the present invention are provided.Fig. 3 be include tool The sectional view of the exemplary gradual change interlayer of the gradation zone of the thickness changed.As shown in Figure 3, gradation zone have this gradually Become the minimum thickness T that first boundary in region measuresminWith the maximum gauge measured at the second boundary of the gradation zone Tmax.In certain embodiments, TminIt can be at least about 0.25, at least about 0.40 or at least about 0.60 millimeter (mm) And/or it is no more than 1.2, is no more than about 1.1 or is no more than about 1.0 mm.In addition, TminCan 0.25 to 1.2 mm, In the range of 0.40 to 1.1 mm or 0.60 to 1.0 mm.In certain embodiments, TmaxCan at least about 0.38, extremely Lack about 0.53 or at least about 0.76 mm and/or be no more than 2.2, be no more than about 2.1 or be no more than about 2.0 mm.This Outside, TmaxIt can be in the range of 0.38 to 2.2 mm, 0.53 to 2.1 mm or 0.76 to 2.0 mm.In certain embodiments, TmaxWith TminBetween difference can at least about 0.13, at least about 0.15, at least about 0.20, at least about 0.25, At least about 0.30, at least about 0.35, at least about 0.40 mm and/or no more than 1.2, no more than about 0.90, be no more than About 0.85, no more than about 0.80, no more than about 0.75, no more than about 0.70, no more than about 0.65 or it is no more than About 0.60 mm.In addition, TmaxWith TminBetween difference can 0.13 to 1.2 mm, 0.25 to 0.75 mm or 0.40 to In the range of 0.60 mm.In certain embodiments, the distance between first and second boundaries of the gradation zone (i.e. " gradual change Peak width ") it can be at least about 5, at least about 10, at least about 15, at least about 20 or at least about 30 centimetres (cm) and/or it is no more than about 200, is no more than about 150, is no more than about 125, being no more than about 100 or be no more than about 75 cm.In addition, the gradation zone width can be in the range of 5 to 200 cm, 15 to 125 cm or 30 to 75 cm.
As shown in Figure 3, which includes the first and second opposite outer extreme edges.In certain embodiments In, the distance between first and second outer extreme edges (i.e. " interlayer width ") can be at least about 20, at least about 40 Or at least about 60 cm and/or be no more than about 400, be no more than about 200 or be no more than about 100 cm.In addition, the interlayer Width can be in the range of 20 to 400 cm, 40 to 200 cm or 60 to 100 cm.In the embodiment described in Fig. 3, First and second boundaries of the gradation zone and the first and second outer extreme edges of the interlayer are inwardly spaced.In such reality It applies in scheme, a part of the only interlayer is gradual change.When the gradation zone merely comprises a part of the interlayer, interlayer is wide Degree and the ratio between gradation zone width can at least about 0.05:1, at least about 0.10:1, at least about 0.20:1, it is at least big About 0.30:1, at least about 0.40:1, at least about 0.50:1, at least about 0.60:1 or at least about 0.70:1 and/or not More than about 1:1, be no more than about 0.95:1, be no more than about 0.90:1, be no more than about 0.80:1 or be no more than about 0.70:1.In addition, the ratio between interlayer width and gradation zone width can be in the ranges of 0.05:1 to 1:1 or 0.30:1 to 0.90:1 It is interior.In an alternate embodiment being discussed below, entire interlayer is gradual change.When entire interlayer is gradual change, gradually Become peak width and be equal to interlayer width, and the first and second boundaries of the gradation zone are located at the first and second distal edges At edge.
As shown in Figure 3, the gradation zone of the interlayer has the angle of wedge (), is defined as extending through wherein first and the Two gradation zone boundaries and the interlayer first (on) the first reference line of two points of the interlayer of surface intersection and extend Pass through the first and second gradation zone boundaries and the interlayer second (under) the second reference of two points of surface intersection The angle formed between line.In certain embodiments, the angle of wedge of the gradation zone can at least about 0.10, at least about 0.13, at least about 0.15, at least about 0.20, at least about 0.25, at least about 0.30, at least about 0.35 or at least big About 0.40 milliradian (mrad) and/or be no more than about 1.2, be no more than about 1.0, be no more than about 0.90, be no more than about 0.85, it is no more than about 0.80, is no more than about 0.75, is no more than about 0.70, being no more than about 0.65 or be no more than about 0.60 mrad.In addition, the angle of wedge of the gradation zone can be in 0.10 to 1.2 mrad, 0.13 to 1.0 mrad, 0.25 to 0.75 In the range of the mrad of mrad or 0.40 to 0.60.
When the first and second surfaces of the gradation zone are respectively plane, the angle of wedge of the gradation zone is simply first (on) surface and second (under) angle between surface.But as hereinafter discussed in more detail like that, in certain embodiment party In case, which may include the variable angular zone of at least one angle of wedge with curve thickness distribution and consecutive variations. In addition, in certain embodiments, which may include two or more constant angular zones, wherein the constant angular region Domain respectively has straight line thickness distribution, but at least two constant angular zones have the different angles of wedge.
Fig. 4-9 instantiates the various gradual change interlayers of embodiment configuration according to the present invention.Fig. 4 is depicted including from interlayer 20 first end edge 24a extends fully into the interlayer 20 of the gradation zone 22 of the second end edge 24b of interlayer 20.At this In kind configuration, the first and second boundaries of gradation zone are located at first and second terminal edge 24a, b of the interlayer.In Fig. 4 The entire gradation zone 22 of the interlayer 20 of description has the constant angle of wedge, be simply interlayer 20 first (on) flat table Face and second (under) angle that is formed between flat surfaces.
Fig. 5 instantiates the interlayer 30 including gradation zone 32 and flat fringe region 33.First boundary of gradation zone 32 35a is located at the first end edge 34a of interlayer 30, and the second boundary 35b of gradation zone 32 is located at gradation zone 32 and puts down Smooth 33 confluce of fringe region.Gradation zone 32 includes constant angular zone 36 and variable angular zone 37.Constant angular zone 36 has Straight line thickness distribution and the constant angle of wedgec, and variable angular zone 37 has the angle of wedge of curve thickness distribution and consecutive variations.It is variable The starting angle of wedge of angular zone 37 is equal to the constant angle of wedgec, and the termination angle of wedge of variable angular zone 37 is zero.Describe in Fig. 5 Interlayer 30 has the constant angle of wedge of the whole angle of wedge greater than entire gradation zone 32c。
Fig. 6 instantiates the interlayer 40 including the gradation zone 42 between first and second planar edge region 43a, b. First boundary 45a of gradation zone 42 is located at gradation zone 42 and the first planar edge region confluce 43a, and gradation zone 42 The second boundary 45b be located at gradation zone 42 and the second planar edge region confluce 43b.Gradation zone 42 includes being located at first And the second constant angular zone 46 between variable angular zone 47a, b.First variable angular zone 47a constitutes the first planar edge region Transitional region between 43a and constant angular zone 46.Second variable angular zone 47b constitutes the second planar edge region 43b and perseverance Determine the transitional region between angular zone 46.Constant angular zone 46 has straight line thickness distribution and the constant angle of wedgec, and first and Two variable angular zone 47a, b have the angle of wedge of curve thickness distribution and consecutive variations.The starting angle of wedge of first variable angular zone 47a Equal to zero, and the termination angle of wedge of the first variable angular zone 47b is equal to the constant angle of wedgec.The starting of second variable angular zone 47b The angle of wedge is equal to the constant angle of wedgec, and the termination angle of wedge of the second variable angular zone 47b is zero.The interlayer 40 described in Fig. 4 has Greater than the constant angle of wedge of the whole angle of wedge of entire gradation zone 42c。
Fig. 7 instantiates the interlayer 50 including the gradation zone 52 between first and second planar edge region 53a, b. The gradation zone 52 of interlayer 50 does not include constant angular zone.On the contrary, the entire gradation zone 52 of interlayer 50 is with curve thickness The variable angular zone of the angle of wedge of distribution and consecutive variations.It is extended through as described above, the whole angle of wedge of gradation zone 52 is used as Wherein first and second boundary 55a, b of gradation zone 52 and interlayer 50 first (on) two points of surface confluce first Reference line " A " with extend through wherein gradation zone 52 first and second boundary 55a, b and interlayer 50 second (under) surface Angle between the second reference line " B " of two points of confluce measures.But in gradation zone 52, the curve thickness Distribution provides the numerous angle of wedge, can be greater than, less than or equal to the whole angle of wedge of entire gradation zone 52.
Fig. 8 instantiate do not include any flat end part interlayer 60.On the contrary, the gradation zone 62 of interlayer 60 constitutes Entire interlayer 60.First and second boundary 65a, b of gradation zone 60 are located at the first and second terminal edges of interlayer 60 as a result, At 64a, b.The gradation zone 62 of interlayer 60 includes the first, second, and third constant angular zone 46a-c, can by first and second Angle region 47a, b separate.First, second, and third constant angular zone 46a-c respectively has straight line thickness distribution, and respectively divides It Ju You not the unique first, second, and third constant angle of wedgec1、Ѳc2、Ѳc3.First variable angular zone 47a serves as first and Transitional region between two constant angular zone 46a, b.Second variable angular zone 47b serve as the second and constant angular zone 46b of third, Transitional region between c.As discussed above, the whole angle of wedge of gradation zone 62 as the first reference line " A " with Angle between second reference line " B " measures.The first constant angle of wedgec1Less than the whole angle of wedge of gradation zone 62.Second The constant angle of wedgec2Greater than the whole angle of wedge of gradation zone 62.The constant angle of wedge of thirdc3Less than the whole wedge of gradation zone 62 Angle.The angle of wedge of first variable angular zone 47a is from the first constant angle of wedgec1It continuously enlarges to the second constant angle of wedgec2.Second The angle of wedge of variable angular zone 47b is from the second constant angle of wedgec2It is continuously reduced to the third angle of wedgec3。
Fig. 9 instantiates the interlayer 70 including the gradation zone 72 between first and second planar edge region 73a, b. First and second boundary 75a, b of gradation zone 72 and first and second external margin 74a, b of interlayer 70 are inwardly spaced.Interlayer 70 gradation zone 72 includes the first, second, third and fourth variable angular zone 77a-d and first, second, and third constant Angular zone 76a-c.First variable angular zone 77a is served as between the constant angular zone 76a of the first planar edge region 73a and first Transitional region.Second variable angular zone 77b serves as the transition between the first constant constant angular zone 76b of angular zone 76a and second Region.Third can be changed angular zone 77c and serve as the transitional region between the second constant angular zone 76b and the constant angular zone 76c of third. 4th variable angular zone 77d serves as the transitional region between the constant angular zone 76c of third and the second planar edge region 73b.The One, the second and constant angular zone 76a-c of third respectively has straight line thickness distribution, and respectively have unique first, Second and the constant angle of wedge of thirdc1、Ѳc2、Ѳc3.As discussed above, the first, second, third and fourth variable angle Region 77a-d has the perseverance from the angle of wedge that can be changed the constant angular zone on 77 side of angular zone on variable 77 other side of angular zone Determine the angle of wedge of the angle of wedge continuous transition of angular zone.
As discussed above, which may include one or more constant angle gradation zones, respectively have There is the width of the overall width less than entire gradation zone.Each gradation zone can have the whole angle of wedge with entire gradation zone The identical or different angle of wedge.For example, the gradation zone may include one, two, three, four, five or more constant Angle gradation zone.When using multiple constant angle gradation zones, the constant angle gradation zone can by variable angle gradation zone that This is separated, and the variable angle gradation zone serves as the transition between adjacent constant angle gradation zone.
In certain embodiments, the width of each constant angle gradation zone can at least about 2, at least about 5, at least About 10, at least about 15 or at least about 20 cm and/or be no more than about 150, be no more than about 100 or be no more than about 50 cm.In certain embodiments, the ratio between overall width of the width of each constant angle gradation zone and entire gradation zone can be with For at least about 0.1:1, at least about 0.2:1, at least about 0.3:1 or at least about 0.4:1 and/or it is no more than about 0.9: 1, it is no more than about 0.8:1, is no more than about 0.7:1, is no more than about 0.6:1 or is no more than about 0.5:1.
In certain embodiments, the angle of wedge of each constant angle gradation zone can at least about 0.13, at least about 0.15, at least about 0.20, at least about 0.25, at least about 0.30, at least about 0.35, at least about 0.40 mrad and/ Or be no more than about 1.2, be no more than about 1.0, be no more than about 0.90, be no more than about 0.85, be no more than about 0.80, no More than about 0.75, it is no more than about 0.70, is no more than about 0.65 or is no more than about 0.60 mrad.In addition, each constant angle The angle of wedge of gradation zone can be in the range of 0.13 to 1.2 mrad, 0.25 to 0.75 mrad or 0.40 to 0.60 mrad. In certain embodiments, the angle of wedge of at least one constant angle gradation zone is at least bigger greatly than the whole angle of wedge of entire gradation zone About 0.01, at least about 0.05, at least about 0.10, at least about 0.20, at least about 0.30 or at least about 0.40 mrad.In certain embodiments, the angle of wedge of at least one constant angle gradation zone is smaller than the whole angle of wedge of entire gradation zone At least about 0.01, at least about 0.05, at least about 0.10, at least about 0.20, at least about 0.30 or at least about 0.40 mrad.In certain embodiments, whole wedge of the angle of wedge of at least one constant angle gradation zone than entire gradation zone Angle is no more than greatly about 0.40, is no more than about 0.30, is no more than about 0.20, is no more than about 0.10, is no more than about 0.05 or be no more than about 0.01 mrad.In certain embodiments, the angle of wedge of at least one constant angle gradation zone is than entire The whole angle of wedge of gradation zone is small to be no more than about 0.40, is no more than about 0.30, is no more than about 0.20, is no more than about 0.10, it is no more than about 0.05 or is no more than about 0.01 mrad.
Figure 10 a and 10b instantiate thickness distribution similar to the interlayer 80 of the interlayer 30 of Fig. 5.The interlayer 80 of Figure 10 a and 10b Vehicle windscreen is configured to by the way that the interlayer to be fixed between two sheet glass.As depicted in Figure 10 a, folder The first end edge 84a of layer 80 can be located at the bottom of windshield, and the second end edge 84b of interlayer 80 can be located at The top of windshield.The gradation zone 82 of interlayer 80 is positioned in the region of the windshield of head-up display to be disposed In.The gradation zone 82 of interlayer 80 includes constant angular zone 86 and variable angular zone 87.As depicted in Figure 10 a, In certain embodiments, gradation zone 82 is between the first side edge 88a and second side edge 88b of interlayer 80 completely across folder Layer 80 extends.Figure 10 b(its be similar to Fig. 5) show interlayer 80 between at the top of the windshield bottom and the windshield Thickness distribution.
When in the Multilayer panel for being assembled in various embodiments according to the present invention, multilayer sandwich described herein can To show desirable property, including desirable acoustics and optical property.Transparency is for describing interlayer described herein One parameter of optical property, and can be measured for example, by measuring the haze value of interlayer.The haze value indicates and incident light The quantization of the opposite light scattered by sample.In some embodiments, multilayer sandwich according to the present invention can have basis ASTM D1003-13-program B using light source C measured under 2 ° of viewing angle be less than about 3%, be less than about 2%, be less than it is big About 1% or the haze value less than about 0.5%.The test spectrophotometer, as Hunterlab UltraScan XE instrument (can It is commercially available from Hunter Associates, Reston, VA) it is carried out on the polymer samples with a thickness of 0.76 mm, it is described poly- It closes object sample and has been laminated to the transparent glass sheet material for the thickness that two pieces respectively have 2.3 mm (available commercially from Pennsylvania Pittsburgh Glass Works) between.
It has also been found that the multilayer sandwich of embodiment configuration according to the present invention is being exposed to extreme processing and/or environment item The tendency of formation frost flower defect when part with reduction.In some embodiments, for example, when being tested according to following procedure, Multilayer sandwich described herein can have no more than about 40%, no more than about 35%, no more than about 30%, be no more than About 25%, be no more than about 20%, be no more than about 15%, be no more than about 10%, be no more than about 5%, be no more than about 2% or Average frost flower formation rate no more than about 1%.
By poly- (ethylene glycol terephthalate) with 7.5 cm internal diameters, 14 cm outer diameters and 0.10 to 0.18 mm thickness (PET) ring is placed centrally at the top of the cm interlayer of 30 cm × 30.The interlayer and PET ring are subsequently clipped in two piece of 30 cm of cm × 30 Transparent glass sheet material between, the component through in advance lamination and high pressure sterilization processing.Gained laminate improves 48 hours at room temperature, Then heated 48 hours at 80 DEG C in conventional ovens.Keep gained laminate cooling, and visually inspects to determine in laminate Frost flower formation rate." frost flower formation rate " is defined as showing the area percentage in the PET ring of frost flower defect.The nine of identical interlayer Above procedure is repeated on the other samples of part, and calculates the average value of frost flower formation rate to determine the average frost flower formation rate of the interlayer.
The multilayer sandwich of embodiment according to the present invention can also show desirable acoustic properties, such as example, by sound Transmission of the sound when passing through the interlayer is reduced as indicated by (sound transmission loss of interlayer).In some embodiments, root The sound transmission loss of multilayer sandwich configured according to the present invention can at least about 35, at least about 35.5, at least about 36, at least About 36.5, at least about 37, at least about 37.5, at least about 38, at least about 38.5, at least about 39, at least about 39.5, at least about 40 dB, at least about 40.5 dB, at least about 41 dB, at least about 41.5 dB or at least about 42 DB, according to ASTM E90(2009) it is measured at 20 DEG C of temperature and the frequency of 3150 Hz, wherein test panel has 80 centimetres Length and 50 centimetres of width, by respectively being constituted with the glass panels of 2.1 or 2.3 mm of thickness.
The sound transmission loss in the one or more of above range may be implemented in multilayer sandwich described herein, has simultaneously There is relatively thin acoustic polymer layer.For example, in some embodiments, which may be implemented to pass as described above Acoustic loss has without one and is no more than 25, is no more than about 20, is no more than about 15, is no more than about 10, is no more than greatly About 5, no more than about 0, no more than about -5 or the polymeric layer of the glass transition temperature no more than about -10 DEG C can have Have greater than about 75, is greater than about 65, is greater than about 55, is greater than about 50, is greater than about 49, is greater than about 45, is greater than about 40, it is greater than about 35, is greater than about 30, is greater than about 25, is greater than about 20, is greater than about 15, is greater than about 10, is greater than about 5, greater than about 4, greater than the about 2, thickness greater than about 1 or greater than about 0.5 micron.
In some embodiments, which may be implemented sound transmission loss as described above, be no more than wherein having 25, be no more than about 20, be no more than about 15, be no more than about 10, be no more than about 5, be no more than about 0, be no more than about- 5 or the glass transition temperature no more than about -10 DEG C polymeric layer can have greater than 50, greater than 55, greater than 60, be greater than 65, greater than 70, greater than 75, greater than 80, greater than 85, greater than 90, greater than 95, greater than the 100, thickness greater than 110 or greater than 120 microns.
Multilayer sandwich described herein can be manufactured according to any suitable method.In general, one or more poly- (ethylene Acetal) resin, it is optionally blended at least one plasticizer and one or more aforementioned additives, can be shaped as layer, the layer It can combine to form multilayer sandwich.The illustrative methods for forming polymeric layer can include but is not limited to solution-cast, compression Molding, injection moulding, melt extrusion, melt-blown and combinations thereof.In some embodiments, two or more polymeric layers may be used also For example, by coextrusion, inflation film, melt-blown, dip-coating, solution coating, scraper, blade, air knife, printing, powder coated, spray It applies and combinations thereof and to be made.
In the various embodiments of the present invention, the layer or interlayer can be formed by extrusion or co-extrusion.It is squeezing out In method, one or more thermoplastic polymers, plasticizer and optionally at least one additives, which can premix to be merged into, to be expected In extrusion device.Other additives, as ACA, colorant and UV inhibitor (it can be liquid, powder or pellet form) can also To use, and can be mixed into before being introduced into extrusion device in thermoplastic polymer or plasticizer.These additives It can be incorporated into fluoropolymer resin, and be ultimately incorporated into gained resin sheet, thus enhance certain properties of the interlayer, and Improve the performance of the compound glass panel or other final products that are formed with the interlayer.
In some embodiments, which can be used laminating method and is formed, and wherein (it can make the layer with interlayer Formed with coetrusion) it is combined into multilayer sandwich under heat and pressure.
In some embodiments, which can be used coetrusion using layer dynode system to be formed.This Class system separates using one or more separating elements in die feeding block and is re-engaged thin polymer melt material Stream is to form the sheet material with alternate polymeric layer.In some embodiments, which may be capable of forming any The layer of quantity, and may for example be capable of forming as described above with totalnA layer of resin sheet.
In general, such layer dynode system may be capable of forming the resin sheet with even number layer.Therefore, such as Fig. 1 and 2 Shown in, when the multilayer sandwich further comprises overlying polymer layer, which can be together with multi-layer sheet It is coextruded or is added in other ways and form final interlayer on multi-layer sheet.Alternatively, the overlying polymer layer (works as presence When) can be added on multi-layer sheet according to any suitable way, one of method including being mentioned above or a variety of, and It can add while forming multi-layer sheet, or be added after it is formed as processing step after squeezing out.
Resin combination, layer and the interlayer of embodiment according to the present invention can use in Multilayer panel, described more Deck panels include polymeric layer or interlayer and at least one rigid substrates.Any suitable rigid substrates can be used, some Rigid substrates described in embodiment can be selected from glass, polycarbonate, biaxial orientation PET, copolyesters, acrylic and its group It closes.When the rigid substrates include polymer material, which may include or does not include hard coat superficial layer.? In some embodiments, which includes a pair of of rigid substrates, and resin sandwich is disposed there between.The panel can be used for more Kind final use application, including for example for windshield and window, aircraft windshield and window, for various transports Using the panel of (such as marine applications, railway applications), structural construction panel (such as window, door, stair, pavement, railing), Decorative building panel, weatherability panel (such as anti-hurricane glass or perspex), ballistic panel and other similar applications.
When being laminated multilayer sandwich described herein between two rigid substrates (such as glass), this method may include At least following steps: (1) two pieces of substrates and interlayer are assembled；(2) assembly is heated via IR radiator or convection device to continue First short time period；(3) assembly is sent into pressure roll to carry out first time degassing；(4) by the assembly through one section Short time period is heated approximately to 60 DEG C to about 120 DEG C, so that the assembly has enough temporary adhesions to seal the folder The edge of layer；(5) assembly is sent into second pressure roll further to seal the edge of the interlayer and allow to be further processed； (6) high temperature high pressure process is carried out to the assembly at 135 DEG C to 150 DEG C of temperature and the pressure of 150 psig to 200 psig About 30 to 90 minutes.As described according to above-mentioned steps (2) some embodiments into (5) will interlayer-glass interfacial degassing Other methods include vacuum bag method and vacuum ring method, both can also be used for forming interlayer of the invention as described herein.
The following examples are intended to illustrate the present invention to instruct those skilled in the art to implement and using the present invention, not anticipate It is limiting the scope of the invention in any way.
Embodiment
Pass through the poly- of the melt blended residual hydroxyl content with 19 weight % and the residual acetate content less than 2 weight % Plasticizer is simultaneously for the triethylene glycol two (2 ethyl hexanoic acid ester) (" 3GEH ") of (vinyl butyral) resin (" resin B ") and 38 phr Gained resin of plastification is squeezed out to form the polymer sheet with a thickness of 760 microns, monolayer control's interlayer (CI-1) is consequently formed.
Comparison interlayer (CI-2) and open interlayer (DI-1 to DI-4) are manufactured according to following method.By being coextruded resin B (it initially uses the 3GEH of 41.5 phr to be plasticized) and Resin A (it is initially melt blended with the 3GEH of 50 phr) forms three layers of comparison Interlayer (CI-2).Gained interlayer includes the outer layer of a pair of of resin of plastification B, clips the internal layer of resin of plastification A formation.Resin A layer and Primary plasticizer content in resin B layer is not at balance, and is distributed between said layers to reach equilibrium state.These layers are each From final plasticizer loading provide in table 1 below.The thickness of A layers of extrusion resin and resin B layer is so that realizing plasticizer After balance, final thickness is identical as shown in table 1.
By the way that by resin B (it initially uses the 3GEH of 41.5 phr to be plasticized) or resin C(, it initially uses the 3GEH of 34 phr to increase Modeling) it is coextruded to Resin A (it is initially plasticized with the 3GEH of 50 phr) including the foregoing 4 × fence cell of two or four Open interlayer (DI-1 to DI-4) is formed in the die feeding block of part.Increase as used by when comparing interlayer CI-2 with construction Mould agent distribution like that, plasticizer of the DI-1 into DI-4 is between resin layer A and B or between resin layer A and C after allowing to squeeze out Distribution is to reach its equilibrium state.A layers of extrusion resin, resin B layer and C layers of resin of thickness are so that reach balance in plasticizer After state, final thickness is as shown in table 1.
It can also be by the way that resin B (being plasticized with the 3GEH of 38 phr) or another residual hydroxy groups with 22 weight % be contained Poly- (vinyl acetal) resin of amount and the residual acetate content less than 2 weight % (resin C is plasticized with the 3GEH of 30 phr) It is coextruded in the die feeding block including 4 × separating element of two or four with Resin A (being plasticized with the 3GEH of 75 phr) To form the open interlayer (DI-1 to DI-4) having more than three polymeric layers.Melt material flow is separated into more by each separating element A relatively thin stock, and the stock is reconfigured to form the resin sheet with multiple alternate resin layers.With two 4 × points Include amounting to 32 polymeric layers every the resin sheet that element is formed, includes with the resin sheet that four 4 × separating elements are formed Amount to 512 polymeric layers.Each disclosed interlayer has 813 microns of integral thickness.In each open interlayer DI-1 to DI-4 In, the thickness of each individual polymeric layer is identical as shown in the following table 1.
It should be understood that other primary plasticizer carrying capacity in resin layer A, B and C can be used, as long as each layer Final plasticizer loading and thickness it is identical as shown in table 1.For example, if the primary plasticizer carrying capacity of resin layer A, B and C point Not Wei 60 phr, 40 phr and 32 phr, similar interlayer can also be constructed, as long as selecting the original depth of these layers to realize The final plasticizer loading and thickness of resin layer A, B and C shown in table 1.
As previously mentioned, according to ASTM E-90(2009) it is measured respectively at a temperature of the reference frequency of 3,150 Hz and 20 DEG C Compare the sound transmission loss of the sample of interlayer CI-1 and CI-2 and each open interlayer DI-1 to DI-4.It the results are provided in the following table 1. In addition, being formed according to the frost flower that preceding method tests the sample of each interlayer, and further visually inspect any position in laminate The frost flower at the place of setting is formed, including the inside and outside region of PET annulus.For the embodiment, any kind of frost flower is shown The laminate for forming (regardless of whether in PET annulus) is labeled as showing frost flower defect, and not formed in or beyond PET ring The laminate of frost flower is labeled as not formed frost flower defect.The interlayer for forming frost flower defect is marked in table 1 with "Yes", without Those of frost flower defect is formed to be marked with "No".
Shown in table 1 as above, the sound transmission loss of open interlayer DI-1 to DI-4 and the sound transmission loss class of comparison interlayer CI-2 Seemingly, still, it is different from comparison interlayer CI-2, open interlayer DI-1 to DI-4 does not form frost flower defect when being exposed to above-mentioned condition.
(made by being coextruded with the second resin of plastification (resin B) the first resin of plastification (Resin A) with forming three layer interlayers With conventional it is coextruded method) manufacture three layers of PVB sheet (PVB-1 to PVB-7).Resulting three-layer interlayer respectively includes a pair by setting Outer (or skin) layer (resin layer B) that rouge B is formed, clip by Resin A formed in (or core) layer (resin layer A).Resin used and The Details: SUMMARY of resulting three-layer PVB sheet is in table 2.
Three layers of PVB sheet in table 2 are used for through combination or are laminated two or more described three layers of PVB sheets to produce The raw multilayer sandwich with two or more layers comprising resin layer A and three or more layers comprising resin layer B carrys out shape At open interlayer DI-5 to DI-15.Open interlayer DI-8 to DI-10 respectively contains the PET(poly terephthalic acid there are two 2 mils Glycol ester) film so that three-layer tablet material to be separated from each other, prevents the migration of plasticizer between sheet material.PVB-1 is with comparing interlayer It (CI-3), only include three layer interlayer.
As previously mentioned, according to ASTM E-90(2009) measurement pair at a temperature of the reference frequency of 3,150 Hz and 20 DEG C The sound transmission loss of sample than interlayer CI-3 and each open interlayer DI-5 to DI-15.It is respectively the glass surface of 2.3 mm with thickness Plate measures CI-3 and DI-5 to DI-12, and is respectively the glass panel measurement DI-13 to DI-15 of 2.1 mm with thickness.As a result it provides In the following table 3.
Shown in table 3 as above, open interlayer DI-5 to DI-15(its have two or more include resin layer A layers and Three or more include the layer of resin layer B) there is sound transmission loss more higher than the sound transmission loss for comparing interlayer CI-3.Open folder For layer DI-5 to DI-7 tool there are two the layer of resin layer A, respective thickness is respectively 76(DI-5 and D-6) and it is 89(DI-7) micro- Rice, and A layers of resin layer of combination thickness is respectively 152(DI-5 and DI-6) and 178(DI-7) micron, and show 40.3 to 41 The sound transmission loss at 3150 Hz of dB, this than comparison interlayer CI-3(its only have one with a thickness of 114 microns of resin layer A, and show the sound transmission loss of 39.9 dB) sound transmission loss it is higher.There are two resin layers for open interlayer DI-13 and DI-15 tool A layers (respectively 114 microns thick, and combination resin layer A is with a thickness of 228 microns) and the biography at 3150 Hz for showing 41.9 dB Acoustic loss.Openly (respective with a thickness of 76 microns, combination resin layer A is thick resin layer A layers there are three interlayer DI-8 to DI-12 tools Degree is 228 microns) and show the sound transmission loss at 3150 Hz of 40.6 to 40.9 dB.Open interlayer DI-14 has three Resin layer A layers a (respective with a thickness of 114 microns, combination resin layer A is with a thickness of 342 microns) and show 42.8 dB Sound transmission loss under 3150, the sound transmission loss than comparing interlayer CI-3 are similar 3 dB high.(it has total all open interlayers At least five layers of meter (B layers of at least two A layers of resin layers and at least three resin layer)) it shows than only having the comparison there are three layer The higher sound transmission loss at 3150 Hz of interlayer.
Although the description for having been combined certain embodiments (including being presently believed to be those of preferred embodiment) is public The present invention is opened, which is intended to for example, and being understood not to limit the scope of the present disclosure.Such as the common skill in this field Art personnel are it will be appreciated that the present invention covers the embodiment in addition to those of detailed description herein.It can be without departing substantially from this hair The modification and variation of described embodiment are made in the case where bright spirit and scope.
It is to be further understood that being provided as provided in the whole text herein for any one-component of the disclosure Any model that any range, numerical value or characteristic can provide in the case of compatibility with any other component for the disclosure It encloses, numerical value or characteristic are used interchangeably, the embodiment with formation with the limit value to each component.For example, interlayer can be formed, It includes poly- (vinyl butyrals) with the residual hydroxyl content in any given range, additionally include any given model Interior plasticizer is enclosed, to be formed within the scope of this disclosure but be difficult to many permutation and combination enumerated.In addition, unless separately saying Bright, the range provided for a kind or a classification (such as phthalic acid ester or benzoic ether) is readily applicable to the kind Member's (such as dioctyl terephthalate) of interior species or the category.

Claims (20)

1. multilayer sandwich, comprising:
First polymer layer comprising the first poly- (vinyl acetal) resin and plasticizer；
The second polymer layer comprising the second poly- (vinyl acetal) resin and plasticizer；
Third polymer layer comprising third poly- (vinyl acetal) resin and plasticizer；
The 4th polymeric layer comprising the 4th poly- (vinyl acetal) resin and plasticizer；With
The 5th polymeric layer comprising the 5th poly- (vinyl acetal) resin and plasticizer,
Wherein the second polymer layer is arranged between described first and the third polymer layer and respectively contacts with it, and And wherein the 4th polymeric layer is arranged between the third and the 5th polymeric layer and respectively contacts with it,
Wherein described second and the 4th polymeric layer respectively have in described first, third and the 5th polymeric layer extremely The glass transition temperature of few one differs at least 3 DEG C of glass transition temperature, and wherein described second and the described 4th The combination thickness of polymeric layer is greater than 75 microns.
2. the interlayer of claim 1, wherein the vitrifying of at least one of described first, third and the 5th polymeric layer Transition temperature is at least 26 DEG C.
3. the interlayer of claim 1, wherein the vitrifying of at least one of described second and described 4th polymeric layer Transition temperature is no more than 20 DEG C.
4. the interlayer of claim 1, wherein described second and the 4th polymeric layer respectively have than described first, third and Low at least 3 DEG C of the glass transition temperature of the glass transition temperature of at least one of 5th polymeric layer.
5. the interlayer of claim 1, wherein at least one of described second and the 4th polymeric layer are micro- with being greater than 50 The thickness of rice.
6. the interlayer of claim 1, wherein first, second, third, fourth and fifth poly- (vinyl acetal) resin is respectively With corresponding first, second, third, fourth and fifth residual hydroxyl content and corresponding first, second, third, fourth He 5th residual acetate content, and wherein at least one of following saying is true:
(i) first, at least one of third and the 5th residual hydroxyl content and second and the 4th in residual hydroxyl content extremely Difference between few one is at least 2 weight %；With
(ii) first, at least one of third and the 5th residual acetate content are with second and the 4th in residual acetate content At least one between difference be at least 2 weight %.
7. the interlayer of claim 6, wherein saying is (i) and (ii) true.
8. the interlayer of claim 6, wherein one of first, third and the 5th residual acetate content and second and four-infirm Maximum difference between one of remaining acetate content is no more than 4 weight %.
9. the interlayer of claim 1, wherein the first polymer layer have the vitrifying than the second polymer layer The glass transition temperature that at least 3 DEG C of transition temperature height, and wherein the 5th polymeric layer has than the 4th polymerization At least 3 DEG C of the glass transition temperature height of glass transition temperature of nitride layer.
10. the interlayer of claim 1, wherein described second and the respective thickness of the 4th polymeric layer be greater than 50 microns.
11. the interlayer of claim 1, wherein at least the plasticizer loading difference between a pair of adjacent polymer layers is at least about 10 phr。
12. multilayer sandwich, comprising:
At least 3 pairs of alternate polymeric layers, wherein the alternate polymeric layer to respectively including:
First polymer layer comprising the first poly- (vinyl acetal) resin and at least one plasticizer；With
The second polymer layer adjacent with the first polymer layer, wherein the second polymer layer includes the second poly- (ethylene Acetal) resin and at least one plasticizer；
Wherein, for it is described at least one of, the residual hydroxyl content of first poly- (vinyl acetal) resin and institute The residual hydroxyl content for stating the second poly- (vinyl acetal) resin differs at least 2 weight % and/or wherein the described first poly- (ethylene Acetal) resin residual acetate content differed with the residual acetate content of the described second poly- (vinyl acetal) resin to Few 2 weight %；
Wherein the second polymer layer has the thickness greater than 50 microns；With
Wherein the interlayer has according to ASTM E90(2009) it is measured at least at 20 DEG C of temperature and the frequency of 3150 Hz The sound transmission loss of 35 dB, wherein test panel has 80 centimetres of length and 50 centimetres of width, respectively has 2.3 by two pieces The transparent glass panel of the thickness of millimeter is constituted.
13. the interlayer of claim 12, wherein the residual hydroxyl content of first poly- (vinyl acetal) resin compares institute State the residual hydroxyl content height at least 2 weight % of the second poly- (vinyl acetal) resin.
14. the interlayer of claim 12, wherein the residual acetate content of first poly- (vinyl acetal) resin with it is described The residual acetate content difference of second poly- (vinyl acetal) resin is no more than 4 weight %, and/or wherein the described first poly- (second Enol acetal) resin the residual hydroxyl content and the described second poly- (vinyl acetal) resin the residual hydroxyl content Differ at least 5 weight %.
15. the interlayer of claim 12, further comprise with the alternate polymeric layer to one of described second The adjacent overlying polymer layer of one of polymeric layer, wherein in the second polymer layer adjacent with the coating The one has glass transition temperature, and wherein the coating has and described second adjacent to the coating The glass transition temperature of the one in polymeric layer differs at least 3 DEG C of glass transition temperature.
16. multilayer sandwich, comprising:
First polymer layer comprising the first poly- (vinyl acetal) resin and at least one plasticizer；
The second polymer layer that is adjacent with the first polymer layer and contacting, wherein the second polymer layer includes second poly- (vinyl acetal) resin and at least one plasticizer；
Third polymer layer that is adjacent with the second polymer layer and contacting, wherein the third polymer layer is poly- comprising third (vinyl acetal) resin and at least one plasticizer；
The 4th polymeric layer that is adjacent with the third polymer layer and contacting, wherein the 4th polymeric layer includes the 4th poly- (vinyl acetal) resin and at least one plasticizer；With
The 5th polymeric layer that is adjacent with the 4th polymeric layer and contacting, wherein the 5th polymeric layer includes the 5th poly- (vinyl acetal) resin and at least one plasticizer,
Wherein described second and the 4th poly- (vinyl acetal) resin respectively have it is poly- with described first, third and the 5th At least one of (vinyl acetal) resin residual hydroxyl content difference at least the residual hydroxyl content of 2 weight % and/or its Described in second and the 4th poly- (vinyl acetal) resin respectively have and first, third and the 5th poly- (vinyl acetal) The residual acetate content difference at least residual acetate content of 2 weight % of at least one of resin, and wherein described the Two and the 4th polymeric layer respectively there is the average thickness greater than 50 microns.
17. the interlayer of claim 16, wherein at least one of described second and the 4th polymeric layer have with it is described The first, the glass transition temperature of at least one of third and the 5th polymeric layer differs at least 3 DEG C of glass transition temperature Degree.
18. the interlayer of claim 16, wherein the interlayer has according to ASTM E90(2009) in 20 DEG C of temperature and 3150 At least sound transmission loss of 35 dB measured under the frequency of Hz, wherein test panel has 80 centimetres of length and 50 centimetres of width Degree is made of two pieces of transparent glass panels respectively with 2.3 millimeters of thickness.
19. the interlayer of claim 16, wherein at least the plasticizer loading difference between a pair of adjacent polymer layers are at least big About 10 phr.
20. the interlayer of claim 16, wherein the glass of at least one of described second and described 4th polymeric layer Change transition temperature and is no more than 20 DEG C.
CN201780081501.9A 2016-12-29 2017-12-14 With enhanced propertied multilayer sandwich Pending CN110114217A (en)

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CN115027111A (en) * 2022-06-06 2022-09-09 中建材（内江）玻璃高新技术有限公司 Composite sound-insulation laminated glass

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