CN101484305B - Laminate material - Google Patents
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- CN101484305B CN101484305B CN200780025305.6A CN200780025305A CN101484305B CN 101484305 B CN101484305 B CN 101484305B CN 200780025305 A CN200780025305 A CN 200780025305A CN 101484305 B CN101484305 B CN 101484305B
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Abstract
A self supporting curved laminate product resulting from curving of a planar precursor, wherein the planar precursor is a self supporting laminate of two sheets of an acrylic thermoplastic, or of sheets including an acrylic thermoplastic, spaced by, but attaching to, an interposed thermoset polyester system, and wherein curving has involved heating of the laminate sufficient to allow its curving without any substantial degradation of the lamination or its component layers.
Description
Invention field
The present invention relates to a kind of laminate material and manufacture method thereof.More specifically but not exclusively say, the present invention relates to comprise laminate material and manufacturing and the manufacturing process of one or more layers mylar internal layer.
Background of invention
In one aspect, the present invention relates to building material technology.Glass is a kind of very common this material.Although glass has many advantages, one of them very significant advantage is the transparency, and glass also has many shortcomings.Glass is very heavy, and is easily broken, and manufacturing and shaping are very difficult.The problem relevant with glass comprises weight, lacks sound insulation and anti-noise character.
We propose to use acrylic material (acrylic).People have used the acrylic material of many versions and kind, for example mainly are for sign, pavement building awning (canopy) and skylight.During having, it to high resistance to impact, also has good scratch resistance.But in many aspects, the character of acrylic material is still not as glass.With the glassy phase ratio, acrylic material needs bigger thickness in some size and spacing.
The discussion of any document, rules, material, device or the goods etc. that comprise in this specification all only is for for the invention provides explanation.And should not regard as and admit that these any or whole contents constituted the part on prior art basis or were the common practise of association area of the present invention before being present in priority date.
The purpose of this invention is to provide a kind ofly from the supporting laminate material, preferably have the advantageous property that one or more are better than glass, particularly when as building or make when using material.
In addition or as an alternative, the purpose of this invention is to provide a kind of laminate material, its can be shaped or moulding.
In addition or as an alternative, the purpose of this invention is to provide a kind of method that is used for making the novelty of laminate material.
In addition or as an alternative, the purpose of this invention is to provide a kind of laminate material, it can provide available selection for the public at least.
Can more clearly understand other purpose of the present invention by following description, below describing only provides with way of example.
Summary of the invention
On the one hand, the present invention relates to the crooked duplexer product of a kind of supporting certainly, plane precursor is crooked to be made by making for it,
Wherein, described plane precursor is the duplexer of supporting certainly of two acrylic compounds thermoplastic sheets, perhaps comprise and separated by the thermosetting polyester system between the centre but be attached to the duplexer of supporting certainly of sheet material of the acrylic compounds thermoplastic of described thermosetting polyester system
Described bending comprises described duplexer is heated to and is enough to reach bending, can not make described duplexer or its form layer simultaneously and produce any significant degraded.
On the one hand, the present invention relates to a kind of from supporting crooked duplexer product, plane precursor is crooked to be made by making for it, wherein, described plane precursor is two acrylic compounds thermoplastic plastic sheets' the duplexer of supporting certainly, perhaps comprise and separated by the thermosetting polyester system between the centre but be attached to the duplexer of supporting certainly of sheet material of the acrylic compounds thermoplastic of described thermosetting polyester system, described bending operation comprises that described duplexer is heated to foot makes its bending, can not make described duplexer or its form layer simultaneously and produce delamination and loss of tensile strength.
On the one hand, the present invention relates to a kind of duplexer product that comprises at least one bending area from supporting, described duplexer product comprises, two or multi-disc acrylic compounds thermoplastic plastic sheet more, perhaps comprise by the thermosetting polyester system between the centre and separating, but be attached to the sheet material of the acrylic compounds thermoplastic of described thermosetting polyester system, the extension at break of described thermosetting polyester system is greater than 150%, described bending area forms in the following manner: from two surfaces of described duplexer shaped region is applied heat, the layer arbitrarily that is heated to the duplexer product that can not make that described shaped region is interior is fused into the temperature of liquid form, can not produce delamination and loss of tensile strength simultaneously.
On the other hand, the present invention relates to a kind of Sparent laminate of supporting certainly product with at least one bending area, described duplexer product has transparent thermosetting polyester system, the extension at break of described transparent thermosetting polyester system is greater than 150%, described thermosetting polyester system is between middle and be attached to the transparent thermoplastic layer of side, the transparent thermoplastic layer of described side is identical or different, and described thermoplastic layer adheres to mutually by following two kinds of mechanism and described thermosetting polyester system:
-with acrylic material in free unsaturated group is crosslinked arbitrarily,
The free monomer solvation of-acrylic material;
Wherein each thermoplastic layer is acrylic material or PETG,
Described bending area forms in the following manner: two surfaces of described Sparent laminate in the shaped region, described shaped region is applied heat, and be heated to the temperature that the layer arbitrarily that can not make in the described shaped region is molten into liquid form.
On the other hand, the present invention relates to a kind of Sparent laminate of supporting certainly product that comprises at least one bending area, described duplexer has between middle and be attached to the transparent heat solidity acrylic compounds thermoplastic layer's of side transparent polyester system, the clear acrylic analog thermoplastic layer of described side is identical or different, described bending area forms in the following manner: two surfaces of described Sparent laminate in the shaped region, described shaped region is applied heat, be heated to and make the layer arbitrarily in the described shaped region be molten into the temperature of liquid form.
Preferably, described heating is carried out at 105-120 ℃.
Preferably, one or two sheet is acrylics, perhaps at least mainly is acrylics.
Preferably, described polyester system is at least part of to be made by following component: (A) carboxylic acid or dicarboxylic acids, one or more provide hydroxyl and/or dihydric component with (B).
Preferably, described polyester system comprises the coreactivity monomer.
Preferred coreactivity monomer is styrene or styrene derivative, perhaps analog.
Preferably, described coreactivity monomer is styrene or styrene analog, and its content in the polyester system is 30-55% (w/w), if styrene most preferably is 35-45% (w/w).
Preferably, the extension at break after described system is solidified is greater than 150% (being preferably greater than 170%).
Preferably, the described content that comprises the unsaturated polyester resin of ethylenic unsaturated group is 45-70% (w/w).
Preferably, described polyester system by or by radical initiator, for example do not rely on the chemical initiator catalysis of ultraviolet light.Perhaps, it can be by the catalysis of free radical ultraviolet initiator.
Preferably, described polyester system has comprised or comprised slaine provides body, to accelerate gelling time when causing.When using the peroxide radical initiator of MEKP (methyl-ethyl-ketone peroxide) and so on, situation especially like this.
Preferably, the content of described metal salt promoter is same order with the content of arbitrarily such initator, perhaps less than the content of described initator.
Preferably, before heat cure, the content of such initator is not more than 2% (w/w) of this system approximately arbitrarily.
Preferably, the content of such initator is less than 1% (w/w) of thermosetting system.
Preferably, stacked being included in of described precursor duplexer arranges the liquid polyesters system between the described sheet material, perhaps at a sheet material this liquid polyesters system is set, and places second sheet material then, makes this system heat cure then.
Preferably, the described mylar system mixture that is following component:
The unsaturated polyester resin that comprises the ethylenic unsaturated group of 45 – 70% (w/w),
The styrene of 30 – 55% (w/w),
Less than the catalyst (for example MEKP) of 2% (w/w),
Initator (for example slaine provides body) less than 2% (w/w).
Preferably, described mylar system is mixed in the temperature range of 18-22 ℃ (preferred about 20 ℃).Preferably, described mylar system (preferred 22 ℃) in 20-24 ℃ temperature range is solidified.
Preferably, described mylar system is mixed in the humidity range of 57-67% (preferred about 62%).Preferably, make described resin in the humidity range of 57-75% (preferred 62-73%, for example about 67%), the heat cure by chemistry initiation and heat release thereof.
Preferably the surface with the adjacent acrylics of polyester system is the face of cleaning, does not namely contain from the releasing agent of any emulsion sheet of removing and/or the material of migration.
Preferably, with solvent cleaning was carried out on the surface of sheet material.
Preferably, before the heat cure of polyester system, will clean facing to the surface of this polyester system described sheet material with isopropyl alcohol.
Preferably, described " without any significant degraded " comprises some distortion of every layer, but can not cause with each described polyester system of adhering to mutually any significant disengaging taking place.
Preferably, in whole BENDING PROCESS, described polyester system between the centre keeps non-liquid form, has namely carried out overstretching, distortion, slippage and/or other change of shape, as if but can not show liquid characteristic, for example showing, it is properties of materials such as rubber.
Preferably, described thermosetting polyester system between the centre is the unsaturated polyester (UP) system that comprises the ethylenic unsaturated group, and reactive monomer is crosslinked together for this system.
Preferably, described polyester system is to provide the system of adhering to each sheet material (not wishing bound by theory) by following any one or two kinds of mechanism
-with acrylic material in free unsaturated group is crosslinked arbitrarily,
The free monomer solvation of-acrylic material.
Preferably, exist chemical attachment (being described crosslinked) and physical adhesion to adhere to (the free monomer solvation that is acrylic material) simultaneously.
Preferably, described polyester system changes into inviscid form in the interface thermosetting of itself and acrylic material, only has remaining viscosity in the position that exists air to lead to the path of material.Preferably, described material has pliable and tough physical characteristic at ambient temperature.
Randomly, described polyester system comprises one or more pigment (pigmentation), flame-retardant additive and filler.
Preferably, described duplexer is transparent.
Preferably, described acrylic compounds sheet material mixes under about 20 ℃ and/or about 65% humidity and/or solidifies.
In yet another aspect, the present invention relates to a kind of self-supporting duplexer product, it comprises two acrylic compounds thermoplastic plastic sheets, perhaps comprise by the thermosetting polyester system between the centre separate but be attached to the sheet material of the acrylic compounds thermoplastic of described thermosetting polyester system, described polyester system between the centre be some or all or at least
Preferably, one or two sheet material is acrylics, perhaps at least mainly is acrylics.
Preferably, cinnamic content is 35-45% (w/w).
Preferably, the extension at break after described system is solidified is greater than 150% (being preferably greater than 170%).
Preferably, described polyester system by or by radical initiator, for example do not rely on the chemical initiator catalysis of ultraviolet light.Perhaps, it can be by the catalysis of free radical ultraviolet initiator.
Preferably, described polyester system has comprised or comprised slaine provides body, to accelerate gelling time when causing.When using the peroxide radical initiator of MEKP (methyl-ethyl-ketone peroxide) and so on, situation especially like this.
Preferably, the content of described metal salt promoter is same order with the content of arbitrarily such initator, perhaps less than the content of described initator.
Preferably, before heat cure, the content of such initator is not more than 2% (w/w) of system approximately arbitrarily.
Preferably, the content of such initator is less than 1% (w/w) of thermosetting system.
Preferably, stacked being included in of described precursor duplexer arranges the liquid polyesters system between the described sheet material, perhaps at a sheet material this liquid polyesters system is set, and places second sheet material then, makes this system heat cure then.
Preferably, the described mylar system mixture that is following component:
The unsaturated polyester resin that comprises the ethylenic unsaturated group of 45 – 70% (w/w),
The styrene of 30 – 55% (w/w),
Less than the catalyst (for example MEKP) of 2% (w/w),
Less than the initator (for example slaine provides body) of 2% (w/w),
Preferably, described mylar system is mixed in the temperature range of 18-22 ℃ (preferred about 20 ℃).Preferably, described mylar system (preferred 22 ℃) in 20-24 ℃ temperature range is solidified.
Preferably, described mylar system is mixed in the humidity range of 57-67% (preferred about 62%).Preferably, make described resin in the humidity range of 57-75% (preferred 62-73%, for example about 67%), the heat cure by chemistry initiation and heat release thereof.
Preferably the surface with the adjacent acrylics of polyester system is the face of cleaning, does not namely contain from the releasing agent of any emulsion sheet of removing and/or the material of migration.
Preferably, with solvent cleaning was carried out on the surface of sheet material.
Preferably, before the heat cure of polyester system, with isopropyl alcohol to described sheet material will facing to this polyester system the surface clean.
Preferably, described " without any significant degraded " comprises some distortion of every layer, but can not cause with each described polyester system of adhering to mutually any significant disengaging taking place.
Preferably, described duplexer carries out BENDING PROCESS under nondestructive heating condition, in this process, described polyester system between the centre keeps non-liquid state, namely can stretch, distortion, slippage and/or other change of shape, as if but can not present liquid characteristic, for example showing, it is properties of materials such as rubber.
Preferably, described polyester system is to provide the system of adhering to each sheet material (not wishing bound by theory) by following any one or two kinds of mechanism
-with acrylic material in free unsaturated group is crosslinked arbitrarily,
The free monomer solvation of-acrylic material.
Preferably, exist chemical attachment (being described crosslinked) and physical adhesion to adhere to (the free monomer solvation that is acrylic material) simultaneously.
Preferably, described polyester system changes into inviscid form in the interface thermosetting of itself and acrylic material, only has remaining viscosity in the position that exists air to lead to the path of material.Preferably, described material has pliable and tough physical characteristic at ambient temperature.
Randomly, described polyester system comprises one or more pigment (pigmentation), flame-retardant additive and filler.
Preferably, described duplexer is transparent.
Preferably, described acrylic compounds sheet material mixes under about 20 ℃ and/or about 65% humidity and/or solidifies.
In yet another aspect, the invention provides a kind of from supporting Sparent laminate, when all layers with this duplexer are heated to one or more when can not make any layer be melt into the temperature of liquid form, described duplexer can be crooked, described duplexer has between middle and be attached to the transparent polyester system of the transparent thermoplastic layer (these plastic layers are identical or different) of side, and described thermoplastic layer adheres to mutually by following two kinds of mechanism and described polyester system:
-with acrylic material in free unsaturated group is crosslinked arbitrarily,
The free monomer solvation of-acrylic material.
In yet another aspect, the invention provides a kind of from supporting Sparent laminate, when all layers with this duplexer are heated to one or more when can not make any layer be melt into the temperature of liquid form, described duplexer can be crooked, and described duplexer has between middle and be attached to the transparent polyester system of the clear acrylic analog thermoplastic layer (these plastic layers are identical or different) of side.
In yet another aspect, the invention provides a kind of thickness greater than 3 millimeters the Sparent laminate of supporting certainly, when all layers with this duplexer are heated to one or more when can not make any layer be melt into the temperature of liquid form, described duplexer can be crooked, described duplexer has between middle and be attached to the transparent polyester system of the transparent thermoplastic layer (these plastic layers are identical or different) of side, and the thickness of described polyester system is at least 0.5 millimeter.
The thickness of described polyester system can account for the 5-40% of described duplexer gross thickness.
Preferably, in any above-mentioned duplexer, the thickness of described polyester system layer is at least 1 millimeter (preferred thickness is the 1-3 millimeter, for example about 2 millimeters).
Preferably, the thickness of described acrylic compounds sheet material is at least 0.5 millimeter.More most preferred thickness is 0.5-5 millimeter (for example about 2 millimeters).
Described duplexer can be symmetrical, in order to make described acrylic layer (thickness and/or material are paired) in pairs, or asymmetric.They can be asymmetric.
In addition or as an alternative, described duplexer can be three layers, five layers, seven layers or more multi-layered plate of symmetry, perhaps is not.Five layer laminates will have the two layers polyester system layer.
In yet another aspect, the invention provides and a kind ofly (preferably be heated at all layers with this duplexer and one or morely can not make that the random layer fusion is under the temperature of liquid form from supporting transparent flat type duplexer, can make described duplexer bending), described duplexer comprises between middle and be attached to transparent polyester system (i.e. Dui Cheng three coating systems of the clear acrylic analog thermoplastic layer (these thermoplastic layers are identical or different) of side, wherein acrylic layer is symmetrical mutually, also the thickness of preferred acrylic layer is identical with polyester layer, described duplexer system with the imagination version (2 millimeters of the thickness of outside acrylic layer, 2 millimeters of polyester system thickness) Xiang Guan performance is: if the imagination is 960 * 470 millimeters rectangle then on minor axis, the version of this imagination can surpass 40 tons powerful loads and fracture and/or delamination do not take place in edge tolerance.
For instance, the mylar system comprises:
The unsaturated polyester resin that comprises the ethylenic unsaturated group of 45-70% (w/w),
The styrene of 30-55% (w/w),
Less than the catalyst (for example MEKP) of 2% (w/w),
Less than the initator (for example slaine provides body) of 2% (w/w),
Thickness by three layer laminates is 2 millimeters, and 2 millimeters and 2 millimeters, when the minor axis 960 millimeters * 470 millimeters rectangular panel pushed, this panel can tolerate the load of 60-80 ton and delamination does not take place.
Therefore the present invention has imagined and duplexer like such duplexer performance classes, and no matter is to use plane form or curve form.
On the other hand, the present invention relates to a kind of at least three layers Sparent laminate, its gross thickness is greater than 3 millimeters, and wherein the mylar system is as the layer that adheres to separately with two acrylic layer, and described mylar system is between described two acrylic layer.
On the other hand, the present invention relates to a kind of at least three layers Sparent laminate, its gross thickness is greater than 3 millimeters, wherein the mylar system as with two acrylic layer adhere to separately the layer, described mylar system is between described two acrylic layer, described duplexer can bend under the situation of non-destructive heating, forms crooked supporting transparent form certainly.
On the other hand, the present invention relates to a kind of at least three layers Sparent laminate, its gross thickness is greater than 3 millimeters, wherein the mylar system as with two acrylic layer adhere to separately the layer, described mylar system is between described two acrylic layer, and described duplexer is the duplexer of above-mentioned any kind.
In yet another aspect, the present invention relates to the application of above-mentioned arbitrary plane type and/or flexure type duplexer or application process with and the structure of gained.
In one aspect of the invention, provide a kind of duplexer, it comprises:
A) first thermoplastic layer,
B) second thermoplastic layer and
C) thermoset resin layer between described ground floor and the second layer, wherein said thermoset resin layer and two layers are bonding, have crosslinked combination to a certain degree between described resin bed and thermoplastic layer.
Preferably, described thermosetting resin is unsaturated polyester resin.More preferably, described thermosetting resin was the solution of polyester in monomer before solidifying.Preferably, described crosslinked combination is the combination that can be used among monomer and the thermoplastic layer between the unsaturated site of combination.
Preferably, described monomer is styrene.
Preferably, the styrene-content of described resin is 30-45%.
Preferably, the extension at break of described resin〉150%; More preferably its extension at break is about 170%.Preferably, the glass transition temperature of described resin is lower than environment temperature.
Preferably, the styrene in the described resin makes that described thermoplastic layer's surface is softening, makes resin to infiltrate through to a certain extent among the described thermoplastic layer.
In one embodiment, at least one or two described thermoplastic layers are PETG glycol ester glycol (polyethylene terphthalate glycol).In another embodiment, at least one or two described thermoplastic layers are acrylic compounds.
Preferably, when described thermoplastic layer is acrylic material, exist crosslinked between the unsaturated methyl methacrylate in acrylic material and the styrene monomer in the resin.
Preferably, by adding free radical inhibitors resin is carried out catalysis; More preferably carry out catalysis by adding the methyl-ethyl-ketone peroxide catalyst.
Preferably, described acrylic material is polymethyl methacrylate (PMMA) or poly-(2-methyl methacrylate (methyl2-methylpropenoate)); Preferably available from SHINKOLITE (TM) acrylic resin of Mitsubishi artificial silk company (Mitsubishi Rayon Japan).
Preferably, described thermoplastic layer has anti-styrene to a certain degree, preferably has the anti-styrene of height.As an alternative or in addition, described thermoplastic layer has anti-cinnamic face coat.
Randomly, one or more in can be are with the following methods handled described thermoplastic sheets:
-scratch resistance coating,
-sunlight screening additive (after preparation, add, perhaps in preparation, add in the material of resin attitude),
-decorative pattern/etching/embossing/japanning,
-apply photographic imagery coating, transfer coated or mirror surface coating,
-can be with vinyl material and metal material (for example aluminium) bonding and be pressed on the outer surface,
-annealing process.
Randomly, described thermosetting resin can comprise one or more following materials, perhaps with following material described thermosetting resin is handled:
-pigment,
-flame-retardant additive,
-filler.
Preferably, duplexer of the present invention is transparent basically, and TV (total visible light ratio) is near 100%.
Preferably, when described thermoplastic sheets was acrylic material, they mixed under about 20 ℃, the perfusion condition of humidity about 65%, solidified under the condition of about 20 ℃ and humidity about 65%.
In another aspect of the present invention, a kind of method of making duplexer is provided, this method may further comprise the steps:
-the resin precursor material is provided,
-catalyst is added described resin precursor material, with the thermosetting resin of formation catalysis,
-thermoset resin layer of catalysis is inserted between the two layers of thermoplastic layer,
-make that the thermosetting resin (resin) of described catalysis and described two layers of thermoplastic layer are bonding.
Make wherein described resin and thermoplastic layer's step for adhering comprise to make that described resin and thermoplastic layer are crosslinked.
Preferably, the thermosetting resin of the catalysis that forms in the first step is unsaturated polyester resin; Be more preferably the solution of polyester in styrene monomer.Preferably, the styrene-content of described resin is 30-45%.Preferably, the extension at break of described resin〉150%.Preferably, the glass transition temperature of described resin is lower than environment temperature.
Preferably, described adhesion step comprises crosslinked between the styrene monomer in described thermoplastic layer and the described resin.Preferably, described step for adhering also comprises with described styrene makes that described thermoplastic layer's surface is softening, makes resin infiltrate to a certain extent among the described thermoplastic layer.
In a preferred form, described thermoplastic layer is acrylic layer, and described step for adhering comprises crosslinked between the unsaturated methyl methacrylate site of the styrene monomer of described resin and described acrylic material.
In one embodiment, described method is batch process, and described step at insertion one deck resin bed between two thermoplastic layers comprises: pouring liquid state (before gelling or solidifying) resin between the thermoplastic sheets of two supports into, and making its curing.
In another embodiment, described method is continuity method, the described step of inserting one deck resin bed between two thermoplastic sheets comprises that making first sheet material of resin or layer advance passes through lamination station, at this station, at least one, preferred two described thermoplastic layers and described resin sheet or layer contact.
In a kind of form of embodiment, described resin is the pregel attitude.
In the another kind of form of this embodiment, described resin is the gel state, is in or near the state of resin gelling.
In the another kind of form of this embodiment, described resin is solid state, the described step that makes resin advance can be included in before the lamination station, near lamination station point or after the lamination station, described resin and/or one or two thermoplastic sheets are heated, make described resin and/or one or two thermoplastic sheets softening at least.
In yet another aspect, provide a kind of laminate material of making according to said method.
In another aspect of the present invention, a kind of method of making crooked laminate material is provided, this method may further comprise the steps:
-the duplexer that duplexer mentioned above is provided or makes according to said method, the extension at break of wherein said thermosetting resin〉150%, glass transition temperature is lower than environment temperature,
-shaped region of described duplexer is heated to forming temperature,
-described duplexer is shaped to required curvature,
-described duplexer is cooled off,
The wherein said step that the shaped region of duplexer is heated comprises that basically all layers (comprising thermoset layer and thermoplastic layer) to duplexer in the shaped region heat.
Preferably, the described step that shaped region is heated comprises from end face and the bottom surface of shaped region inner stacks body shaped region is applied heat.
Preferably, the condition of described heating steps (comprising forming temperature and in the duration of heat one or two) is not enough to make arbitrary layer of duplexer in the described heating region to anneal.
Preferably, the described step that shaped region is cooled off comprises and makes described duplexer be cooled to environment temperature.
Preferably, the described step that duplexer is formed comprises base material placed on mould or the template, to one or more zones of the duplexer adjacent with shaped region exert pressure (can only be gravity).
In yet another aspect, provide a kind of laminate material or goods of bending of making according to said method, perhaps combined the goods of crooked stacked body region.
Definition
In this article, term " and/or " expression " with " or " or ", perhaps comprise both of these case simultaneously.
In this article, add plural number and/or the singulative that " one or more " represent this noun simultaneously in the noun front.
In this specification and claims, term " comprise " expression " at least part of by ... form "; That is to say that when explanation contained the specification of " comprising " and the statement in claims, can also have this term in each statement was feature beyond that of beginning explained.Relevant term was also explained with similar mode as " comprising " and " containing ".
In this article, can clearly find out, comprise chemistry polymerisation that cause and/or that ultraviolet light causes between unsaturated polyester resin and its ethylenic unsaturated group and the coreactivity monomer about " thermosetting " of polyester system.In case such heat cure has taken place, even remain pliable form (when not containing surrounding air, being non-sticky preferably), but described material still can deform under described heat cure acrylic material sheet material is shaped the temperature (namely being higher than environment temperature) of required or selected rising again, and any duplexer can not the take place remarkable degraded of (comprising adhering to of polyester system and acrylic material).
In this article, term " (making) bending " (with and subform arbitrarily, for example " bending " or " bending ") comprise that any precursor duplexer three-dimensional structure that can make departs from the mechanical treatment of its plane duplexer, the for example bending of arbitrary shape, any protrusion, fold arbitrarily etc., comprise the only crooked or whole bending of a part of whole precursor duplexer sheet materials.
In this article, a kind of plane or crooked sheet material preferably represented in term " duplexer ", and wherein outer sheet material (for example thermoplastic sheets) and the polyester system material between the centre extend basically jointly.But, situation not necessarily so in some applications, that is to say that if necessary, outer sheet material can not match each other, and/or one or two outer sheet material is with respect to the scope between the polyester system of centre, for example, if necessary, the some parts of total duplexer can be so that an outer sheet material be directly fixed on another, and in other zone of total duplexer, then have the polyester system between these sheet materials.
In this article, any method that can change sheet form of term " shaping " expression includes but not limited to make sheet material bending, moulding, stretching, compression, bending or arches upward.
In this article, term " anti-styrene " expression thermoplastic sheets can tolerate the ability of cinnamic corrosiveness/etch.May be dissolved or be dissolved in cinnamic ability by styrene with the sheet material opposing relevant.For example styrene is present in a kind of preferred thermoplastic resin.
In this article, term " transparency " expression allow that light is not distorted by window, loss of clarity or change the propagation of light.
In this article, term " mist degree " expression darkness or turbidity.This may take place owing to resin is incompatible with outer sheet material.For example the inner surface of sheet material may be subjected to stress, can react by its surface isolation, can cause complete delamination under serious situation.
" elongation " or " extension at break " be sample damage or fracture before tensile amount as the gauge of its initial length percentage.
About " glass transition temperature " of resin expression resin the temperature of reversible variation takes place, under this temperature, resin changes flexible or flexible state quite suddenly into from hard, glassy state or crisp state.
Brief Description Of Drawings
With reference to the accompanying drawings, the present invention is only described by way of example, in the accompanying drawing:
Fig. 1: the end perspective view that is the Sparent laminate made of principle according to the present invention;
Fig. 2: the end perspective view that is the transparent multilaminar plate made of principle according to the present invention;
Fig. 3 a, 3b, 3c: be to use the present invention obtainable curved shape, bellows-shaped and 90 ° of angles after the hot forming step.
Fig. 4: be before the laminated sheet hot forming, the characterization of molecules figure of unsaturated polyester resin;
Fig. 5: be that laminated sheet is thermoformed into after a kind of required form, the characterization of molecules figure of unsaturated polyester resin;
Fig. 6: the figure of resin material that is the fire-retardant and foaming of display application;
Fig. 7: be a kind of preferred hot forming heating process;
Fig. 8 a, 8b, 8c: the side view that is the anchor clamps of Fig. 3;
Fig. 9 a and 9b: a part that has shown the technology of embodiment 3;
Figure 10: shown owing to resin is inhaled into the delamination that wrong rubber-like dam sealer (dam seal) causes;
Figure 11: the situation that display light is propagated in duplexer of the present invention;
Figure 12: the form that shows a kind of continuous manufacturing.
Detailed description of the invention
The present invention relates to a kind of laminate material, it comprises the thermoset resin layer between two-layer or more multi-layered thermoplastic sheets.Preferred thermoplastic sheets is acrylic material or PETG glycol (P.E.T.G.).
Fig. 1 has shown a kind of such duplexer, and it has the outer sheet material 1 of acrylic material or P.E.T.G., and the internal layer 2 of resin.The thickness of the duplexer when finishing can be according to the thickness that inserts the resin between the described thermal plasticity slice, and the quantity of employed thermoplastic sheets and resin and thickness and change.Fig. 2 has shown so a kind of multi-layer laminate.
We have carried out some trials, use various forms of plastic sheets and protective cover that duplexer is provided.Be for the substitute as glass although develop the present invention at first, be used for building and building industry, in light weight owing to laminate panel of the present invention, intensity is high and can be shaped, so the present invention has various application.For example, described panel can be shaped or process to build hull, vehicle structure (comprising monocoque assembly and outer panels), furniture, household electrical appliance and many kinds and make commodity.Therefore should be seen as building and manufacturing material.
An embodiment the simplest of laminate material of the present invention is the individual layer thermosetting polyester resin (as shown in Figure 1) that is clipped between two layers of thermoplastic acrylic material or the P.E.T.G..
A kind of method of preferred manufacturing duplexer sheet material is continuous manufacture, and this method is put two sheet materials together, injects unsaturated polyester resin under the required correct temperature and humidity condition of the solidification process of unsaturated polyester resin.Described resin is bonding with outer sheet material.A kind of other manufacture method is batch process, and this method comprises two outer sheet materials are assembled in anchor clamps or the of equal value utensil in the mode that be arranged in parallel, then resin is poured into or is injected between the described sheet material.
Another kind method is that described resin is made sheet-form or the conitnuous forms with desired thickness.Described continuous resin can be rolled then, preserve at cylinder, can be used at any time introducing in the manufacturing process.After ready, can heat two outer thermoplastic sheets, be pressed on any side of the resin (it can heat) that solidifies, form the solid lamination.Therefore must be to bonding control the between described resin and the sheet material.
Another aspect of the present invention relates to and a kind of duplexer being formed or the method for moulding, and the ability of duplexer to be formed.In case made duplexer, just be heated to subsequently and can form or the temperature of moulding it, then described duplexer is shaped or is formed into required curvature and configuration.The present invention includes with single and complicated curvature duplexer is formed.Fig. 3 a, b and c have shown the example of possible warp architecture.
A) thermoplastic sheets
The preferred outer sheet material of described duplexer can be acrylic compounds or P.E.T.G. sheet material.
Acrylic compounds is represented the material be made up of molding and hot formed various transparent thermoplastic resin, and described resin is made by acrylic material and derivative thereof, and is made by natural material source (for example oil and natural gas).P.E.T.G. represent glycol-modified terephthalate ethylene glycol (glycol-modified terephthalate glycol).
When a kind of preferred thermosetting resin comprised styrene, above-mentioned all materials preferably itself all had cinnamic chemical resistance.The sheet material of anti-styrene deficiency (being dissolved in styrene or cracked sheet material when namely contacting with styrene probably) obtains the adherence of difference, the destruction that also can cause sheet surface easily owing to corrosion reaction takes place will carrying out bonding contact-making surface.
A kind of alternative method for anti-styrene condition be at sheet material with before resin contacts, apply anti-styrene coating at sheet material.This is a kind of protective finish as the barrier layer between described sheet material and the resin, and this is that those skilled in the art can expect.
Compare with P.E.T.G, the acrylics sheet of standard is a kind of more cost-efficient material, and it has good optical character, and scratch resistance is relatively poor.In addition, the crosslinking degree of acrylic material structure is more little, more is applicable to duplexer of the present invention because as mentioned below, free methyl methacrylate site can with resin crosslinks.But all material of use all comprises within the scope of the present invention.Described duplexer can comprise two-layer (or more multi-layered) acrylic material; Perhaps two-layer (or more multi-layered) P.E.T.G.
B) resin material
Those skilled in the art can understand, and have many thermosetting resins two thermoplastic sheets can be bonded together.But, be applicable to that the resin of duplexer of the present invention must have following characteristic
-unsaturated polyester resin
-extension at break characteristic is enough to allow described duplexer hot forming.Preferred elongation surpasses 150; More preferably elongation approximates or greater than 170%.
-lower glass transition temperatures, it is lower than environment temperature.
-preferably use styrene as monomer.Preferred styrene-content is 40-45%.Most of mylar is by the viscosity of the solution composition of polyester in monomer, the liquid of light color.The styrene addition is up to 50% viscosity that can reduce resin, will help to make that resin is easy to handle.Described styrene also can play an important role, and namely can get up by the strand " crosslinked " with polyester, makes resin become solid-state from liquid curing, can not produce any accessory substance simultaneously.For this duplexer invention, we think that styrene also has makes the thermoplastic layer of outer sheet material soften, thereby helps the effect of described adhesion process.For the acrylic compounds sheet material, styrene can also be crosslinked with undersaturated methyl methacrylate site.
-for the application in molding, add some supplementary prods and will be of value to mylar.Specifically, need catalyst among the present invention.Catalyst uses soon and not long ago added in the resin system, with initiated polymerization.Catalyst can not participate in chemical reaction, and only makes this process activate.Also can use promoter to accelerate described solidification process.
When adding catalyst, in the presence of cinnamic, in polymerization process, styrene can make that polymer chain is crosslinked, forms complicated tridimensional network.Here it is solidification process.
Before carrying out molding, carry out resin compound preparation time, need in addition careful.Must carry out meticulous stirring to resin and any additives, make to add before the catalyst that all components are disperseed equably.This stirring must be abundant, because any air in the introducing resin compound all can influence the quality of final moulded work.When carrying out with layers of reinforcement stacked the time, fully stir with regard to particular importance, because otherwise can form bubble in the duplexer that makes, this can make the intensity of structure reduce.Another very important aspect is amount adding promoter (if you are using) and the catalyst with careful measurement, with the control polymerisation, obtains best material character.If catalyst amount is too much, can cause gelling too rapid, I haven't seen you for ages causes curing not enough and catalyst amount is crossed.
A kind of cinnamic alternative monomer is methyl methacrylate.This is also included within the scope of the present invention.
Preferred resin
A kind of preferred resin that we use is the NC007 resin.This is a kind of flexible, low viscosity, transparent unsaturated polyester resin in styrene monomer.It preferably promotes (prepromoted) (namely be pre-mixed, prepare burden in batches) in advance before adding catalyst.Our recommendation should use the MEKP catalyst of the medium activity of 0.75-2% to carry out gelling and curing.MEKP (methyl-ethyl-ketone peroxide, a kind of radical initiator) is the catalyst that adds mylar and vinyl ester resin.Because catalyst and mixed with resin, chemical reaction (as indicated above) takes place, produce heat, make resin solidification (sclerosis).
NC007 typical liquid character:
| Viscosity at 25 ℃ | 1.5ps |
| Gelling time under 25 ℃, 1%MEKP | 45 minutes |
| Volatile content | 36% |
| Outward appearance | Transparent baby pink |
The NC007 representative physical properties:
| Extension at break % | 170% |
| Hot strength | 3.2mPa |
Performance and the feature of this resin in the hot forming process is very important for the success of duplexer.
The percentage elongation % ability of our preferred resin approximates or is higher than 150%.The extension at break of this specific resin is about 170%.It must work at 105-120 ℃.Under these temperature, we observe malleability and increase, make molecular energy stretch, fixing, can keep its elongation and bonding with sheet surface after the cooling.This can be referring to Fig. 4 and Fig. 5.Fig. 4 shows the laminate construction before being shaped, and it comprises resin 41 and thermoplastic layer 42.
(a) in heating process, along with the duplexer product malleability that becomes is higher, molecular resin begins to change shape and expansion.When beginning heating process before shaping and the forming process, along with the duplexer bending forming, the molecular structure of the internal resin in the duplexer changes shape, becomes more elongated form from circular and honeycombed, along the surperficial elongation of duplexer.
(b) when the temperature of all layers reaches required 105-120 ℃ forming temperature, begin to form.The time that temperature begins to produce required infiltration will be depended on the thickness of the lamination of shaping.Resin 41 when Fig. 5 has shown heating and thermoplastic layer 42 structural change.
Described product can carry out stacked, experiences the hot forming process then, and this process comprises final products are heated, crooked or be configured as shape arbitrarily, the cooling back keeps its shape, can not cause delamination and loss of tensile strength simultaneously, and this is a surprising result.Environment and factor in order to ensure the necessary control of forming process success make the duplexer product just in time change molecular structure in the correct time, realize forming successfully and don't infrastructure product together.
The catalyst that is used for resin solidification
As mentioned above, need to use catalyst to make resin solidification.It is as the initator that makes resin solidification.Being suitable for general catalyst type of the present invention is radical initiator, preferred MEKP (methyl-ethyl-ketone peroxide catalyst).A kind of catalyst that we have successfully used is catalyst (MEKP40%) QC of our numbering F00826.This is a kind of MEKP catalyst that comprises following composition:
| Repefral/DPG passivator (phlegmatiser) | 30-70% |
| Methyl-ethyl-ketone peroxide | 30% |
| Methyl ethyl ketone | 0-10% |
| 2,4-pentanedione peroxide | 0-10% |
Its SADT (SADT) is about 60 ℃.
Gelling and hardening time; Step
Gelling time represents that catalyst and resin have changed the moment of half-hard state at least or stable state into from unsettled liquid state.If the bonding early part of curing or (with outer sheet material) is interfered, then may cause final delamination.Yet, in the process in gelling stage, for some time, at this moment can handle, cut and store sheet material before solidifying fully, be used for complete hardening time.It is important sheet material not to be lifted, crooked or make its pressurized, but make sheet material along the smooth bed surface of ventilation or smooth banded loading bay/conveyer slides and mobile.
The hardening time-expression catalyst and resin solidify fully, has been bonded in the moment on the sheet surface fully.
The time of solidifying fully and solidifying will be depended on the manufacturing process of employing.By making the amount maximum of catalyst and/or promoter, and the NC007 system is heated, will significantly accelerate hardening time.But no matter use which kind of method, the period of storage before recommending to use is 12 hours.
C) preparation of duplexer
As indicated above, the method for three kinds of main manufacturing duplexers of the present invention or similar duplexer is arranged.A kind of batch process (for example using anchor clamps that sheet material is held in place), a kind of continuity method, in production line, resin is poured into or added between the sheet material, perhaps use three solid sheet materials (two thermoplastic and resin), in heating, they are placed in contact.Shown batch process among the embodiment.Usually in batch process, use the blade of mechanical assistance with the catalyst mix of a certain amount of resin and respective amount.It was stirred 2 minutes, it was left standstill 2 minutes, perhaps vibrate, to remove excessive air bubble.Then this formulation is directly poured in the cavity sample that remains in the support, used the funnel that thin brass screen is arranged further to help to mix, help further to remove the air bubble that is mingled with.
A kind of continuity method of form is shown in Figure 12.This comprises premixed resin is applied two outer thermoplastic sheets.Its version comprises (still runny) resin that use simply is pre-mixed; (glue) resin that partly solidifies and the resin that solidifies fully heat it then, make it softening, apply then.The resin 121 that partly solidifies and the crust 122 of rolling have been shown among the figure.Described duplexer continues to arrive portable crawler belt pressure plare 124 by pressure roller 123.Outward flange dam rubber or crawler belt rotation outward flange seal is (is used for prevent liquefy in the manufacture process resin overflow) chosen wantonly.
Should be noted that the thermoplastic sheets that manufacturer provides often has protection plastic sheet or protection sheet.These protection plastic sheets or protection sheets can be on a face or two faces.They should be removed before the preparation duplexer.
D) bonding between acrylic material/P.E.T.G and the resin.
As mentioned before, bonding between the resin is the important feature of the present invention.In preferred embodiment, described resin comprises the styrene-content of 30-45%.This styrene plays an important role in preferred bonding formation.Do not wish to be subject to following theory, we think that the styrene that exists can make resin can carry out certain infiltration so that outer thermoplastic layer's surface is softening.In addition, we think that it can be crosslinked with outer thermoplastic layer, produce bonding.For example, for the outer sheet material of acrylic compounds, the styrene monomer of described resin can be crosslinked with the methyl methacrylate site of any remnants of acrylic material.
(e) bending/shaping of duplexer
Hot forming or the method for forming are a kind of preferred manufacturing process.It comprises by required heat being concentrated on specific zone rather than the system with whole sheet material is carried out baking oven heating, and makes smooth duplexer sheet material be configured as required shape.Therefore, the specific region of described sheet material can bend at a certain temperature/be shaped, and under this temperature, described acrylic material or P.E.T.G can soften, described unsaturated polyester resin changes consistent, makes panel or sheet material can be configured as required shape.
In general, in the art, form by the bar shaped shaping.This comprises that facing sheet material from one heats, and relies on radiant heating source, makes described heating source by whole sheet material before bending.
For the non-laminated sheet of the standard of routine, described one-sided heating is effectively and acceptable.But, for the not preferred this method of our duplexer (but still can adopt under certain conditions).
The temperature and time that need to see through our laminated sheet sample is very crucial, because if temperature is too high, overlong time, the annealing process that occurs may take place not wish.With the side generation annealing effect that is heated that required time of our laminated sheet of rod/see through when heating from a side and temperature may cause sheet material that is shaped of single fire-bar, cause that outer sheet material cracks, chip or fracture, make and in forming process, cause delamination by the sandwich layer cracking.We adopt simultaneously the thermal source that heats from top and bottom, make it possible to deeper penetrate the core of lamination.For specific stepped construction, can need certain temperature and time to obtain suitable malleability, prevent that the sheet surface from annealing and delamination and defective taking place.Therefore it is important not surpass correct forming temperature and the time.
F) Ren Xuan feature
I) antiscratch coatings (Marcoating)
Can use optional antiscratch coatings to improve wearability or chemical resistance.Although the duplexer of dual coating (namely applying in the outside of duplexer) can provide maximum protection, for the application of a side of a contact sheet, the duplexer of one-sided coating can provide advantage economically.
Ii) UV protection
We can comprise in described thermosetting resin that the UV inhibitor is to improve the anti-UV of duplexer.Described anti-UV performance enough improves described duplexer as the performance (object in the protection building) of construction material, but also can prolong the life-span of duplexer self.
Iii) color/painted/transparent
Can be by using colored or painted thermoplastic sheets, for duplexer provides colour/painted incrustation.Can make opaque and translucent duplexer by suitably selecting sheet material.Perhaps can use transparent thermoplastic sheets, we can carry out painted or dyeing to thermosetting resin, and this is well known by persons skilled in the art.Can carry out painted to resin compound with pigment.Even the addition of pigment only is about 3 weight % of weight resin, also must carry out careful consideration to the selection of suitable paint material, because pigment is easy to influence curing reaction, use inappropriate pigment can make the quality of final duplexer descend.
Iv) fire retardant
As shown in Figure 6, fire proofing can be added in the thermosetting resin 60, described thermosetting resin 60 is clipped between the outer thermoplastic sheets 42.But the possibility of result of doing like this can cause transparency to descend.
V) filler
For comprising following a variety of causes, we can also use packing material in resin:
-in order to reduce the cost of moulding article
-in order to promote moulding technology
-in order to make moulding article have specific character
The addition of filler is up to 50% of weight resin usually, but such addition can influence flexural strength and the hot strength of duplexer.Use filler can be of value to the stacked or casting of thick parts, otherwise significant heat release heating may take place.Add some filler and also help to improve the anti-flammability of duplexer.
Vi) other possibility
For the requirement in the building industry and needs attractive in appearance, can be with other vinyl-based, metal decking, for example aluminium sheet and flame-retardant materials combination and be pressed on the skin of described resin sheet.We can also be arranged on converter (transfer), goods and object (for example solar energy acquisition panel (solar pick up panel)) within the resin formulation within the cavity, make solar energy window plate (solar glazing panel).
(g) advantage of duplexer of the present invention
With the glassy phase ratio, a preferred embodiment of duplexer sheet material of the present invention provides following one or more advantages:
Improved optical clarity
Be easy to make
Wearability
In light weight, weight only is half of glass
Chemical resistance
Intensity, with the glassy phase ratio, impact strength improves
Improved sound insulation
Machinability-can be expertly with sawing cut, brill and matching plane
Hear resistance
The hot forming ability
H) blue effect/muddiness (Blue effect/Hazing)
Sometimes the product duplexer may have muddiness or blue stripe (lining).This is a kind of owing in following three kinds of reasons often:
1) because the refraction effect that the fibre optics effect of sheet material and formulation causes for example when the edge of described sheet material is subjected to illumination, can absorb light, make light propagate (seeing Figure 11) along the length of sheet material.When solidifying, if there is significant distortion in sheet surface outside, perhaps the complications of light propagation path then can cause internal reflection, cause the outward appearance of smoke-like azury.
2) incorrect catalyst mixture may cause the internal cavity formulation to present muddiness, rather than has the anaclasis character identical with the acrylic compounds sheet material, and this also can cause internal reflection.
3) also may make that the internal cavity sheet surface is polluted slightly owing to there is the not anti-styrene of certain percentage.
Blue muddy remedial measure:
Can the outward flange of sheet material be sealed, with propagation against sunshine;
Guarantee the smooth surface that anchor clamps or other permanent plant result are formed for solidifying;
Guarantee to use correct catalyst mix percentage
Guarantee correct sheet material/styrene percentage
Use the translucent tone of certain limit.
Test
Embodiment 1-preferred prescription
(Mitsubish Rayon, that Japan) produces is called as Shinkolite to use Mitsubishi artificial silk company
TM300 millimeters * 300 millimeters succeeding vat die casting mould the sample of acrylic material.They are in position in case distortion is set in 30 degree angles and pours in anchor clamps, make any air bubble to rise.Can apply vibration to accelerate the release of any air.
Resin and mixture of catalysts are as follows:
In the solidification process that carries out in heating cabinet, described sample potting compound can keep vertical in anchor clamps.Perhaps can stop up and enter hole (being used for filling the hole that enters of material), sample keeps flat then, is used for solidifying at heating cabinet.
In general, sample should be placed earlier at least 8 hours, handled then.In order to accelerate this process, can adopt the back to solidify.
Back curing can be that certain hour prepares catalyst in resin before perfusion, and gelling time is suitable when make introducing cavity, and can not cause on the platform gelling time in the sheet material long, thereby delays speed of production.Ideally, when this process continuously when mobile sheet material carries out, described sheet material should can cut into certain-length and storage at any time in the gelling stage about 5 meters after.The catalyst of sheet material and resin is more many more many with heating in filling process, and also will significantly accelerate hardening time.We can also add gelling promoter.
Cleaning and the preparation of embodiment 2-sheet material cavity side
Because some manufacturers can apply the pollution that may bring with the various adhesives of protecting outer packing plastic to use, may must carry out this step operation.In simple terms, remove adhesive glue with suitable cleaning agent.We had used methylated spirit (industrial alcohol and family expenses alcohol), but found that isopropyl alcohol is most preferred.Preferred cleaning agent will depend on the different housing materials that different manufacturers use.
Perhaps, we use does not have protective finish or the sheet material of only single face use or acrylic compounds sheet material or the P.E.T.G. sheet material of roll form.Described protective finish will be stayed the outside (being that the side that sheet material contacts with resin does not have protective finish) of duplexer sheet material.
A kind of resin that is preferred for the duplexer manufacturing is our NC007 resin.This is a kind of styrene unsaturated polyester resin of dissolving.
Following table B has shown that we pour into the perfusion Study on Conditions of this resin to P.E.T.G. and acrylic compounds sheet material.
Size: 300 millimeters * 300 millimeters * 2 millimeters thick
The temperature of specimen sheet material, mixing and time
(all samples all clean with methylated spirit)
Fig. 9 a has shown the end-view of perfusion equipment.Outward flange sealing/dam rubber is to be made by the wide 25 millimeters closed pore pvc foam seal band 91 with single adhesive surface.After having prepared 300 millimeters * 300 millimeters sample sheets (acrylic material or PETG make) 92 and cleaning, described band is launched, cut into certain length, remove boundary belt from a side, expose adhesive.Then band 91 is centered on the outer edge setting of described sheet material 92 with binder side form down.The junction of band 93 on the angle need seal with the polyester compatibility sealant of Soudal High Tak sealant or equivalence.Then Soudal High Tak sealant is put on the exposed end face of described pvc band, for top-sheet provides adhesive seal.
It is very important escaping for potting resin and air in gap 94 between two drift angles.Described dam rubber must can be compatible with the resin formulation, otherwise resin can infiltrate in the dam seal, makes resin leave described sheet material along outward flange, causes delamination, as shown in figure 10.Figure 10 has shown because resin immerses in the rubber dam seal 99, has caused delamination and the air gap 98.
When mixing, need carefully, mixing machinery device speed can not be too fast, otherwise can make that inflation too much if this thing happens, then needs to spend a period of time to make bubble transfer to the surface, just otherwise need curing mechanism is vibrated in the formulation.
When pouring into, a spot of air may enter in the formulation, when bubble rises to the surface, sometimes outer peripheral bubble may be attached to the lateral edge of rubber, this can't throw into question, because the edge can be cut away after solidifying, the bubble in the sheet material can not cause delamination or pollution, but damages attractive in appearance.
Referring to Fig. 8 a, b and c (sectional view, side view and perspective view) have made chuck apparatus 80 and have been used for all samples.This makes sheet material 81 to fix abreast, and resin pours into from the top.
Described anchor clamps are made with the acrylic resin sheet material 81 of 15 millimeters thick, and are with 10 millimeters ribs, 82 horizontal supports, in position with nut 83.The outward flange that it is important anchor clamps can not tension, otherwise will show the outward appearance of concave surface on the final product, causes sample to have visible distortion.
Embodiment 4-annealing
Discuss as preamble, the anti-styrene of outer thermoplastic sheets is an important feature of the present invention.We preferably invent and use the sheet material with intrinsic anti-styrene.But, can also before being combined into duplexer, anneal to sheet material, make it have anti-styrene.
Following Table A relates to the annealing of the sample sheets of the acrylic compounds sheet material that is derived from various plastic sheet manufacturer and PETG sheet material, sample sheets be of a size of thick 3 millimeters * long 150 millimeters * wide 75 millimeters, with the isopropyl alcohol cleaning, place on the smooth non-sticky surface of cold baking oven then.Some samples are placed between the sheet material, in case bubble or distortion.They are heated to described condition, it was cooled off in 1 hour time.
And then sample cleaned, dam rubber being put on outer edge seal, (under specific humidity and temperature conditions) perfusion resin formulation NC007 places the environment of predefined control temperature and humidity then, makes completion of cure.
Table A
Preferred sheet material is the Shinkolite available from Mitsubishi artificial silk company.
Generally, the cracking situation of sample obtains significantly to improve.The result of annealing research shows can make it have anti-styrene.But it is low to do efficient like this, and this method cost height.Although be within the scope of the invention therefore, annealing is not preferred step or feature.
The shaping of embodiment 5 – duplexers/folding
We have tested a large amount of different combinations, measure their hot forming ability.The internal cavity barrier layer that a kind of preferred duplexer is outer by two opposed 2 millimeters acrylic compounds sheet material and 2 millimeters resin formulations form is formed, and their formation is 6 millimeters sandwich material altogether, and perhaps laminated material is for testing.The acrylic compounds sheet material that uses is Shinkolite (Mitsubishi artificial silk company), but other supplier also can provide suitable acrylic material.Described internal cavity material is made up of the unsaturated polyester resin formulation of the catalyst that comprises 0.75 (w/w), and for example every liter of resin formulation comprises 7.5 gram catalyst, forms described sandwich/laminate samples, and gross thickness is 6 millimeters.
Four samples that prepared 300 millimeters * 300 millimeters * 6 millimeters thick.The sheet material of pre-perfusion pours into 6 hours hardening times, gel setting time 1 hour under 20 ℃ of room temperatures, 65% humidity.Sheet material places the atmosphere of the control of sealing, and temperature sets in advance at 20 ℃, and humidity is 65%.
We attempt accurately to make the optimum temperature by the obtainable maximum curvature of heat forming technology.
Equipment: smooth bed fan baking oven, have the flat bottom flaggy of inner teflon net, in case contingent bonding with oven interior of test products also has sealed glass and observe door, be used for observing.
Method: sample faced down to be placed on the teflon baking oven bottom, and the oven temperature of preheating is 110 ℃, heats 10-12 minute.
Use the hand of wearing mitten to pick up sample sheets then and carry out angle (corner) test.When the edge is in the malleability stage, flat scraper is slided into below the laminated sheet, it is shifted out, in case distortion and unnecessary excessive movement in advance take place.
Manufacturing process: at first make the shaped structure of various lamination MDF sheet material bending, will place from the sheet material that baking oven takes out on the estrade then, when sheet material was held and is processed into selected shape like this, mobile chance was limited.In order to make the breakdown point of the maximum and discrimination test of stress, employing 45 and various acute angle (various degrees ofshapness) when crooked.
Sheet material with heat directly places on the mould then, forms with hand operated, obtains the general shape of mould, then after stage carry out clamping, fixing, original position is solidified, and solidifies again.This is shown among Fig. 7.Thermal source 71 is the two-sided thermals source that put on duplexer 70.For our duplexer, the single face heating is undesirable.
Forming results:
Do not ftracture
Under the situation that is not having pressure forming and force to be shaped, make sample sheets form and when keeping anticipated shape, only at the center with along outward flange generation delamination.
The result: we find under all situations of using serious crooked (being equal to or greater than 45 degree), need make lamination form and outside fully combine closely in the same manner, sample sheets is suppressed between identical outside sweep, therefore make sample sheets form cavity between outer mold, the pressure of 2000 (2kilos) is enough.Preferably before the demoulding, suppress 12-15 minute time.
Related to main points or the whole place with known equivalent technique at above description list of references, these contents of equal value also all are included within the present invention, list separately as these contents.
Although the mode with embodiment has been described the present invention in conjunction with the specific embodiment, should be appreciated that and under the prerequisite that does not deviate from the scope of the invention or spirit, to improve and/or to improve.
In addition, when describing feature of the present invention or aspect according to Ma Kushi group (Markush group), it will be recognized by those skilled in the art that the present invention also can describe the present invention according to arbitrarily independent part or subgroup among the described Ma Kushi group thus.
Claims (38)
1. duplexer product that comprises at least one bending area from supporting, described duplexer product comprises,
Two or multi-disc acrylic compounds thermoplastic plastic sheet more, perhaps comprise and separated by the thermosetting polyester system between the centre but be attached to the sheet material of the acrylic compounds thermoplastic of described thermosetting polyester system, the extension at break of described thermosetting polyester system is greater than 150%
Described bending area forms in the following manner: from two surfaces of described duplexer shaped region is applied heat, the layer arbitrarily that is heated to the duplexer product that can not make that described shaped region is interior is fused into the temperature of liquid form, can not produce delamination and loss of tensile strength simultaneously.
2. product as claimed in claim 1 is characterized in that, described heated perimeter is 105-120 ℃.
3. product as claimed in claim 1 or 2 is characterized in that, one or two sheet material is acrylics, perhaps at least mainly is acrylics.
4. product as claimed in claim 1, described polyester system is at least part of to be made by following component: (A) carboxylic acid or dicarboxylic acids, one or more provide hydroxyl and/or dihydric component with (B).
5. product as claimed in claim 4 is characterized in that, described thermosetting polyester system comprises the coreactivity monomer.
6. product as claimed in claim 5 is characterized in that, described coreactivity monomer is styrene or styrene derivative or analog.
7. product as claimed in claim 5, described coreactivity monomer is styrene or styrene analog, its content in the polyester system is 30-55% (w/w).
8. product as claimed in claim 7 is characterized in that, cinnamic content is 35-45% (w/w).
9. product as claimed in claim 1 is characterized in that, described elongation is greater than 170%.
10. as claim 1-2, each described product is characterized in that among the 4-8, and described polyester system is that content is the mylar that comprises the ethylenic unsaturated group of 45-70% (w/w).
11. as claim 1-2, each described product is characterized in that among the 4-8, described polyester system by or by radical initiator catalysis.
12. product as claimed in claim 11 is characterized in that, uses peroxide radical initiator.
13. product as claimed in claim 12 is characterized in that, described initator is MEKP, i.e. methyl-ethyl-ketone peroxide.
14. product as claimed in claim 13 is characterized in that, comprises metal salt promoter.
15. product as claimed in claim 11 is characterized in that, before heat cure, the content of such initator is not more than 2% (w/w) of polyester system approximately arbitrarily.
16. product as claimed in claim 15 is characterized in that, the content of such initator is less than 1% (w/w) of thermosetting system.
17. as claim 1-2, each described product among the 4-8, it is characterized in that, the lamination operation of described duplexer is included between the described smooth sheet material liquid polyesters system is set, perhaps at a smooth sheet material this liquid polyesters system is set, place the second smooth sheet material then, make this system heat cure then.
18. product as claimed in claim 17 is characterized in that, described mylar is the mixture of following component:
The unsaturated polyester resin that comprises the ethylenic unsaturated group of 45 – 70% (w/w),
The styrene of 30 – 55% (w/w),
Less than the MEKP of 2% (w/w) and
Slaine less than 2% (w/w) provides body.
19. product as claimed in claim 18 is characterized in that, described mylar system is mixed in 18-22 ℃ temperature range.
20. product as claimed in claim 18 is characterized in that, described mylar system is solidified in 20-24 ℃ temperature range.
21. product as claimed in claim 18 is characterized in that, described mylar system is mixed in the humidity range of 57-67%.
22. product as claimed in claim 18 is characterized in that, makes the heat cure in the humidity range of 57-75% of described resin system.
23. product as claimed in claim 18 is characterized in that, the acrylics adjacent with the polyester system or the surface of any acrylics are the faces of cleaning, namely do not contain from the releasing agent of any emulsion sheet of removing and/or the material of migration.
24. product as claimed in claim 23 is characterized in that, with solvent cleaning is carried out on the surface of described sheet material.
25. product as claimed in claim 24 is characterized in that, before the heat cure of polyester system, will clean facing to the surface of this polyester system this sheet material with isopropyl alcohol.
26. as claim 1-2, each described product among the 4-8, it is characterized in that, in BENDING PROCESS, described polyester system between the centre keeps non-liquid form, namely carried out overstretching, distortion, slippage and/or other change of shape, but can not show liquid characteristic, describedly can not show liquid characteristic and refer to show it and be the characteristic of elastomeric material.
27. as claim 1-2, each described product is characterized in that among the 4-8, described product is transparent.
28. as claim 1-2, each described product is characterized in that among the 4-8, the thickness of described polyester system layer is at least 0.5 millimeter, accounts for the 5-40% of duplexer gross thickness.
29. product as claimed in claim 28 is characterized in that, its thickness is at least 1 millimeter.
30. the Sparent laminate of supporting certainly product with at least one bending area, described duplexer product has transparent thermosetting polyester system, the extension at break of described transparent thermosetting polyester system is greater than 150%, described thermosetting polyester system is between middle and be attached to the transparent thermoplastic layer of side, the transparent thermoplastic layer of described side is identical or different, and described thermoplastic layer adheres to mutually by following two kinds of mechanism and described thermosetting polyester system:
-with acrylic material in free unsaturated group is crosslinked arbitrarily,
The free monomer solvation of-acrylic material;
Wherein each thermoplastic layer is acrylic material or PETG,
Described bending area forms in the following manner: two surfaces of described Sparent laminate in the shaped region, described shaped region is applied heat, and be heated to the temperature that the layer arbitrarily that can not make in the described shaped region is molten into liquid form.
31. the Sparent laminate of supporting certainly product that comprises at least one bending area, described duplexer has between middle and be attached to the transparent heat solidity acrylic compounds thermoplastic layer's of side transparent polyester system, the clear acrylic analog thermoplastic layer of described side is identical or different, described bending area forms in the following manner: two surfaces of described Sparent laminate in the shaped region, described shaped region is applied heat, be heated to and make the layer arbitrarily in the described shaped region be molten into the temperature of liquid form.
32. as claimed in claim 31 oneself supports Sparent laminate, it is characterized in that the thickness of described duplexer is greater than 3 millimeters, the thickness of described polyester system is at least 0.5 millimeter, and each thermoplastic layer is acrylic material or PETG.
33. as claimed in claim 32 from supporting the Sparent laminate duplexer, it is characterized in that described thermosetting polyester system can account for the 5-40% of duplexer gross thickness.
34., it is characterized in that the thickness of described thermosetting polyester system layer is at least 1 millimeter as claim 32 or 33 described duplexers.
35. it is as claimed in claim 31 from supporting Sparent laminate, described duplexer and thickness outside acrylic layer are 2 millimeters, the core thickness of thermosetting polyester system is that the relevant performance of symmetrical version of 2 millimeters the imagination is: if the imagination is 960 * 470 millimeters rectangle then on minor axis, the version of this imagination can surpass 40 tons powerful loads and fracture and/or delamination do not take place in the edge tolerance.
36. as claimed in claim 35 from supporting Sparent laminate, it is characterized in that described mylar system is the form that comprises following component:
The unsaturated polyester resin that comprises the ethylenic unsaturated group of 45 – 70% (w/w),
The styrene of 30 – 55% (w/w),
Less than the MEKP of 2% (w/w) and
Slaine less than 2% (w/w) provides body,
When the thickness of three layer laminates is 2 millimeters, in the time of 2 millimeters and 2 millimeters and when the minor axis 960 millimeters * 470 millimeters rectangular panel pushed, this panel can tolerate the load of 60-80 ton and delamination does not take place.
37. a method of making crooked laminate material, this method may further comprise the steps:
The smooth duplexer of the flat sheet of acrylic compounds and/or PETG thermoplastic is provided, described flat sheet is identical or different, has thermosetting polyester resin between described sheet material, the extension at break of described thermosetting resin〉150%, glass transition temperature is lower than environment temperature
The shaped region of described duplexer is heated to forming temperature,
Described duplexer is shaped to required curvature,
Described duplexer is cooled off,
Wherein, the described step that the shaped region of duplexer is heated comprises that basically all layers--comprising thermoset layer and thermoplastic layer--to duplexer in the shaped region heat.
38. method as claimed in claim 37 is characterized in that, the step that shaped region is heated comprises from two surfaces of shaped region inner stacks body shaped region is applied heat.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310298404.9A CN103552289B (en) | 2006-05-23 | 2007-05-22 | Laminate material |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NZ547452 | 2006-05-23 | ||
| NZ54745206A NZ547452A (en) | 2006-05-23 | 2006-05-23 | Self supporting curved laminate made from acrylic thermoplastic and thermoset polyester |
| NZ551963 | 2006-12-08 | ||
| NZ55196306 | 2006-12-08 | ||
| PCT/NZ2007/000123 WO2007136282A2 (en) | 2006-05-23 | 2007-05-22 | Laminate material |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310298404.9A Division CN103552289B (en) | 2006-05-23 | 2007-05-22 | Laminate material |
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| Publication Number | Publication Date |
|---|---|
| CN101484305A CN101484305A (en) | 2009-07-15 |
| CN101484305B true CN101484305B (en) | 2013-08-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200780025305.6A Active CN101484305B (en) | 2006-05-23 | 2007-05-22 | Laminate material |
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| NZ (1) | NZ547452A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ547452A (en) * | 2006-05-23 | 2008-10-31 | Nu Cleer Systems Ltd | Self supporting curved laminate made from acrylic thermoplastic and thermoset polyester |
| EP3597394B1 (en) * | 2017-03-14 | 2022-06-01 | DIC Corporation | Method for producing molded body |
| KR102249961B1 (en) * | 2017-08-08 | 2021-05-11 | 알프스 알파인 가부시키가이샤 | Input device manufacturing method and input device |
| US20200086549A1 (en) * | 2018-09-13 | 2020-03-19 | Casio Computer Co., Ltd. | Three-dimensional object and method for manufacturing the same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB706096A (en) * | 1950-08-04 | 1954-03-24 | Ernest Bader | Manufacture of laminated articles using unsaturated polyester resins |
| CN1075151A (en) * | 1992-01-13 | 1993-08-11 | 三井东压化学株式会社 | Laminated transparent plastic material and polymerisable monomer |
| JP2002325661A (en) * | 2001-04-27 | 2002-11-12 | Ibiden Co Ltd | Display shelf for commercial goods |
| CN1760458A (en) * | 2005-11-16 | 2006-04-19 | 辽宁警官高等专科学校 | Light-light reflecting road traffic marker band |
| CN101484305A (en) * | 2006-05-23 | 2009-07-15 | 纽克列尔体系有限公司 | Laminate material |
-
2006
- 2006-05-23 NZ NZ54745206A patent/NZ547452A/en unknown
-
2007
- 2007-05-22 CN CN200780025305.6A patent/CN101484305B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB706096A (en) * | 1950-08-04 | 1954-03-24 | Ernest Bader | Manufacture of laminated articles using unsaturated polyester resins |
| CN1075151A (en) * | 1992-01-13 | 1993-08-11 | 三井东压化学株式会社 | Laminated transparent plastic material and polymerisable monomer |
| JP2002325661A (en) * | 2001-04-27 | 2002-11-12 | Ibiden Co Ltd | Display shelf for commercial goods |
| CN1760458A (en) * | 2005-11-16 | 2006-04-19 | 辽宁警官高等专科学校 | Light-light reflecting road traffic marker band |
| CN101484305A (en) * | 2006-05-23 | 2009-07-15 | 纽克列尔体系有限公司 | Laminate material |
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| Publication number | Publication date |
|---|---|
| CN101484305A (en) | 2009-07-15 |
| NZ547452A (en) | 2008-10-31 |
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