CN1270889A - Laminate artical using liquid-resistant film and double side sheet - Google Patents

Abstract

A laminate panel having desired characteristics even though the materials having these desired characteristics are not compatible in at least one aspect, is disclosed . One of the substances having the desired characteristics may be moved away from the other substance and a different substance compatible with the substances may be used between the two substances. For example, the laminate panel includes a liquid impermeable layer that substantially prevents the penetration of moisture. The panel also includes a layer of a balancing substance disposed close to the liquid impermeable layer to balance another layer of the laminate panel. A kraft paper sheet coated with the balancing substance on one side and a substance providing good bonding with the liquid impermeable layer on the other side, may be used to provide the desired balancing characteristic.

Description

Adopt the laminate of anti-liquid film and double side sheet

The present invention relates generally to, for example can be used for the production of the laminated product of floor, sales counter and desktop and wallboard, more particularly, relate to the system and the method that adopt laminated material to produce these products that comprise anti-liquid film, described laminated material scribbles identical or different material independently on its opposing face.

In these years obviously improved the ability of imitated natural material.For example, the decorative laminate product have substituted natural material in furniture, cabinet, counter top, floor and other surperficial structure.In these are used each, combination with decorative surfaces can be applied to sandwich layer or ground, i.e. glued board, flakeboard, particieboard, medium density fibre board (MDF), high density fiberboard and other alternative ground.Usually, the substrate layer reverse side that will be fixed to ground moves or provides other effect so that balance is ostentatious.Well known, traditional high-pressure laminating product are along with the increase of ambient humidity or minimizing and expand or shrink.Known in addition, chronically the plate complex is exposed to liquid, as water (for example, overflow),, but also ground is had a negative impact not only to traditional laminate through sub-floor.

In general, the combination with decorative surfaces of laminate complex is as the laminate flooring of Fig. 1 design.High-pressure laminating product 10 can comprise the thin veneer sheet material 11 that is added with aluminium oxide that is impregnated with protection material such as melamine resin, and described protection material can provide color fastness, hardness, chemical resistance and to the patience of of short duration chance water.This high-pressure laminating product 10 can adopt the decoration sheet 12 that is positioned under the veneer sheet material 11 and be positioned at the brown paper sheet material 13 and 14 that is impregnated with phenolic resins under the decoration sheet.

Traditionally, the design of substrate layer is similar.As shown in Figure 1, the substrate layer of high-pressure laminating product 10 can comprise the brown paper sheet material 16 that is impregnated with phenolic resins that is positioned under the ground 15 and 17 and the balance layer 18 that is positioned at the veneer paper that is impregnated with the protection material under brown paper sheet material 16 and 17.In the laminate of floor, this protection material can be a melamine resin.Usually substrate layer and decorative layer all use a kind of suitable adhesives to ground 15.

One of ordinary skill in the art will appreciate that above-mentioned decorative layer and substrate layer are illustrative, therefore narration of the present invention can not be confined to said structure.

(for example, by being bonded together several laminate floorings) is being installed afterwards, these decorative laminate product will stand the environment different with the substrate laminate.That is the decorative laminate product that, expose will stand the temperature and humidity fluctuation of indoor environment.On the contrary, the substrate laminate temperature and humidity that will stand the sub-floor that this laminate flooring imposes on changes.In addition, if substrate laminate long term exposure is in liquid, as water, for example through the overflow of sub-floor, not only to the substrate laminate but also ground is had a negative impact.But traditional floor is unreasonable in design or others, therefore can not deal with the environmental differences that decorative laminate product and substrate laminate are exposed.

A kind of creationary solution is, in order to prevent the infiltration of moisture, enter substrate layer as steam or moisture, use the impermeable layer of a kind of liquid in the bottom of substrate layer, as the styrene-maleic anhydride copolymer layer to prevent moisture basically, as seeing through of aqueous water.This creative solution is disclosed in the U.S. Patent application of above referenced common transfer in detail, is entitled as " laminate ".

Although can obviously improve the resistance to water of whole complex in the substrate with liquid impermeable barrier introducing laminate flooring in a preferred embodiment of U.S. Patent application (being entitled as " laminate "), but the decorative laminate product also can increase the sensitiveness of low humidity condition, because in this preferred embodiment, the melamine layer in the substrate laminate is replaced by the liquid impermeable barrier.In general, the mobile meeting of melamine layer 11 under the low humidity condition causes the floor bending, that is, its side is bent upwards (positive curve).This positive curve on floor visually is tangible.

In a preferred embodiment of the U.S. Patent application (being entitled as " laminate ") of above-mentioned reference, described substrate layer comprises the liquid impermeable barrier on the outer surface that directly is bonded to one of which floor resin impregnating brown paper.According to the preferred embodiment of the U.S. Patent application (being entitled as " laminate ") of above-mentioned reference, the veneer balance layer of melamine process is not introduced in the substrate laminate, because can not form enough bondings between liquid impermeable barrier and the melamine layer.Attempted increasing resin impregnating brown paper sheet material in the substrate laminate number and weight obtaining strong substrate, with balance and/or offset decorative laminate product because of humidity drive mobile.But when the melamine process veneer sheet material with two-layer or multilayer was used for the decorative laminate product with the raising wearability, the undercapacity of the strong substrate that these effort produce moved with balance decorative laminate product.

Therefore, this area needs a kind of advantage of utilizing the advantage of melamine balance layer and utilizing the liquid impermeable barrier to be produced, and comes producing zone to press the system and the method for product.

The purpose of these and other, feature and technological merit are realized by a kind of like this system and method, promptly in this system and method, make layer with desirable characteristics, as balance layer can with have desirable characteristics another the layer, be used in combination in laminate as the liquid impermeable barrier, although these layers with desirable characteristics are not allowed mutually.

Therefore; in one embodiment of the invention; the preferred stress produce owing to protection material moving in decorative layer for balance; for example prevent the positive curve of complex; simultaneously in order to give this complex, as the liquid impenetrability, with the balance sheet material with another kind of desirable characteristics; be placed on the inside of substrate laminate as the melamine impregnated sheet, and the liquid impermeable barrier is placed on the outside.To have the 3rd layer of excellent bonding characteristic, adjacent to the liquid impermeable barrier, and the balance sheet material that will comprise melamine and so on balance material is just adjacent to the resin impregnating layer as the resin impregnating layer.Therefore, changed in the design of traditional laminate the order of each sheet material in the substrate laminate, can make the balance sheet material no longer is outermost layer.Therefore, in this embodiment of the present invention, melamine layer and liquid impermeable barrier are isolated mutually by the intermediate layer, adopt the complex of this substrate laminate just to have the resistance to liquid of planarization and enhancing simultaneously like this.

But should be appreciated that above-mentioned embodiment provides from the balance layer of two kinds of sheet materials of laminate outer surface taking-up at least.But the layer that may need to have this desirable characteristics is placed in the different aspects of this laminate.For example, for appropriate balance has the complex of the characteristic material relevant with last outer surface or decorative laminate product, may need the end outer surface of balance layer near the substrate laminate.Therefore, if laminate flooring has the last outer surface of melamine dipping overlay coating as decorative cover, need so to make the end outer surface of the close laminate of melamine balance layer as far as possible with overlay coating on the appropriate balance.

Therefore, in another embodiment of the present invention, in order to produce required balance quality, can use and on one side, scribble the material that can produce first kind of desirable characteristics, as the balance material (as, melamine), and on another side, scribbles the laminated material of the another kind of material that can produce the required balance characteristic, as the brown paper sheet material.Be used to produce the system of this laminated material and the common transfer U.S. Patent application that method is disclosed in above-mentioned reference in detail, be entitled as " being used for system and method that double side sheet is handled ".Therefore, in this embodiment, this brown paper sheet material can be adjacent to giving the layer of laminate with another kind of desirable characteristics, as the liquid impermeable barrier, and the liquid impermeable barrier is pressed close on the surface that phenolic resins is applied, the melamine coating surface is the liquid impermeable barrier dorsad, the layer with required balance characteristic can be placed on very the aspect near the laminate outside like this.

The advantage that different embodiments of the present invention discussed above produced is that prior art is not available.For example, so the laminate of structure is because introducing liquid impermeable barrier has liquid, and as the impenetrability of water and have equilibrium response, this complex just keeps smooth basically under the temperature and humidity condition of broad like this.In addition, in another above-mentioned embodiment, the balance material can be pressed close to the outer surface of laminate, because balance melamine layer can produce required equilibrium response so only by brown paper sheet material phenolic resins layer coated side and liquid impermeable barrier and separate with the outer surface of this complex.In typical laminate, the outmost surface that the veneer sheet material constitutes these decorative laminate product is flooded as the melamine of decorative laminate product in the surface of ready to balance.Therefore, the outside of the preferably close substrate laminate of balance material.

In addition, laminated material, as be used for the laminated material such as the brown paper sheet material of this embodiment, and available relatively large balance material soaks into as melamine, and this laminate can keep smooth like this.Because brown paper can absorptance be used for the more melamine of traditional veneer sheet material of prior art substrate laminate, so can provide more melamine resin on the unit are sheet material to this laminate, can obtain stronger balance layer like this.Therefore, in another embodiment, planarization is that the intensity by the substrate laminate realizes, this substrate laminate can prevent that the melamine layer forward of decorative laminate product from peeling off this complex.The prior art veneer sheet material that is impregnated with the balance material can only use limited amount balance material, thus the melamine layer of decorative laminate product not ability peel off.

In addition,, can eliminate, can reduce the cost when producing this laminate like this using the demand of discrete balance sheet material (normally a kind of veneer sheet material of costliness) by using a kind of laminated material of on the apparent surface, handling with identical or different material.

Therefore, a technological merit of the present invention provided a kind of can with decorative panel, the impermeable lamination product of liquid that use as the floor.

Another technological merit of the present invention has provided a kind ofly has required equilibrium response in case the under extreme conditions crooked hydrophobic laminate of laminate.

A technological merit more of the present invention has provided a kind of laminate that has the liquid impermeable barrier and balance layer is arranged near this liquid impermeable barrier.

Another technological merit of the present invention has provided a kind of impermeable floor of liquid laminate with wooden substrate material.

Another technological merit of the present invention has provided a kind of have sandwich layer or ground of being made up of alternative ground (ASM) and the impermeable floor of the liquid laminate with required balance characteristic.

Another technological merit of the present invention has provided a kind of water-fast floor laminate, and wherein balance layer is positioned at from the outside minimum distance of laminate.

Aforementioned content has quite briefly provided various characteristics of the present invention and technological merit, can understand better about detailed description of the present invention like this.Below will describe other characteristics of the present invention and advantage, they have constituted the theme of claim of the present invention.Those skilled in the art should be appreciated that, disclosed viewpoint and particular often can be used as the basis and change or design other structure to realize the purpose identical with the present invention.Those skilled in the art be also to be understood that purport of the present invention and the scope that these suitable structures do not deviate from appended claims to be proposed.

In order to understand the present invention and advantage thereof more comprehensively, now in conjunction with the accompanying drawings with reference to following description, wherein:

Fig. 1 is the schematic diagram of prior art laminate;

Fig. 2 is the schematic diagram according to the substrate of first embodiment of the invention;

Fig. 3 is the schematic diagram according to the substrate of second embodiment of the invention;

Fig. 4 is the schematic diagram according to the substrate of third embodiment of the invention;

Fig. 5 is the schematic diagram according to the substrate of four embodiment of the invention;

Fig. 6 is the schematic diagram according to the substrate of fifth embodiment of the invention; With

Fig. 7 is the results list that carries out experiment test on the floor of using Fig. 4 laminate.

Fig. 2 is the laminate of one embodiment of the invention, as the schematic diagram of substrate laminate.In embodiment shown in Figure 2, laminate 20 comprises the one deck with desirable characteristics, as liquid impermeable barrier 21, is preferably the styrene-maleic anhydride copolymer layer.Styrene-maleic anhydride copolymer is preferably by NOVA Chemicals, the DYLARK  that Inc makes.Will be compatible with this layer with desirable characteristics and with the laminated material of this layer bonding excellence with desirable characteristics, as resin impregnating layers of kraft paper 22 adjacent to this layer, as liquid impermeable barrier 21 with desirable characteristics.

Styrene-maleic anhydride copolymer but also has good heat endurance except having the outstanding bonding characteristic with resin impregnating brown paper.This excellent bonding characteristic of styrene-maleic anhydride copolymer is because carboxyl is present on the maleic anhydride of this copolymer, thereby can be bonded on the phenolic resins.Therefore, according to the present invention, can use many polymer with the required bonding characteristic of generation with the impermeable lamination product of liquid with carboxyl.Carboxyl is connected on the phenolic resins to obtain highly stable laminate.Styrol copolymer is owing to hydrophobic is difficult for permeation liquid, as water.Certainly, as long as adopt other material to obtain laminate of the present invention, so just can use polymer with other characteristic and/or chemical composition or unsaturated monomer with generation to liquid, as the impenetrability of water and above-mentioned adhesive property.These polymer comprise α, beta-unsaturated carboxylic acid and α, the beta-unsaturated acid acid anhydride, as the maleic anhydride of crotonic acid, acrylic acid, methacrylic acid, sorbic acid, cinnamic acid, maleic acid, fumaric acid, tetrabydrophthalic anhydride, dodecenyl succinic acid anhydrides and alkyl replacement, as dimethyl maleic anhydride.Except styrene, olefinic type monomers can be carried out copolymerization as ethene, propylene or 1-butylene and above-mentioned unsaturated monomer.In addition, the polymer of olefinic type monomers can carry out grafting with above listed unsaturated monomer as polyethylene or polypropylene.

Because in a preferred embodiment Fig. 2 liquid impermeable barrier of making by styrene-maleic anhydride copolymer have with material (except can in laminate, producing the material of second kind of desirable characteristics, excellent bonding characteristic as the balance material outward), this material that therefore can produce second kind of desirable characteristics is removed from the liquid impermeable barrier.Therefore, in embodiment shown in Figure 2, balance layer 23 is preferably the laminated material that is soaked with the balance material, floods the veneer sheet material adjacent to resin impregnating layers of kraft paper 22, away from liquid impermeable barrier 21 as melamine resin.Therefore, embodiment shown in Figure 2 provides a kind of and can prevent the liquid impermeable barrier of moisture penetration in the substrate laminate.In addition; in this preferred embodiment; by offseting the pressure that is produced by corresponding decorative laminate product (not providing among the figure) layer; the balance layer 23 of embodiment shown in Figure 2 provides required equilibrium response to complex, thus balance architectural surface, as have the protection material (as; melamine) overlay coating; can prevent the complex bending like this, that is, make complex keep smooth basically.

Usually, the thickness of Fig. 2 liquid impermeable barrier 21 is 5 mils, and the thickness of resin impregnating layers of kraft paper is the 7-11 mil.Therefore, in this embodiment of the present invention, can produce the outer surface 12-16 mil of the balance layer 23 of second kind of desirable characteristics apart from laminate, this depends on the thickness of liquid impermeable barrier 21 and resin impregnating layers of kraft paper 22.But may need according to concrete purposes, the balance layer 23 that can produce second kind of desirable characteristics shifts near or away from the outer surface of laminate.For example, in typical decorative laminate product, the layer with protection material is the outmost surface on the decorative cover, and the balance layer 23 that it may preferably make Fig. 2 embodiment is close outer surface on substrate surface as far as possible.

Therefore, another embodiment of the present invention shown in Figure 3 comprises a kind of laminated material 32, as the brown paper sheet material, on its one side, scribble the material that can produce first kind of desirable characteristics, as balance material (as, melamine), and on another side, scribble the another kind of material that can produce desirable characteristics, as has a material (as, phenolic resins) of excellent bonding characteristic.This laminate provides and describes at above referenced common transfer U.S. Patent application (being entitled as " being used for system and method that double side sheet is handled "), incorporates it into the present invention as a reference at this.

In the embodiment depicted in fig. 3, the laminate 30 that makes progress the end of from comprises liquid impermeable barrier 31; Laminated material 32 is as the brown paper sheet material that applies phenolic resins and scribble melamine on another side on its one side; And another kind of laminated material 33, as resin impregnating brown paper 33.In the embodiment of Fig. 3, the phenolic resins coated side of brown paper sheet material 32 is towards liquid impermeable barrier 31 because styrene-maleic anhydride copolymer has the excellent bonding characteristic with phenolic resins, although it and be not easy to adhere on the melamine.Liquid impermeable barrier 31 provides first kind of desirable characteristics to this laminate, as makes this laminate water-fast basically.Resin impregnating brown paper 33 can be adjacent to the melamine resin coated side of laminated material 32.

Usually, the thickness of Fig. 3 liquid impermeable barrier 31 is 5 mils, and the thickness of melamine/resin impregnating brown paper 32 is the 7-11 mil, and this depends on the kind of used brown paper.Suppose to use phenolic resins and melamine resin to soak into brown paper 32 with 1: 1 ratio, melamine can be (5+3.5 or) 8.5 mils to (5+5.5 or) 10.5 mils from the distance of this laminate outer surface so.Therefore, the balance layer that can produce second kind of desirable characteristics in Fig. 3 embodiment is the 8.5-10.5 mil from the distance of the outer surface of this embodiment that exemplifies, and this depends on the thickness of the liquid impermeable barrier 31 that can produce first kind of desirable characteristics in Fig. 3 embodiment and the thickness of melamine/resin impregnating layers of kraft paper 32.In brown paper 32, the ratio of phenolic resins and melamine resin can change with the equilibrium response that increases sheet material and reduce the bonding characteristic of sheet material, as described in the U.S. Patent application (being entitled as " being used for system and method that double side sheet is handled ") of above-mentioned reference.Therefore, the distance of balance material absciss layer pressure product outer surface also depends on the resin content in the brown paper sheet material 32.In embodiments of the invention, the balance material compared with embodiment shown in Figure 2 more near the laminate outer surface.When balance material layer and protection material layer during along complex center symmetric arrays, this complex obtains optimum balance.

The protection number of plies on decorative cover is 1 o'clock, and embodiment of the present invention shown in Figure 3 provides required characteristic, as liquid impenetrability and equilibrium response.But in other cases, for example the protection number of plies on decorative cover surpasses 1, and for example in commercial or other high mill occasion of the bigger wearability of needs, this embodiment may not have desirable characteristics, as suitable equilibrium response.In these cases, the melamine in the protective layer on the decorative cover is just very strong, and laminate upwards can be stretched more, causes positive curve.This effect is particularly evident under dried and low humidity condition.Therefore, need on the substrate of laminate or balanced surface, have a large amount of balance materials to offset this supplementary protection layer.

Therefore, in the embodiment depicted in fig. 4, comprised an extra play 43, as on one side, scribbling the material that can produce desirable characteristics, as balance material (as, melamine), on another side, scribble identical or different material with desirable characteristics, as have the material of excellent bonding characteristic, as the brown paper sheet material of phenolic resins.The laminate 40 of embodiment shown in Figure 4 upwards comprises liquid impermeable barrier 41 end of from, laminated material 42, as scribbling phenolic resins on the one side and on another side, scribbling the brown paper sheet material of melamine resin, with another laminated material 43, as scribbling melamine resin on the one side and on another side, scribbling the brown paper sheet material of phenolic resins.In the embodiment of Fig. 4, the phenolic resins coated side of brown paper sheet material 42 is towards liquid impermeable barrier 41, because styrene-maleic anhydride copolymer has the excellent bonding characteristic with phenolic resins.Liquid impermeable barrier 41 provides first kind of desirable characteristics to laminate, as makes this laminate water-fast basically.Brown paper sheet material 43 can be adjacent to laminated material 42, and the melamine face of brown paper sheet material 43 is the melamine face of neighbour's laminated material 42 then.In the embodiment depicted in fig. 4, if desired, the phenolic resins layer can be near the ground (not shown), as non-wood substrate material to bond with ground.

Usually, the thickness of the liquid impermeable barrier 41 of Fig. 4 is 5 mils, and the thickness of melamine/resin impregnating brown paper 42,43 is the 7-11 mil, and this depends on the kind of used brown paper.Suppose to use phenolic resins and melamine resin to soak into brown paper with 1: 1 ratio, the balance material can be (5+3.5 or) 8.5 mils to (5+5.5 or) 10.5 mils from the distance of this laminate outer surface so.Therefore, balance layer is the 8.5-10.5 mil from the distance of the outer surface of this laminate, and this depends on the thickness of liquid impermeable barrier 41 and the thickness of melamine/resin impregnating layers of kraft paper 42.As above in the discussion to Fig. 3 embodiment, can change the ratio of phenolic resins and melamine resin.Therefore, the distance of balance material absciss layer pressure product outer surface also depends on the resin content in the brown paper sheet material 42.

For the multi-protective layer on the appropriate balance decorative cover and keep complex smooth, the laminate that the laminate of Fig. 4 preferably has than Fig. 3 has more melamine.The prior art substrate has used the special overlay matrix material with the melamine resin dipping.But there is the brown paper of melamine resin sheet material to obtain adopting on phenolic resins and the another side having on the one side, to add the melamine of aequum, as described in above referenced common transfer U.S. Patent application (being entitled as " being used for system and method that double side sheet is handled ").Although in this preferred embodiment, only half brown paper floods with melamine, can increase the amount of melamine according to concrete application.An advantage of embodiment shown in Figure 4 is, because brown paper has more resin than the traditional veneer sheet material with the melamine resin dipping on the unit sheet material, so can comprise a large amount of balance materials in the substrate laminate.In addition, in the embodiment of Fig. 4, used two-layer double treatment brown paper sheet material producing better equilibrium response, as by producing the multi-protective layer that higher intensity and deflection are come the balance decorative cover.Therefore, in this embodiment, complex can owing to melamine in the substrate laminate high concentration and under high and low humidity maintenance smooth.In addition, so the laminate of gained is water-fast owing to there is the liquid impermeable barrier, therefore can be not crooked when overflow or in water.

In the described embodiment of Fig. 4, although the melamine face of brown paper 42 is towards the melamine face of brown paper 43, in other embodiments, brown paper 43 can turn around, the phenolic resins face of brown paper 43 can be towards the melamine face of brown paper 42, to obtain the laminate of balance like this.

Fig. 5 has provided a kind of alternate embodiment of embodiment of the present invention shown in Figure 4, and wherein the phenolic resins of Fig. 4/melamine layer 43 substitutes with melamine/melamine layer 53.The laminate 50 of embodiment shown in Figure 5 upwards comprises liquid impermeable barrier 51 end of from, laminated material 52, as the brown paper sheet material that on its one side, applies phenolic resins and on another side, scribble melamine, and another kind of laminated material 53, as scribbling the brown paper sheet material of melamine resin on two-sided.In the embodiment of Fig. 5, the phenolic resins coated side of brown paper sheet material 52 is towards liquid impermeable barrier 51 because styrene-maleic anhydride copolymer has the excellent bonding characteristic with phenolic resins, although it and be not easy to adhere on the melamine.The another kind of brown paper sheet material 53 that scribbles melamine resin on two-sided only adjacent bed is pressed the melamine coated side of material 52.If desired, the extra play that is impregnated with the brown paper 54 of phenolic resins can be positioned on the layer 53.In another embodiment, extra play 54 can flood with other resin, or does not exist, and this does not deviate from purport of the present invention.

As mentioned above, on two-sided, scribble same substance, can avoid using the veneer matrix material that is impregnated with melamine for the veneer matrix material of balance decorative cover as the dual coating sheet material 53 of melamine.Usually, veneer matrix material is more expensive more than brown paper sheet material.Therefore, Fig. 5 embodiment of the present invention advantage is the production cost that has reduced the impermeable lamination product of liquid.In addition, can control the balance amount of substance according to the required amount of veneer type melamine impregnated sheet of balance decorative cover.Therefore, the amount of dipping melamine can increase or reduce according to concrete purposes.

Fig. 6 has provided a kind of alternate embodiment of embodiment of the present invention shown in Figure 5, and wherein the melamine of Fig. 5/melamine layer 53 substitutes with traditional melamine dipping veneer sheet material 63.Like this, the laminate 60 of embodiment shown in Figure 6 upwards comprises liquid impermeable barrier 61 end of from, and laminated material 62 is as the brown paper sheet material that applies phenolic resins and scribble melamine on another side on its one side; And another kind of laminated material 63, as melamine resin dipping veneer sheet material.In other embodiments, anyly be suitable for using resin, all can be used as laminated material 63 as the sheet material of melamine resin dipping.In the embodiment of Fig. 6, the phenolic resins coated side of brown paper sheet material 62 is towards liquid impermeable barrier 61 because styrene-maleic anhydride copolymer has the excellent bonding characteristic with phenolic resins, although it and be not easy to adhere on the melamine.But the melamine face of melamine dipping veneer sheet material 63 neighbour's laminated materials 62.If desired, the extra play that is impregnated with the brown paper 64 of phenolic resins can be positioned on the layer 63.In other embodiments, extra play 64 can flood with other resin, or does not exist, and this does not deviate from purport of the present invention.

Experiment shows that the embodiment of aforesaid laminate of the present invention can produce improved equilibrium response.The effect that melamine balance sheet material is added in the substrate laminate provides in table 7.When experimentizing, two 7 ' * 5 ' floors are installed in environmental control room on the particle plank floor apparatus.The sheet material that uses polyurethane binder will constitute every floor bonds together.The first floor A has adopted the substrate laminate of design as shown in Figure 4, comprise one deck styrene-maleic anhydride copolymer, the two brown paper of handling of a slice phenolic resins/melamine resin, wherein the phenolic resins treatment surface is close to the styrene-maleic anhydride copolymer layer, second two brown paper of handling of phenolic resins/melamine resin, wherein the melamine resin treatment surface is towards the melamine process surface of first sheet material, and the phenolic resins treated side of second brown paper is adjacent to ground.The second floor B has adopted and has comprised one deck styrene-maleic anhydride copolymer and three substrate laminates with 140 pounds of brown paper of phenolic resins processing.The installation and the final crooked situation on different floors have been provided in the table of Fig. 7.In the table of Fig. 7, negative value represents that this floor is downwards towards the bending of sub-floor.Upwards leave the bending of sub-floor on the occasion of this floor of expression.All values is all represented with inch.

At 0-3 days, indoor temperature remained on 70 °F, and relative humidity remains on 50%.At the 3rd day, start cycles technology in humidity chamber, wherein temperature and humidity changed 4 times in one day.Every day in 3-6 days, indoor temperature that keeps and relative humidity are 110,0% relative humidity (7 hours); 70,30% relative humidity (5 hours); 50,95% relative humidity (7 hours); With 70,30% relative humidity (5 hours).At the 7th day, temperature is changed back to 70 °F, relative humidity is set to 50%.Experimental result provides in the table of Fig. 7.

As can be seen, the floor B sheet material of being made up of styrene-maleic anhydride copolymer showed lower hogging bending at the 0th day, and this can be found out by the mean value in " INSTALLED (the installation) " hurdle in Fig. 7 table.On the other hand, the floor A sheet material of being made up of the laminate of embodiment shown in Figure 4 showed higher hogging bending at the 0th day.In addition, compare with the floor B sheet material of being made up of the liquid impermeable barrier that does not have balance layer, the floor A sheet material of being made up of laminate of the present invention showed lower positive curve at the 7th day, and this can be found out by the mean value in " FINAL (the finally) " hurdle in Fig. 7 table.The positive curve of complex is undesirable, because the seam between the plank can upwarp, seems uncomfortable.This can produce the impression of having broken in this surface, therefore impairs this surperficial outward appearance.The relative floor of complex B, floor complex A shows higher positive curve.In addition, the positive warpage of floor B is visible fully, and the warpage of floor A is then invisible.Therefore should be clear, the laminate of aforesaid embodiment of the present invention has improved equilibrium response.

As mentioned above, the floor A that comprises the substrate of Fig. 4 embodiment of the present invention shows before and after installing than the floor B with conventional design obviously and consistent hogging bending.Therefore, floor or other laminate of producing according to the preferred embodiment of the invention tends to have consistent hogging bending.This hogging bending generally is invisible concerning casual observer.But opposite is, even the positive curve of a little also can be found in the typical environment that laminate is installed.In addition, under harsh environmental condition, laminate is past to the forward crooked as the flooring product in the preferred embodiment.Therefore, by in this laminate, producing a little consistent hogging bending, can rely on this positive curve that took place afterwards of payment, and obtain a kind of product of excellence, because avoid or eliminated visible positive curve.Therefore in a preferred embodiment, adopted a certain amount of balance material, as melamine, this material produces aforesaid initial hogging bending in laminate owing to its characteristic.For example, have been found that the two-layer melamine balance material of use can produce above-mentioned consistent and slight hogging bending.

Different embodiments of the present invention discussed above thinks can be used for the example of substrate laminate of the present invention.Decorative layer can be a various forms, can adopt the laminate layer of various compound modes.Therefore only otherwise deviate from purport of the present invention, each layer of above-mentioned substrate laminate can change to remedy the variation in the decorative layer.In addition, aforesaid liquid impermeable barrier of the present invention and balance layer can use under the situation that does not have corresponding use decorative layer and/or ground as required.For example, the sheet material that has liquid impermeable barrier and a balance layer on its one side or all faces can any orientation use, and it is impermeable and can curved surface to obtain liquid, and need not to use corresponding decorative layer.

The laminate of prior art uses various wood-base materials, as glued board, flakeboard, particieboard, medium density fibre board (MDF), high density fiberboard etc. as ground.Although above-mentioned different embodiments of the present invention can be used the ground of any kind of, as wooden base and non-wood substrate material, the present invention especially uses by substituting the ground that ground (ASM) is made.These ASM can comprise non-wood core material or ground, as synthetic or non-cellulose ground, as reclaim materials such as plastic bottom material, ASB/PC, nylon, PVC, polystyrene, any polyolefin, they can be separately or as required with similar or non-similar material, be used in combination as calcium carbonate, magnesium hydroxide, talcum, clay, glass fibre, carbon fiber, fire retardant, antismoke agent, wollastonite.Compared with the traditional laminate that uses wooden substrate material, the deflection that non-wood substrate material is lacked makes that the use of above-mentioned different embodiments laminate is desirable more, can provide required characteristic to laminate like this, as intensity and balance quality.

In above-mentioned different embodiments of the present invention, balance layer moved apart outer surface and towards laminate inside, because the liquid impermeable barrier is difficult for adhering on the balance layer with above-mentioned example materials.But the present invention is not limit by this, and in other embodiments, the layer that can produce the layer of first kind of desirable characteristics and can produce second kind of desirable characteristics can move apart or near the outer surface of this laminate.For example, the liquid impermeable barrier can move apart outer surface and towards laminate inside under the situation that does not deviate from purport of the present invention.Therefore, scribbling the laminate material that scribbles phenolic resins on melamine resin and the another side on its one side can be outermost layer, and wherein the melamine layer outward.The liquid impermeable barrier can be placed on the phenolic resins coating surface of this laminate material of neighbour subsequently.In addition, only otherwise deviate from purport of the present invention, can use the laminated material more than 2 layers, this laminated material scribbles the material that can produce desirable characteristics on its one side, and scribbles the similar and different material that can produce desirable characteristics on another side.In addition, can use different each layer generations to be different from above-mentioned characteristic or function.Therefore, the present invention can be used for providing the structure of the bonds well with desirable characteristics, is difficult for bonding even have the material of these characteristics.

Those skilled in the art should be appreciated that, although above liquid impermeable barrier and the balance layer when describing embodiment of the present invention, mentioned, but the present invention is not limited thereto, therefore various narrations of the present invention can be used for need with two kinds of materials mutually near and these two kinds of materials any occasion that can not bond mutually.In addition, although with regard to the substrate laminate various embodiments have been discussed, the present invention can be used for the decorative cover of laminate.

Although described the present invention and advantage thereof in detail, should be appreciated that, only otherwise deviate from purport of the present invention, can carry out various variations, replacement and change by the claims definition.In addition, the application's scope is not limited to the particular in the described technology of specification, machine, production, material composition, device, method and step.Those of ordinary skills can find out from disclosure of the present invention, can according to the present invention adopt present existence or to develop later on have various technologies, machine, production, material composition, device, method and a step that substantially the same function maybe can reach substantially the same result.Therefore, appended claims means that these technologies, machine, production, material composition, device, method or step are included in its scope.

Claims (117)

1. laminate that is used for final products wherein comprises:

The ground floor of first kind of material of first kind of desirable characteristics can be provided in described final products;

Can produce the second layer of second kind of material of second kind of desirable characteristics in described final products, wherein said first kind and second kind of material are not being allowed aspect at least one mutually, and wherein said first and second layers mutual close; With

The 3rd layer of the third material, at least a compatible in wherein said the third material and described first kind and the second kind of material, and wherein said the 3rd layer between described first and second layers so that between them, make close mutually.

2. the laminate of claim 1, wherein said the third material also with described first kind and second kind of material in another kind of compatible.

3. the laminate of claim 1, wherein said incompatible aspect is a bonding characteristic.

4. the laminate of claim 1, the described first kind of desirable characteristics in the wherein said final products is resistance to water.

5. the laminate of claim 1, wherein said first kind of material are to prevent the styrene-maleic anhydride copolymer of moisture penetration in the described final products basically.

6. the laminate of claim 1, the described second kind of desirable characteristics in the wherein said final products is consistent with the 4th layer non-architectural characteristic of described final products.

7. the laminate of claim 1, wherein said second kind of material be can the 4th layer of the described final products of balance in the melamine resin of the 4th kind of material.

8. the laminate of claim 1, wherein said final products are selected from floor, sales counter, desktop, exterior wall, interior wall, baffle plate, roof, surface plate and workbench.

9. the laminate of claim 1, wherein said the third material is a phenolic resins, its easily with described first kind of material and described second kind of material bonding.

10. the laminate of claim 1, wherein said second kind of material and described the third material are applied on the opposing face of laminated material.

11. the laminate of claim 10, wherein said laminated material is a brown paper.

12. the laminate of claim 11, the wherein said second layer depends in part on the selected penetration degree of described second kind of material in the described brown paper from the distance of described ground floor.

13. the laminate of claim 10, it also comprises:

On opposing face, scribble the another kind of laminated material of described second kind of material and described the third material.

14. the laminate of claim 13, wherein said another kind of laminated material is positioned near described a kind of laminated material, and second kind of material coating surface of described another kind of laminated material is towards second kind of material coating surface of described a kind of laminated material.

15. the laminate of claim 10, it also comprises:

Scribble the another kind of laminated material of described second kind of material on it is two-sided, wherein said another kind of laminated material is attached adjacent to second kind of material coating surface of described laminated material.

16. the laminate of claim 15, wherein said another kind of laminated material is the brown paper sheet material.

17. the laminate of claim 15, wherein said another kind of laminated material is the veneer sheet material.

18. the laminate of claim 15, wherein said another kind of laminated material are to be suitable for the sheet material that soaks into resin.

19. the laminate of claim 18, wherein said resin is selected from phenolic resins and melamine resin.

20. the laminate of claim 6, it also comprises:

Between described the 4th layer and the described second layer adjacent to described the 4th layer decorative layer.

21. the laminate of claim 20, it also comprises:

Ground between the described decorative layer and the described second layer.

22. the laminate of claim 21, wherein said ground are non-wood substrate material.

23. the laminate of claim 1, wherein said first and second kinds of material requirements are positioned on the same aspect of described laminate.

24. a method that is used to produce laminate may further comprise the steps:

Definite first specific character that will give described laminate;

The first kind material of described laminate with described first specific character given in selection;

Definite second specific character that will give described laminate;

Selection is given described laminate with second kind of material of described second specific character, and described first kind of material that wherein can produce described first specific character do not allowed aspect at least one mutually with described second kind of material that can produce described second specific character;

Make the ground floor that comprises described first kind of material close mutually with the second layer that comprises described second kind of material; And

Select with described first kind and second kind of material in the third at least a compatible material, the 3rd layer of wherein said the third material between the described ground floor and the described second layer.

25. the method for claim 24, wherein said the third material also with described first and second kinds of materials in another kind of compatible.

26. the method for claim 24, wherein said the third material be easy to described first and second kinds of materials at least a bonding.

27. the method for claim 26, it is phenolic resins that described the third material of described bonding characteristic wherein can be provided.

28. the method for claim 24, described first characteristic that wherein will give described laminate is the liquid impenetrability.

29. the method for claim 28, described first kind of material that wherein can generate the liquid impenetrability is styrene-maleic anhydride copolymer.

30. the method for claim 28, wherein said first kind of copolymer that material is first monomer and second monomer.

31. the method for claim 30, wherein said first kind of monomer is selected from ethene, propylene and 1-butylene.

32. the method for claim 30, wherein said second kind of monomer is to be selected from α, beta-unsaturated carboxylic acid and α, the unsaturated monomer of beta-unsaturated acid acid anhydride.

33. the method for claim 32, wherein said α, the beta-unsaturated acid acid anhydride is selected from tetrabydrophthalic anhydride, dodecenyl succinic acid anhydrides and dimethyl maleic anhydride.

34. the method for claim 32, wherein said α, beta-unsaturated carboxylic acid are selected from crotonic acid, acrylic acid, methacrylic acid, sorbic acid, cinnamic acid, maleic acid and fumaric acid.

35. the method for claim 28, wherein said first kind of material are by with α, beta-unsaturated carboxylic acid is grafted on the polymer that is selected from polyethylene, polypropylene or polybutene and the material that obtains.

36. the method for claim 28, wherein said first kind of material are by with α, the beta-unsaturated acid acid anhydride is grafted on the polymer that is selected from polyethylene, polypropylene or polybutene and the material that obtains.

37. the method for claim 24, described second specific character that wherein will give described laminate is an equilibrium response.

38. the method for claim 37, described second kind of material that wherein can generate described equilibrium response is melamine resin.

39. the method for claim 37, it is further comprising the steps of:

Determine the third characteristic of giving described laminate by the 4th kind of material, wherein said second kind of material balance described the third characteristic of described laminate.

40. the method for claim 39, wherein said the 4th kind of material is melamine resin.

41. the method for claim 39, wherein said the third characteristic are that it can protect laminate to avoid the influence of external factor by described the 4th kind of protection feature that material provides.

42. the method for claim 24, wherein said first kind of material are not easy and described second kind of material bonding.

43. the method for claim 24, the step of wherein said the third material of selection is further comprising the steps of:

Determine described second kind of amount of substance, to apply first of first kind of laminated material and to give described laminate with described second specific character; And

Use described second kind of material of described definite amount to apply described first of described first kind of laminated material.

44. the method for claim 43, it is further comprising the steps of:

Determine described the third amount of substance, to apply second of first kind of laminated material and to give described first kind of laminated material with described compatible properties; And

Use described the third material of described definite amount to apply described second of described first kind of laminated material.

45. the method for claim 44, it is further comprising the steps of:

Place described first kind of laminated material, described the third material coated side of wherein said first kind of laminated material is towards the described ground floor of described laminate.

46. the method for claim 45, it is further comprising the steps of:

Use second kind of material to apply first of second kind of laminated material, to give described laminate with described second specific character; And

Use described the third material to apply second of described second kind of laminated material.

47. the method for claim 46, it is further comprising the steps of:

Place described second kind of laminated material, described second kind of material coated side of wherein said second kind of laminated material is towards described second kind of material coated side of described first kind of laminated material.

48. the method for claim 45, it is further comprising the steps of:

Use second kind of material to apply second kind of laminated material on two-sided, wherein said second kind of laminated material is adjacent to described second kind of material coating surface of described first kind of laminated material.

49. the method for claim 48, wherein said second kind of laminated material is the brown paper sheet material.

50. the method for claim 48, wherein said second kind of laminated material is the veneer sheet material.

51. the method for claim 48, wherein said another kind of laminated material are to be suitable for the sheet material that soaks into resin.

52. the method for claim 51, wherein said resin is selected from phenolic resins and melamine resin.

53. the method for claim 24, it is further comprising the steps of:

Determine described second kind of amount of substance, generate required physical characteristic when comprising the described laminate of described first kind of material, described second kind of material and described the third material in generation.

54. the method for claim 53, wherein said physical characteristic are the hogging bendings of described laminate.

55. the method for claim 54 wherein need not to regulate the characteristic of other layer of described laminate, described hogging bending can reach with expecting.

56. a floor comprises:

The ground floor of protection material on the described floor of protection that can avoid the influence of external factor;

Second decorative layer of adjacent described ground floor is to provide required combination with decorative surfaces to described floor;

The 3rd layer of resin impregnating brown paper, wherein said second decorative layer is between described the 3rd layer and described ground floor;

The 4th layer of brown paper;

The layer 5 of balance material, but the described ground floor of the described protection material of wherein said layer 5 balance, wherein said the 4th layer between described the 3rd layer and described layer 5;

The layer 6 of the impermeable material of liquid, the impermeable material of wherein said liquid are not easy and described balance material bonding, and wherein said layer 5 and described layer 6 are close mutually; And

The layer 7 of bonding material, wherein said bonding material are easy to be bonded on described balance material and the impermeable material of described liquid, and wherein said layer 7 is between described layer 6 and described layer 5.

57. the floor of claim 56, it also comprises:

Ground between described the 3rd layer and described the 4th layer.

58. the floor of claim 57, wherein said ground are wooden substrate materials.

59. the floor of claim 58, wherein said wooden substrate material selects glued board, flakeboard, particieboard, medium density fibre board (MDF) and high density fiberboard.

60. the floor of claim 57, wherein said ground are non-wood substrate materials.

61. being selected from, the floor of claim 60, wherein said non-wood substrate material reclaim plastics, acrylonitrile-butadiene-styrene (ABS) (ABS) copolymer, nylon, polystyrene, polyolefin and PVC.

62. the floor of claim 61, wherein said non-wood substrate material comprises inorganic filler.

63. the floor of claim 57, it also comprises:

The 8th layer of resin impregnating brown paper, wherein said the 8th layer between the 3rd layer on resin impregnating brown paper and described ground.

64. the floor of claim 63, wherein the described layer 5 with the balance material is coated on the relative reverse side of brown paper sheet material with the described layer 7 of bonding material.

65. the floor of claim 64, wherein said layer 5 depends in part on the penetration degree of described balance material in described brown paper sheet material from the distance of described layer 6.

66. the floor of claim 65, it also comprises:

Protection the 9th layer of material, giving the protection feature of described floor to strengthen, and wherein said the 9th layer between the described ground floor and the described second layer.

67. the floor of claim 66, wherein said the 4th layer scribbles described balance material and described bonding material on opposing face, and wherein said the 4th layer balance material coating surface is towards described layer 5.

68. the floor of claim 66, wherein said the 4th layer scribbles described balance material on two-sided.

69. resin impregnating is used for wherein said the 4th layer in the floor of claim 66.

70. the floor of claim 69, it also comprises:

The tenth layer of melamine resin dipping veneer sheet material, the wherein said ten layer between described the 4th layer and described layer 5.

71. the floor of claim 56, wherein said protection material is a melamine resin.

72. the floor of claim 56, wherein said balance material is a melamine resin.

73. the floor of claim 56, the impermeable material of wherein said liquid is a styrene-maleic anhydride copolymer.

74. the floor of claim 56, wherein said bonding material is a phenolic resins.

75. the floor of claim 56, wherein said layer 5 and layer 6 require to be placed on the same position on described floor.

76. a floor comprises:

Can protect described floor to avoid the ground floor of protection material of the influence of external factor;

The second layer of balance material, but the described ground floor of wherein said second kind of described protection material of material balance;

Can generate the 3rd layer of material of the impermeable characteristic of liquid, wherein said material is not easy to be bonded on the described balance material, the wherein said second layer and described the 3rd layer mutual close; And

The 4th layer of bonding material, wherein said bonding material is bonded on described balance material and the impermeable material of described liquid easily, wherein said the 4th layer between the described second layer and described the 3rd layer.

77. the floor of claim 76, it also comprises:

Ground between the described ground floor and the described second layer.

78. the floor of claim 77, wherein said ground are wooden substrate materials.

79. the floor of claim 77, wherein said ground are non-wood substrate materials.

80. the floor of claim 77 wherein is coated in the described second layer of balance material and described the 4th layer of bonding material on the opposing face of brown paper sheet material.

81. the floor of claim 80, it also comprises:

The layer 5 of protection material, to give the protection feature of described floor to strengthen, wherein said layer 5 is between described ground floor and described ground.

82. the floor of claim 81, it also comprises:

The layer 6 of brown paper sheet material, wherein said layer 6 scribble described balance material and described bonding material on opposing face, the described balance material coating surface of wherein said layer 6 is towards the described second layer.

83. the floor of claim 76, wherein said protection material is a melamine resin.

84. the floor of claim 76, wherein said balance material is a melamine resin.

85. the floor of claim 76, the described material that wherein can generate the impermeable characteristic of liquid is a styrene-maleic anhydride copolymer.

86. the floor of claim 76, wherein said bonding material is a phenolic resins.

87. the floor of claim 76, wherein said layer 5 and layer 6 require to be placed on the same position on described floor.

88. the floor of claim 76, it also comprises:

Adjacent to the 7th decorative layer of described ground floor, in order to provide required combination with decorative surfaces to described floor; And

The 8th layer of resin impregnating brown paper, wherein said the 7th decorative layer is between described ground floor and described the 8th layer.

89. the decorative panel as the floor comprises:

Decorative layer; And

The substrate layer that is attached to described decorative layer, wherein said substrate layer comprises:

The impermeable sublayer of first liquid can prevent moisture penetration basically;

The second layer of poising agent is used at least one sublayer of the described decorative layer of balance, wherein said first and second layers mutually near and be difficult for bonding mutually; And

The 3rd layer of binding agent, wherein said binding agent easily with described first and second layers in the bonding of one deck at least, wherein said the 3rd layer between described first and second layers.

90. the decorative panel of claim 89, the impermeable sublayer of wherein said liquid is the styrene-maleic anhydride copolymer layer.

91. the decorative panel of claim 89, wherein said poising agent are melamine resin.

92. the decorative panel of claim 89, the wherein said second layer are melamine dipping veneer sheet materials.

93. the decorative panel of claim 89, the wherein said second layer and described the 3rd layer are the opposing faces of brown paper sheet material, wherein said poising agent is that melamine resin and described binding agent are phenolic resins.

94. the decorative panel of claim 93, the described phenolic resins coating surface of wherein said brown paper sheet material is connected to the impermeable sublayer of described liquid.

95. the decorative panel of claim 94, it also comprises:

Be impregnated with the 4th brown paper sheet material of phenolic resins, wherein said the 4th brown paper sheet material is adjacent to the described second layer, away from the impermeable sublayer of described first liquid.

96. the decorative panel of claim 94, it also comprises:

The 5th balance layer, wherein the described second layer of poising agent is between described the 5th balance layer and the impermeable sublayer of described first liquid.

97. the decorative panel of claim 96, wherein said the 5th balance layer is the brown paper sheet material, scribbles melamine resin on its one side, scribbles phenolic resins on the another side.

98. the decorative panel of claim 97, the melamine resin coated side of wherein said the 5th balance layer are connected on the described melamine coated side of described second balance layer.

99. the decorative panel of claim 93, the phenolic resins coated side of wherein said brown paper sheet material is towards the impermeable sublayer of described first liquid.

100. the decorative panel of claim 89, wherein said binding agent are phenolic resins.

101. the decorative panel of claim 100, it also comprises:

Be impregnated with another brown paper sheet material of phenolic resins, wherein said another brown paper sheet material is adjacent to the described second layer of poising agent, away from described the 3rd layer of binding agent.

102. a method of producing laminate may further comprise the steps:

Select first kind of material, to give described laminate with first kind of desirable characteristics;

Select second kind of material, to give described laminate with second kind of desirable characteristics, wherein said first kind of material and described second kind of material are not being allowed at least in one aspect mutually;

Make the ground floor that comprises described first kind of material close mutually with the second layer that comprises described second kind of material;

The third material of selection and described first kind and second kind substances compatible, the 3rd layer of wherein said the third material between the described ground floor and the described second layer; And

Determine described second kind of amount of substance, generate required physical characteristic when comprising the described laminate of described first kind of material, described second kind of material and described the third material in generation.

103. the method for claim 102, wherein said physical characteristic are the hogging bendings of described laminate.

104. the method for claim 103 wherein need not to regulate the characteristic of other layer of described laminate, described hogging bending can reach with expecting.

105. the method for claim 104, it is further comprising the steps of:

Use described second kind of material of described definite amount to apply first of first kind of laminated material.

106. the method for claim 105, it is further comprising the steps of:

Determine a certain amount of described the third material that is coated on second of described first kind of laminated material, to give described first kind of laminated material with described compatible properties;

Use described the third material of described definite amount to apply second of first kind of laminated material; And

Place described first kind of laminated material, described the third material coated side of wherein said first kind of laminated material is towards the described ground floor of described laminate.

107. the method for claim 106, it is further comprising the steps of:

The 4th layer of the 4th kind of material is provided, wherein said first kind of laminated material balance described the 4th layer.

108. the method for claim 107, it is further comprising the steps of:

The layer 5 of described the 4th kind of material is provided, and wherein said layer 5 is adjacent to described the 4th layer.

109. according to the method for claim 108, it is further comprising the steps of:

Use described second kind of material of scheduled volume to apply first of second kind of laminated material, the described scheduled volume of wherein said second kind of material is based on the required hogging bending that will provide to the gained laminate;

Use the third material to apply second of described second kind of laminated material; And

Place described second kind of laminated material, described second kind of material coated side of wherein said second kind of laminated material is towards described second coated side of described first kind of laminated material.

110. the method for claim 102, wherein said first kind of desirable characteristics is the liquid impenetrability.

111. require 102 method, wherein said second kind of desirable characteristics is equilibrium response.

112. the method for claim 102, wherein said first kind of material is styrene-maleic anhydride copolymer.

113. the method for claim 102, wherein said second kind of material is melamine resin.

114. the method for claim 102, wherein said the third material is a phenolic resins.

115. the method for claim 102, wherein said the 4th kind of material is melamine resin.

116. the method for claim 105, wherein said first kind of laminated material is the brown paper sheet material.

117. the method for claim 109, wherein said second kind of laminated material is suitable for soaking into resin.

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