CN1942255A - Coated substrate - Google Patents
Coated substrate Download PDFInfo
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- CN1942255A CN1942255A CNA200580011919XA CN200580011919A CN1942255A CN 1942255 A CN1942255 A CN 1942255A CN A200580011919X A CNA200580011919X A CN A200580011919XA CN 200580011919 A CN200580011919 A CN 200580011919A CN 1942255 A CN1942255 A CN 1942255A
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- China
- Prior art keywords
- melamine
- formaldehyde resin
- base material
- dispersion
- lining base
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
- B05D3/0263—After-treatment with IR heaters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/20—Wood or similar material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31942—Of aldehyde or ketone condensation product
- Y10T428/31949—Next to cellulosic
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Finished Plywoods (AREA)
Abstract
The invention relates to a method to coat a substrate with a melamine-formaldehyde resin comprising the following steps: a) Applying a layer of powderous melamine-formaldehyde A resin to a substrate, b) Melting the melamine-formaldehyde resin by IR- or NIR- radiation, c) Optionally applying an ink, dye solution or pigment dispersion to the with molten melamine-formaldehyde resin coated substrate, d) Optionally applying a layer of melamine-formaldehyde resin B to the coated substrate from step b) or c), e) laying the coated substrate in the laminating press, f) Optionally heating the coated substrate from the previous steps in a laminating press for a certain amount of time, g) Increasing the pressure in the laminating press and keeping the laminate under pressure for a certain amount of time. The invention also relates to the coated substrate and its use.
Description
The present invention relates to the method for coated substrate (substrate).The invention still further relates to by available lining base material of this method (coated substrate) and the purposes in postforming technology thereof.
The method of coated substrate can be learnt from US 3730828, the document has been described the post-formable base material that is coated with ornamental barrier plate, and this ornamental barrier plate is made of the common chemical cellulose wood-fibred with the narrow melamine-formaldehyde resin dipping of the molar ratio range of formaldehyde completely crued, not plasticizing and melamine.By assembling a plurality of layers of kraft paper with the melamine-formaldehyde resin of not plasticizing and stopping that top board is with the preparation lamination.By with being placed on a period of time in the laminating machine under high pressure and the high temperature of these stacks, these all carrier layer are formed in the lamination.The shortcoming of the lamination that obtains thus is it can't be curved complicated shape and do not rupture and/or broken along two (or more a plurality of) cross one another axle.
Described a kind of stratiform pre impregnated material among the WO 99/13000, it comprises the one or more layered vector layers with the uncured resin dipping.This carrier is layered porous polymer.Layered porous polymer can be open foam of polymers of non-woven layer shaped polymer, stratiform or microporous barrier.Layered porous polymer floods with resin, afterwards need be dry under 100-160 ℃ temperature.After drying with the carrier stack that obtains.Subsequently, at high temperature solidify formed intermediate products then by at first making pre impregnated material (prepreg) distortion, or, pre impregnated material can be processed into the final products of shaping by deforming step and curing schedule are merged into a step.Shortcoming according to the pre impregnated material of WO 99/13000 is that this stratiform pre impregnated material comprises at least two kinds of components that must at first obtain in different steps: layered porous polymer and (the pre-preg stage) uncured resin.
WO 00/53666 has described a kind of pre impregnated material that comprises one or more porous carrier flaggies, and wherein the porous carrier plate is by still uncured resin dipping, and carrier comprises the meltable polymer that mixes with cellulose or regenerated cellulose or its mixture.WO 00/53667 has described a kind of pre impregnated material that comprises one or more porous carrier flaggies, and wherein by still uncured resin dipping, carrier is based on the porous carrier of regenerated cellulose wholly or in part to the porous carrier plate.WO 00/53688 has described a kind of pre impregnated material that comprises one or more porous carrier flaggies, and wherein the porous carrier plate comprises at least a fibre shape cellulose ester.These are that the initial period in the pre-preg stage promptly needs at least two kinds of components based on the shortcoming as the system of the porous polymer of carrier and (the pre-preg stage) uncured resin.
The objective of the invention is to overcome above-mentioned shortcoming and a kind of method with the melamine-formaldehyde resin coated substrate is provided, this method is compared simpler with the method for prior art, and can make coated base material still have the favorable mechanical performance.And the favorable mechanical performance be the lining base material carry out under the postforming situations such as (post-forming) necessary subsequently.
Above-mentioned purpose realizes by the method that may further comprise the steps:
A) layer that will comprise melamine-formaldehyde resin A is coated on the base material, forms the lining base material thus;
B) alternatively, with IR radiation or the described lining base material of NIR radiation treatment;
C) alternatively, ink, dye solution or pigment dispersion are coated on the described lining base material;
D) alternatively, will comprise melamine-formaldehyde resin B the layer be coated on derive from step b) or c) described lining base material on;
E) described lining base material is placed in the forcing press;
F) alternatively, in described forcing press, described lining base material is heated the quantitative time;
G) pressure in the described forcing press of raising, and under pressure, keep the described quantitative time of lining base material.
In the method for the invention, do not need the carrier such as paper or other cellulosic-based material or porous polymer is flooded and drying.In fact, in one embodiment of the invention, the layer that comprises melamine-formaldehyde resin A does not comprise such carrier.Similarly, preferably, the layer that optionally comprises melamine-formaldehyde resin B does not comprise carrier.In this case, flood with dry prior art with needs and to compare, the present invention can reduce the required space and the equipment of technology of coated substrate.Another advantage of method of the present invention is that the stack respectively of each layer no longer is necessary.Another advantage of method of the present invention is that coating directly is coated on the base material that needs to apply for long-term the use, for example the front of the surface of cabinet or kitchen cabinet.There is not independent " pre-preg stage " in this method.
If the layer on the lining base material does not comprise carrier, method then of the present invention also has the following advantages: the method lining base material that can get can carry out postforming step along two or more bending shafts to it thus; This postforming step is also referred to as three-dimensional (3D-forming).And, owing to preferably do not have carrier, reduced the waste material amount that produces in the lining substrate preparation process.
In the step a) of method of the present invention, a layer is coated on the base material, and this layer comprises melamine-formaldehyde resin A.The coating of this layer causes having formed the lining base material.Melamine-formaldehyde resin A is understood that with melamine and the formaldehyde resin as the primary structure unit.Melamine-formaldehyde resin A also can contain: other construction unit, for example urea; Flexibilizer, for example diethylene glycol and sugar; And other compound well known by persons skilled in the art, for example catalyst.In addition, according to the present invention, formaldehyde can partially or completely be replaced by another kind of suitable compound; The example of such compound is an alkanol hemiacetal, for example methyl acetaldehyde acid methanol hemiacetal (GMHA) and the 3rd page of disclosed hemiacetal of WO 03/101973 A2.Melamino-formaldehyde resin A can comprise or even form by following substances basically: the combination of any appropriate of the resin (melamine-formaldehyde resin D) of the resin of powder type (melamine-formaldehyde resin C), dispersion form, the resin (melamine-formaldehyde resin E) of liquid form or these resins.A kind of preferred embodiment in, melamine-formaldehyde resin A comprises at least 40wt%, 50wt%, 60wt%, 70wt% even 80wt%, 90wt% or Powdered melamine-formaldehyde resin C and/or the melamine-formaldehyde resin dispersion D of 100wt% basically.This advantage that has is to have reduced the possibility of resin transfer in the base material.Preferably do not use carrier; Because the present invention does not less even need at high temperature impregnated carrier to be carried out drying, this method is favourable from economy and ecological view.The weight ratio of Powdered melamine-formaldehyde resin C and melamine-formaldehyde resin dispersion D (representing with relative weight percentage) can change in wide region, for example 1%: 99%-99%: 1%, more preferably 10%: 90%-90%: 10%, 25%: 75%-75%: 25%, or 40%: 60%-60%: 40%.More preferably, melamine-formaldehyde resin A is made up of Powdered melamine-formaldehyde resin C basically.This advantage that has is, finishes in the pattern that is formed by ink, dye solution or pigment dispersion (can at optional step c), sees below) can remain intact to the full extent.Method of the present invention this preferred embodiment in, Powdered melamine-formaldehyde resin C is coated on the substrate surface, thereby forms layer.Powder here reaches and hereinafter is meant the solid of being made up of granule, and wherein the size of particle is usually less than 250 μ m, preferably less than 100 μ m.Compare with using smaller particles, very big particle is difficult to evenly distribute at substrate surface, and then makes at optional step c) in the resolution ratio of the coated pattern that forms by ink, dye solution or pigment dispersion relatively poor.The thickness of layer is not particular importance, and can select in wide region, for example 20-500 μ m.Preferred layer thickness is 50-250 μ m.Thicker layer helps covering the defective on the substrate surface, and thin layer is more favourable for postforming, should average out by between.How obtaining powder from melamine-formaldehyde resin, this it is known to those skilled in the art that." Kunststoff Handbuch, the 10-Duroplaste " that W.Becker, D.Braun showed that can publish in 1998 with reference to Carl Hanser Verlag, particularly with reference to " Melaminharze " chapter, the 41st page and other.Glass transition temperature (the T that can be used for the Powdered melamine-formaldehyde resin C in the step a)
g) should be enough high, so that it at room temperature exists with the powder type long-term stability.If T
gNot high enough, then resin particle can condense and powder can be lost its form and stability.T
gDesired value be at least 30 ℃, preferred 40 ℃, more preferably 60-90 ℃.T
gShould be lower than the step f) of carrying out this method and/or the temperature of step g); Because work as T
gWhen being higher than the temperature of step f), thereby resin can not melt and can't flow.Therefore, T
gUsually should be lower than 140 ℃, preferably be lower than 120 ℃.
Melamine-formaldehyde resin A can comprise melamine-formaldehyde resin dispersion D alternatively.In this manual, melamine-formaldehyde resin dispersion D is understood to mean a kind of like this system, wherein for example the liquid of water or alcohol is continuous phase, and this continuous phase comprises undissolved granule, and described particle comprises the melamine-formaldehyde of uncured, partly solidified or complete cure states.The preparation method of this dispersion describes in WO97/07152, EP 1099726 A2 and US 6245853 B1 etc. to some extent.Described particle itself can be a liquid or solid.Although the size of discrete particles can change in wide region, preferably its weight average size between 0.1 μ m and 100 μ m, more preferably 0.5-75 μ m, 1-50 μ m, 1.5-25 μ m, or even 1.75-15 μ m, or 2-10 μ m, or 5 μ m.Such dispersion itself is known; Be known that equally in order to obtain stable dispersion, the use of dispersant/protecting colloid normally favourable or even necessary.In this manual, term " is stablized " can have two implications: behind the one, dispersion preparation, discrete particles keeps not separating out, noncondensing or do not precipitate at least 30 minutes (even at least 1 hour, or preferably at least 24 hours); Perhaps its two, under the situation of separating out, condensing or precipitating, can easily it be disperseed once more by stirring at discrete particles.
As general recommendation, should note preferably avoiding the cohesion degree of discrete particles too high, so that these particles can't carry out the curing of method of the present invention in the mode that particle is bonded to each other.Similarly, should note preferably avoiding the state of cure of discrete particles too high, so that these particles can't carry out the further curing of method of the present invention in the mode that particle is bonded to each other.
The list of references of being quoted discloses the various suitable dispersant that is used to prepare stable melamine-formaldehyde resin dispersion D.In general, dispersant is usually derived from solid-state or liquid long-chain polymer, and described polymer is converted to the form that is dissolvable in water as in the liquid of dispersant continuous phase; This conversion is known, can comprise at high temperature handling described liquid, may be by means of other compound such as acid or alkali.Described dispersant is after with the liquid form preparation, and its pH preferably is lower than 9, more preferably less than 8 even 7; This advantage that has is, dispersant the do not slow down cohesion and/or the curing reaction of resin, and even may advantageously quicken these reactions (seeing below) to the discussion of step g).
Yet the shortcoming of known suitable dispersant is that the solids content of dispersion is quite low; For example in WO 97/07521, solids content is about 25%.The cumulative percent by weight of the whole compounds outside solids content is defined as dewatering calculates with raw material used in the preparation.Find surprisingly, comprise styrene maleic anhydride copolymer or be specially suitable by the dispersion of its derived compounds.More specifically, to be higher than the aqueous solution of 1500 styrene maleic anhydride copolymer be preferred to molecular weight.Therefore, the invention still further relates to the dispersion of liquid or solid melamine-formaldehyde resin particle in the liquid of preferred water or alcohol, described dispersion comprises dispersant, described dispersant comprises styrene maleic anhydride copolymer, described copolymer preferred processed so that its may be dissolved in the continuous phase of dispersion.In this manual, the term styrene maleic anhydride copolymer can refer to copolymer itself or the treated polymer in order to make its continuous phase that can be dissolved in dispersion.The advantage of using described copolymer is the stable melamine-formaldehyde resin dispersion D that can obtain solids content height (that is, greater than 30%, preferred 35%-65%).Preferably, the mean molecule quantity of styrene maleic anhydride copolymer (Mw) is greater than 1500,3000,10000,50000 even 100000; Preferably, described molecular weight Mw at the most 3000000 or 2000000, and more preferably at the most 1000000.The styrene in the copolymer and the mol ratio of maleic anhydride can change in wide region according to the present invention, and preferred 1: 0.1-1: 1, more preferably 1: 0.5-1: 1.Be known that the styrene maleic anhydride copolymer aqueous solution can be by at high temperature preparing with this copolymer of alkali treatment in water.The example of suitable styrene maleic anhydride copolymer is Scripset
520 (suppliers: Hercules; Molecular weight about 350000; The mol ratio of styrene and maleic anhydride is 1: 1).In another aspect of the present invention, styrene maleic anhydride copolymer also can be used for generating the stabilising dispersions of melamine particle in the liquid of for example water or alcohol.
Can be before melamine-formaldehyde resin and/or particle form reaction, during or in melamine-formaldehyde/liquid system, add dispersant afterwards.Depend on the specific nature of dispersant, liquid etc., also depend on the particle size that expectation obtains, the addition of dispersant can change in wide region.Preferably, melamine-formaldehyde dispersion D contains the dispersant of 0.01wt%-10wt%, more preferably 0.05wt%-7.5wt%, 0.2wt%-5wt% or 1wt%-3wt%.
Melamine-formaldehyde resin A can comprise liquid melamine-formaldehyde resin E alternatively.The preparation of liquid melamine-formaldehyde resin E it is known to those skilled in the art that, for example can know from above mentioned list of references " Kunststoff Handbuch, 10-Duroplaste " (" Melaminharze " chapter).In a kind of preferred implementation, melamine-formaldehyde resin A comprises liquid melamine-formaldehyde resin E and melamine-formaldehyde resin dispersion D.This advantage that has is, the lining base material that only comprises the liquid melamine-formaldehyde resin E of same amount (representing with solids content) with melamine-formaldehyde resin A is wherein compared, and the glossiness of the lining base material after the curing (being after step g) is finished) is higher.The weight ratio of liquid melamine-formaldehyde resin E and melamine-formaldehyde resin dispersion D (representing with relative weight percentage) can change in wide region, for example 1%: 99%-99%: 1%, more preferably 10%: 90%-90%: 10%, 25%: 75%-75%: 25%, or 40%: 60%-60%: 40%.Especially, for improving glossiness, 98%: 2%-85%: the combination of liquid melamine-formaldehyde resin E between 15% and melamine-formaldehyde resin dispersion D is preferred.Whether the layer that comprises melamine-formaldehyde resin A that no matter is coated on the base material comprises for example carrier of d é cor paper, all can be observed the raising of glossiness.In the present invention's a kind of embodiment in this respect, in order fully to help improving glossiness, and do not carry out step d).
When melamine-formaldehyde resin A comprised liquid melamine-formaldehyde resin E and melamine-formaldehyde resin dispersion D, Resin A may have the pasty state form.This advantage that has is it to be coated with in simple and controllable mode.
Melamine-formaldehyde resin A preferably can form non-porous layer after the curing of step g), thereby avoids contained component (for example water or air) to diffraction of light.Diffraction can cause " bluring " pattern.Be 1-3 by the ratio (mol ratio) that makes melamine in the Resin A and formaldehyde, can advantageously reach above-mentioned requirements.Alternatively, melamine-formaldehyde resin A can be by partial cross-linked before it is coated on the base material.Depend on the accurate composition of melamine-formaldehyde resin A, the precrosslink rate influences fluid ability.If precrosslink is carried out excessively, then Resin A can't be fully mobile, and can not remove whole contained components (for example air) by compacting.Those skilled in the art can easily determine the precrosslink rate of expectation.
The another kind of method that improves the possibility that forms non-porous layer is by selecting melamine-formaldehyde resin A so that it comprises the mixture of aforesaid Powdered melamine-formaldehyde resin C and melamine-formaldehyde resin dispersion D.
Melamine-formaldehyde resin A also can comprise color reaction material, for example pigment.In the case, the coating that finally obtains has the more or less color of homogeneous usually, and does not have specific discernible pattern.Under the situation of the such homogeneous color of needs, can omit optional step c), but may still need in step d), on layer A, to increase transparent top coat, thus obtain better outward appearance and durability.When in coating, needing d é cor pattern, then need step c) and d).
If melamine-formaldehyde resin A comprise Powdered melamine-formaldehyde resin C or even form by Powdered melamine-formaldehyde resin C basically, then described Powdered melamine-formaldehyde resin C should have such one group of character, so that it is at optional step b) in thawing after form porous layer.When resin particle melted, they flowed toward each other.Depend on the environment of flowing stage, and the given sufficiently long time, finally contact fully each other of melt granules, thus non-porous layer finally formed.Yet for optional step c), preferred or even must need have to a certain degree porous layer; This advantage that has is that the pattern that is coated with by ink, dye solution or pigment dispersion can remain intact in subsequent step of the present invention to a greater extent.In order to keep the porous of layer, when the time span of flowing stage when being medium, the temperature during the flowing stage is unsuitable too high.When the time that is used to flow more in short-term, then temperature should be higher.Therefore, should in determining the parameter of amount of flow, these find balance.Those skilled in the art can easily determine appropriate condition by normal experiment.
The kind of base material can for example be timber and wood-base materials, paper, metal, glass and plastics according to the final use of lining base material.The example of wood-base materials is MDF (medium-density fiberboard) and HDF (high density fiberboard), OSB (oriented wood chipboard), particle board, glued board.The lining base material can be used for widely applying, for example pallet, washbasin, earthenware, door, kitchen countertop, furniture and metope, cabinet, window-frame and laminate flooring.
According to the character of melamine-formaldehyde resin A and to the demand of lining base material, before carrying out step b), implement drying steps a1), may be useful, expectation or even necessary.Such drying steps itself is known, can carry out according to the guidance that those skilled in the art can get.
Optional step b in method of the present invention) in, the resin of coating is handled with infrared (IR) or near-infrared (NIR) radiation.Radiation in the near infrared range is meant the radiation of wavelength between 0.8 μ m and 1.5 μ m.If melamine-formaldehyde resin A comprises or even be made of then preferred especially implementation step b basically Powdered melamine-formaldehyde resin C); This advantage that has is to make layer have more caking property.The type of infra-red radiation can freely be selected in principle; Layer (for example thickness reaches 5 μ m) for thin preferably uses conventional IR radiation, and for thicker layer (reaching 0.5mm), preferably uses NIR to guarantee having suitable Temperature Distribution on whole layer thickness.The duration of radiation is depended on the intensity of radiation and the characteristic of processed resin.If melamine-formaldehyde resin A comprises or even form by Powdered melamine-formaldehyde resin C basically, if particularly adopted optional step c), then the duration of radiation and intensity should be enough to obtain the caking property layer, and also have maximum porosity.This can easily be determined by normal experiment by those skilled in the art.
At optional step c) in, d é cor pattern is coated on the lining base material.The coloured material that is used to form this pattern can be an ink, perhaps the dye solution in water, solvent or the polymer, the perhaps pigment dispersion in water, solvent or the polymer.Coloured material can be solid or liquid, and can be coated with by imaging technique arbitrarily, " Handbook of Imaging Materials " (Arthur S.Diamond ed. for example, Marcel Dekker, 1991) printing of Ke's formula (off-set printing) and the roller printing described in, ink jet printing, heat transmission printing, toner printing (tonerprinting) etc.
At optional step d) in, the layer that comprises melamine-formaldehyde resin B is coated on step a), b) and c) on the lining base material of back gained.Melamine-formaldehyde resin B can be with the form of liquid, dispersion, powder or these any combination.A preferred implementation, melamine-formaldehyde resin B is with powder type basically; This advantage that has is to have reduced the possibility that resin penetrates into the layer of following lining base material.According to the required character of final coating, the character of melamine-formaldehyde resin B can change, and preferably, resin B is a powder type, its T
gScope is identical with above-mentioned Powdered melamine-formaldehyde resin C; It is preferably at subsequent step f) and g) in temperature under have good flowability, and be solidified into transparent and anti-zoned top coat, so that the layer of its below or pattern are as seen, and by at next step f) or subsequent step f) and g) in by common reaction provide to its below layer excellent adhesion.For the layer that prevents the below is subjected to ambient influnence and deterioration, can in melamine-formaldehyde resin B, add stabilizing agent (for example hindered amine as light stabilizer (HALS)) and UV absorbent.In addition, in order to ensure better anti-zoned property, can in this resin, add for example inorganic filler of clay, silica and corundum and so on.Preferably, in order to keep optical transparency, use filler particles less than 300 nanometers.
At execution in step e) before, if optional step b), c) and d) in one be implemented, then depend on the character of melamine-formaldehyde resin A and, implement drying steps d ' the demand of lining base material) may be useful, expectation or or even necessary.Such drying steps itself is known, can carry out according to the guidance that those skilled in the art can get.
At step a) and optional step b), c), d) and d ') afterwards, the base material that will be covered in step e) places forcing press.Forcing press itself is known to those skilled in the art; An example of known pressure machine is a laminating machine.If the step before the step e) of the inventive method has been to carry out in forcing press, then the step e) base material that can be interpreted as only will being covered is stayed in the forcing press.
The lining base material in step f), is heated the quantitative time after being placed in the forcing press in forcing press.The absolute duration is not crucial.Time and temperature are independently, and promptly the gained result is relevant with time and temperature, but this result both can obtain by high temperature and relative short time, also can obtain by lower temperature and long period.For example, the time can change in 1-3 minute, and temperature can change in 100-140 ℃.Should weigh select time and temperature, so that state of cure can provide the acceptable matter relevant with the Kiton test with the glossiness of lamination.
Advantageously, at subsequent step g) in exert pressure before, the lining base material in step f) by precuring.Carry out this precuring and enter on base material or its side to reduce or to prevent that resin from flowing under pressure and preventing that resin is absorbed, this can have a negative impact to machinery and/or optical characteristics of lining base material.For example, by pre-cure step of the present invention, the possibility of (being formed in optional step c on the lining base material) image blur is lowered.For this purpose, can for example before the lining base material is loaded into wherein, forcing press be preheated.Perhaps, for example by using IR or NIR radiation, the lining base material can be pretreated in independent step, thereby obtain partly solidified coating.When using pigment, ink or dyestuff in the step c), above-mentioned two kinds of situations all can make resolution ratio better.Also discovery preheats or preliminary treatment has all obtained better top coat.
In step g), the lining base material stands high pressure, and keeps the quantitative time under pressure.The purpose of step g) is to make the layer in the lining base material reach partly solidified at least, but preferably solidifies fully.Pressure, time and temperature conditions are the common used conditions in curing field that contains the lamination of melamine.
The invention still further relates to the base material that the obtainable melamine of the method according to this invention-formaldehyde applies.This base material has the favorable mechanical performance.According to its further purposes, need satisfy various requirement, for example anti-zoned property, pliability, durability, chemical-resistant, wearability, cold brittleness (cold check) (crack resistance when being temperature shock).Depend on the final use of base material, some is more even more important than other in the above-mentioned character.According to the final use of lining base material, also need satisfy apparent requirement sometimes equally.
Compare with the lamination (at first prepare pre impregnated material, afterwards it is pressed on the base material) of prior art, the melamine that can get-formaldehyde coated substrate according to the present invention present improvement coating the layer and base material between adhesiveness.
The invention still further relates to the purposes of lining base material in postforming technology that the method according to this invention can get; This advantage that has is, the possibility of the lasting structural damage of lining base material (particularly its layer) is significantly reduced even is eliminated.
The invention still further relates to the melamine-formaldehyde resin of mol ratio between the 1-3 purposes in the method for the invention of formaldehyde and melamine.
Further set forth the present invention by following examples, but the present invention is not limited to these embodiment.
Embodiment 1
By formaldehyde and melamine mol ratio is that 1.7 commerce can get resin (Madurit MW 909) to form solids content is 65% melamine-formaldehyde resin, and with the ammonium sulfate of 3wt% to its catalysis, obtain Powdered melamine-formaldehyde resin C by it being carried out spray-drying.The spray-dried resin C of 0.018 gram is coated on the plank; The surface area that applies is 2cm * 6cm.Therefore melamine-formaldehyde resin A is made up of Powdered melamine-formaldehyde resin C fully.Suppressed this plate 4 minutes with the pressure of 69bar; Temperature during compacting is 140 ℃.As a result, compare with the known lamination of being made by impregnated carrier, the glossiness of lining base material is high and the surface is hard.
Embodiment 2
Moisture melamine-formaldehyde resin (Madurit MW 909) the preparation solids content that can be got by commerce is 65% resin, and with the ammonium sulfate of 3wt% to its catalysis, thereby obtain liquid melamine-formaldehyde resin E.In this embodiment, melamine-formaldehyde resin A100% is made up of described liquid melamine-formaldehyde resin E.Resin A is coated on the MDF plate; Layer thickness is 120 μ m; The surface area that applies is 10cm * 15cm.Suppressed this plate 4 minutes with the pressure of 26bar; Temperature during compacting is 140 ℃.As a result, the glossiness of lining base material is high and surperficial hard.
Embodiment 3
Preparation melamine-formaldehyde resin dispersion D
The preparation dispersion:
Preparation styrene maleic anhydride copolymer (Scripset
520, supplier: aqueous solution Hercules).Under agitation, in 455 gram water, slowly add 61 gram Scripset
520.After obtaining suitable non-caking slurries, add the NaOH aqueous solution of 50 gram 25wt%.Exothermic reaction takes place, and temperature rises to about 40 ℃.Then, under agitation material is heated to 80 ℃ and kept 45 minutes.If desired, pH is regulated (only heightening) to 6.5.
Synthetic MF dispersion: the pH that will add 406 gram 38.5wt% formalins of 199 gram water with 2M NaOH transfers to 9.0.Add 394 gram melamines; Then mixture is heated to backflow.After the melamine dissolving and obtaining settled solution, mixture is cooled to 82 ℃.Add the dispersant solution that 145 grams prepare previously then, use HNO
3The pH of mixture is transferred to 7, simultaneously this solution of vigorous stirring.After about 15 minutes, observe the unexpected transition point (promptly bleaching) of solution.This solution becomes shallow white opacity dispersion from milky.After transition point, the congealing reaction of this dispersion is proceeded 9 minutes, it is cooled to 20 ℃ then.After beginning to cool down 1 minute, the pH of dispersion is transferred to 8.6 with 5M NaOH.Need about 8 grams.When stirring, solution is cooled to 20 ℃ and it is stored in the plastic bottle.The solids content of the dispersion that obtains is 55%, and the mol ratio of its formaldehyde and melamine is 1.65.Dispersion is stable in a couple of days.
Preparation lining base material
With little doctor roll synthetic resin dispersion D is coated on the beech plate.In this embodiment, melamine-formaldehyde resin A100% is made up of resin dispersion D.After the wet dispersion of coating, coating presents white.At room temperature after the drying, coating becomes white surface.Under 150 ℃, in forcing press, suppress the lining base material 3 minutes of this drying with 30bar.After the compacting, obtain having the base material of as clear as crystal coating.
Embodiment 4
By being that 1.7 liquid melamine-formaldehyde resin E mixes with the melamine-formaldehyde dispersion D of embodiment 3 preparations with the formaldehyde and the mol ratio of melamine, preparing and comprise the two melamine-formaldehyde resin A of liquid melamine-formaldehyde resin E and melamine-formaldehyde dispersion D.The solids content of melamine-formaldehyde resin A is 58%, wherein 55% is derived from liquid melamine-formaldehyde resin E, and 3% is derived from melamine-formaldehyde dispersion D.In addition, melamine-formaldehyde resin A comprises the wetting agent Netzmittl PAT959/9 of 0.2wt% and the release agent of 0.2wt% (release agent) PAT-2523.
Munksjo D é cor paper (80g/m with melamine-formaldehyde resin A dipping 20cm * 20cm
2) the carrier fritter of form, then 100 ℃ dry 420 seconds down.Under 100kN and 190 ℃, impregnated paper carrier is laminated on the MDF plate then with 50 seconds.As known to persons skilled in the art, these conditions are representative conditions of the so-called LPL of preparation (being the low pressure lamination).Surprisingly, be 120 20 ℃ of glossiness of measuring the lamination of gained down, approximate the glossiness of HPL (high pressure laminating).As known to persons skilled in the art, the glossiness of the known LPL that makes with the single-steeping carrier is lower than HPL, is generally 95-100 when measuring down for 20 ℃.
Claims (7)
1. the method for coated substrate comprises step:
A) layer that will comprise melamine-formaldehyde resin A is coated on the base material, forms the lining base material thus;
B) alternatively, with IR radiation or the described lining base material of NIR radiation treatment;
C) alternatively, ink, dye solution or pigment dispersion are coated on the described lining base material;
D) alternatively, will comprise melamine-formaldehyde resin B the layer be coated on derive from step b) or c) described lining base material on;
E) described lining base material is placed in the forcing press;
F) alternatively, in described forcing press, described lining base material is heated the quantitative time;
G) pressure in the described forcing press of raising, and under pressure, keep the described quantitative time of lining base material.
2. method as claimed in claim 1, wherein said layer and the optionally described layer that comprises melamine-formaldehyde resin B that comprises melamine-formaldehyde resin A do not comprise carrier.
3. as the method for claim 1 or 2, wherein melamine-formaldehyde resin A comprises Powdered melamine-formaldehyde resin C and/or melamine-formaldehyde resin dispersion D.
4. method as claimed in claim 1, wherein melamine-formaldehyde resin A comprises melamine-formaldehyde resin dispersion D, and wherein said melamine-formaldehyde resin dispersion D comprises dispersant, and described dispersant comprises styrene-maleic anhydride copolymer.
5. pass through as the available lining base material of the method for any one among the claim 1-4.
6. the purposes of lining base material as claimed in claim 5 in postforming technology.
7. the dispersion of liquid or solid melamine-formaldehyde resin particle in liquid, described dispersion comprises dispersant, it is characterized in that, and described dispersant comprises styrene maleic anhydride copolymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP04076083.7 | 2004-04-08 | ||
| EP04076083A EP1584378A1 (en) | 2004-04-08 | 2004-04-08 | Coated substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1942255A true CN1942255A (en) | 2007-04-04 |
Family
ID=34896061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200580011919XA Pending CN1942255A (en) | 2004-04-08 | 2005-04-08 | Coated substrate |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US20070224438A1 (en) |
| EP (2) | EP1584378A1 (en) |
| JP (1) | JP2007532343A (en) |
| CN (1) | CN1942255A (en) |
| AU (1) | AU2005230952A1 (en) |
| BR (1) | BRPI0509615A (en) |
| CA (1) | CA2559795A1 (en) |
| EA (1) | EA011590B1 (en) |
| MY (1) | MY145516A (en) |
| NO (1) | NO20065139L (en) |
| TW (1) | TW200613067A (en) |
| WO (1) | WO2005097874A2 (en) |
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-
2004
- 2004-04-08 EP EP04076083A patent/EP1584378A1/en not_active Withdrawn
-
2005
- 2005-04-07 TW TW094111061A patent/TW200613067A/en unknown
- 2005-04-08 BR BRPI0509615-4A patent/BRPI0509615A/en not_active IP Right Cessation
- 2005-04-08 EA EA200601878A patent/EA011590B1/en not_active IP Right Cessation
- 2005-04-08 WO PCT/NL2005/000272 patent/WO2005097874A2/en active Application Filing
- 2005-04-08 US US10/594,395 patent/US20070224438A1/en not_active Abandoned
- 2005-04-08 AU AU2005230952A patent/AU2005230952A1/en not_active Abandoned
- 2005-04-08 CN CNA200580011919XA patent/CN1942255A/en active Pending
- 2005-04-08 JP JP2007507262A patent/JP2007532343A/en not_active Withdrawn
- 2005-04-08 EP EP20050737677 patent/EP1735112A2/en not_active Withdrawn
- 2005-04-08 CA CA 2559795 patent/CA2559795A1/en not_active Abandoned
- 2005-04-08 MY MYPI20051570A patent/MY145516A/en unknown
-
2006
- 2006-11-07 NO NO20065139A patent/NO20065139L/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538800B (en) * | 2009-04-23 | 2012-06-13 | 合肥市东方美捷分子材料技术有限公司 | Thermoplastic resin coating film material and preparation method thereof |
| CN103459153A (en) * | 2011-04-12 | 2013-12-18 | 瓦林格创新股份有限公司 | A powder mix and a method for producing a building panel |
| CN103459153B (en) * | 2011-04-12 | 2016-06-08 | 瓦林格创新股份有限公司 | Mixture of powders and the method producing building panel |
| CN104903105A (en) * | 2013-01-11 | 2015-09-09 | 瓦林格创新股份有限公司 | A method of producing a building panel |
| CN104903105B (en) * | 2013-01-11 | 2017-07-28 | 瓦林格创新股份有限公司 | The method for manufacturing building panelling |
Also Published As
| Publication number | Publication date |
|---|---|
| EA200601878A1 (en) | 2007-02-27 |
| EA011590B1 (en) | 2009-04-28 |
| TW200613067A (en) | 2006-05-01 |
| BRPI0509615A (en) | 2007-09-18 |
| AU2005230952A1 (en) | 2005-10-20 |
| WO2005097874A2 (en) | 2005-10-20 |
| MY145516A (en) | 2012-02-29 |
| US20070224438A1 (en) | 2007-09-27 |
| CA2559795A1 (en) | 2005-10-20 |
| WO2005097874A3 (en) | 2006-03-02 |
| EP1735112A2 (en) | 2006-12-27 |
| NO20065139L (en) | 2007-01-08 |
| EP1584378A1 (en) | 2005-10-12 |
| JP2007532343A (en) | 2007-11-15 |
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