CN100500427C - Resin-covered metal sheet, pattern sheet for resin -covered metal sheet, and process for the production of resin-covered metal sheet - Google Patents

Abstract

A resin-covered metal sheet excellent in durability (resistance to moist heat) which is obtained by laminating a metal sheet with a laminated sheet consisting of at least two unstretched layers (layers A and B) made mainly of a polyester resin via an adhesive with the layer B side employed as the adhesive surface, wherein the laminated sheet has a total thickness of 65 to 300mum and a pigment for coloring and hiding is incorporated mainly into the layer A, with the layers A and B having thicknesses of 50 to 250mum and 15 to 80mum respectively and with the amount of the pigment component contained in the layer B being limited to at most 10 parts by weight per 100 parts by weight of the resin component. Further, resin-covered metal sheets having good embossed appearance can be provided by the use of a current embossing machine used in embossing flexible PVC sheets.

Description

The design thin plate that resin-covered metal sheet, resin-covered metal sheet are used and the manufacture method of resin-covered metal sheet

Technical field

The present invention relates to be used for tame electrical article external packing such as AV machine or air conditioner cover, three-ply board system furniture, steel furniture, elevator upholstery, and the resin-covered metal sheet of the excellent in te pins of durability of building interior ornament materials purposes such as window material, bathroom, unit (unit bath) wall material, bathroom, unit ceiling material, dividing plate, design thin plate that resin-covered metal sheet is used and the manufacture method of resin-covered metal sheet.Further relate to anti-wound property, excellent in workability, and the excellent in te pins of durability under the hygrothermal environment be applicable to purposes such as bathroom, unit, and be applicable to that dividing plate etc. has the resin-covered metal sheet covering purposes, that do not use the Halogen resin of embossed pattern design, design thin plate that resin-covered metal sheet is used and the manufacture method of resin-covered metal sheet.

Background technology

The resin-covered metal sheet that in the past was used for such use is, utilizing the painted soft PVC of pigment is the laminated product of thin plate (below be called " flexible PVC thin plate ") and the goods that covered the flexible PVC thin plate of having given the embossed pattern design on synthetic resin formed product or three-ply board, wood fiber plate, metallic plate etc.

The advantage of flexible PVC thin plate is listed below:

1. the adaptability excellence is given in embossing, therefore can obtain the good cladding material of design.

2. the anti-key element of the two rule back ofs the body that general thermoplastic resin has is that the property taken into account of processability and surperficial injured property is comparatively good.

3. with the compatibility excellence of various additives, carried out the raising research of additive all the year round, therefore improved against weather, especially light fastness stability easily rerum natura.

In addition, also laminate by calendering system embrane method easily, therefore the time-consuming system film of extruding is compared with cleaning when the colour changing, also has very big advantage for the expansion of multicolour pattern.

As the method for giving embossing for the rectangular thin plate continuity of this flexible PVC, the general method of using is, the thin plate behind the system film heated again make it softening, uses the roller that is carved with the embossing decorative pattern (below be called the embossing plate roller) to push down the continuously transfer printing decorative pattern.The contact-type that the method for heating thin plate can be considered to heat as the metallic roll that is contacted with after the heating, the non-contact type that under the condition of touch roll not, heats with infrared heater, storage heater etc. etc.In actual manufacturing line, can use any means wherein, but be used in combination mostly usually, the equipment with this a succession of operation is called embossing gives machine.

Give machine the design that can be very easy to exchange loading and unloading embossing plate roller generally in vogue for this embossing, by preparing multiple embossing plate roller, can be easily and change the embossing decorative pattern economically, be the embossing adding method that is adapted to small lot batch manufacture therefore.The flexible PVC thin plate is given machine to this embossing giving of embossed pattern design also has excellent adaptability.

Though the flexible PVC thin plate has these features, but produce influences such as hydrogen chloride gas and other chlorine-containing gas problems during the polyvinyl chloride resin heavy metal compound problem that is subjected to causing, the VOC problem that causes by some plasticizer or stabilizing agent or endocrine disturbance problems in role, burning in recent years, be restricted in the use by some stabilizing agents.From using the comprehensive carrying capacity of environment viewpoint of polyvinyl chloride resin and non-operating position, its quality is still indeterminate, but the polyvinyl chloride resin is not used in users' strong request of these goods.

Therefore, by cooperating the soft composition based on the phenylethylene of vistanexes such as polypropylene or copolyalkenamer etc., obtaining near soft PVC is the goods of resin rerum natura, is resin with the soft PVC that replaces this pigmentary resin layer.In this constituted, vistanex is the resistance to chemical reagents excellence basically, and humidity resistance is also relatively better, therefore is suitable for purposes such as bathroom, unit.Further, polypropylene-based thin plate still can roll the system film, aspect small lot batch manufacture or corresponding color and no less than flexible PVC.Also have, though that polypropylene-based thin plate and PVC thin plate are compared the temperature range that can give embossing is narrower, need more precise dose control, advantage is can directly use the embossing that in the past is used for the PVC thin plate is given continuously embossing basically to give machine.But, when cooperating soft composition in a large number, also poor when the anti-wound property in surface is resin than the use soft PVC in order to give required processability.On the contrary, be resin-covered metal sheet when identical if make its anti-wound property and soft PVC, then can't obtain sufficient processability, therefore can't be extensive use of.Also have, polyolefin is the material of cementability difference in essence, therefore compares with flexible PVC, is giving the printed patterns design or will carry out more researchs aspect metallic plate bonding stacked, or appending many operations.Also have, consider, have the problem of peeling off in time with the interface of metallic plate from the durability aspect.

(1) gives the necessity of humidity resistance

As the scheme that solves processability and surface these two opposites of anti-wound property, selling on the market in recent years has the metallic plate that covers polyester based resin.But general polyester based resin is the hydrolysis and the material of embrittlement gradually under hygrothermal environment, when therefore under hygrothermal environments such as bathroom, unit, using, and the possibility that has appearance change in time or peel off etc. with metallic plate.

The thin plate that has carried out the stretch crystallization processing in the known polyester based resin can increase substantially humidity resistance.Also developed a kind ofly,, realized the technology of firm bonding force and good humidity resistance simultaneously by near under the condition of not losing non-bonding plane side crystalline orientation fusion lamination surface side surface bonding when stacked with the substrate metal plate.

But, when being used for purposes such as bathroom, unit, need giving machine with the embossing of giving design and give relief pattern the surface.But, the thin plate that carries out behind the stretch orientation is difficult to carry out, be heated to the temperature that can give embossed pattern and be the mylar fusing point when above stretch orientation will disappear.

Also have, cover on the thin plate of resin-covered metal sheet and add pigment in order to give design and hidden ground, but be subjected to the restriction conditions such as processability of preferred bright color and resin-covered metal sheet during purposes such as bathroom, unit, the thickness of laminated thin plate is restricted, therefore, use titanium oxide pigments as the disguised high pigment of white color system in the substrate more.In order to regulate its tone, need to use colored inorganic pigment or organic pigment simultaneously.For inorganic pigments such as titanium oxide pigments, himself play the deterioration catalyst action of mylar sometimes, and the impurity in the pigment promotes the polyester deterioration too.Also have, except pigment particles is special circumstances such as tabular form, the space that in general is formed between pigment particles and the resin matrix will increase the permeability of moisture in the lamella thickness direction.This also can become the reason that promotes mylar self deterioration, and during resin-covered metal sheet constituted simultaneously, the moisture that sees through increased the danger that generation is peeled off between thin plate layer and the metallic plate with corroding metal plate surface.

Therefore,, make the thin plate that does not add pigment and add titanium oxide base pigment, when making resin-covered metal sheet, can confirm that the latter's humidity resistance is compared significantly inferior with the former at the mylar that uses same composition.

But,, but be equal to the commodity value that loses as upholstery construction material purposes resin-covered metal sheet when not adding pigment no matter how guarantee durability easily.Therefore, improve the various tests that Chinese white adds the durability of system, wherein an example is exactly that pigment particles is carried out surface treatment with the method for deactivation catalyst activity and add method such as various catalyst inert agents.But its effect is abundant inadequately, and in general the method for pigment particles being carried out the special surface processing significantly improves cost, and the dispersiveness that gets both also is the problem of difficulty.

On the other hand, use a kind of being called arranged in the resin-covered metal sheet of flexible PVC thin plate " high minute surface product " material, this formation is to print at the flexible PVC thin sheet surface, further at good biaxial stretch-formed PET (PETG) film of its surperficial stacked flatness.

At this moment, promptly use not stretch and replace the flexible PVC thin plate,, see through, can obtain comparatively good humidity resistance so suppress moisture by this layer because of there is the PET film of biaxial stretch-formed mistake in its top layer by the polyester based resin sheeting of white color system pigment coloring.Also have, because of having the specular reflective of excellence, thus be applicable to the bathroom, unit, but this formation still can't obtain to give the goods of embossed pattern.

(2) give embossing stable on heating necessity

It is the amorphism polyester based resin etc. of representative that so-called PETG is also arranged, by having the adaptive goods of calendering system film to the research of lubricant etc.But with flexible PVC system or polyolefin thin plate were identical in the past, when using embossing to give machine to give embossing (calendering system embrane method), problem has appearred in the embossing hear resistance to the thin plate that is made of this resin.The embossing hear resistance is that the answer of its embossing is to be greatly little character when representing that embossed pattern design sheet or embossed pattern design sheet covered metal plate are in high temperature in the user mode process, and recovering little situation is the embossing good heat resistance.

Be that embossing is given and be can be understood as, after giving distortion to the viscoelastic body after the heating, the operation of freezing to be out of shape by cooling is if but be heated to the temperature of giving distortion to the distortion after freezing once again, the reply phenomenon that then deforms.Thereby, then need to improve the temperature of giving distortion if improve the embossing hear resistance.On the other hand, though can be described as the amorphism polyester based resin of giving calendering system film by the research lubricant, but give temperature (by thin plate temperature and the decision of embossing plate roll temperature) if improve distortion in order to improve the embossing hear resistance, then the fusion tension force of thin plate self significantly descends, the thin plate phenomenons such as the width of cloth, fold even thin plate fracture that contract take place, and can't give satisfied embossing hear resistance.

Its result, in actual environment for use, spill under the situation of Hot Coffee as the skin-material of desk etc. the time, perhaps under the situation as the bigger tame electric machine cabinet of internal calorific power, because of the embossing of embossing hear resistance deficiency part shoals or disappearance etc., cause bad order easily.

On the other hand, when utilizing extrusion molding to make the polyester based resin film, it is also conceivable that casting roller (casting roll) for the embossing patterned roll but not common mirror roller, the resin of the molten condition that flows out from the T mould is given the method (extruding the system embrane method) of embossing.This method can obtain higher embossing hear resistance easily, and can not consider that polyester based resin has or not transfer printing embossed pattern under the crystalline condition.But, can effectively make the thin plate film of small lot and various tones with calendering system embrane method and compare, extrude the system embrane method and when colour changing, lose more time and raw material, be not suitable for small lot batch manufacture.

Also have,, consider with holding together, do not give dark embossing or intricate detail embossing etc. into the air angle from release property about the embossing decorative pattern, more to the restriction of decorative pattern.Further, it is big that the diameter of casting roller is generally given the knurling rolls of machine than embossing, and the casting roller of getting all the ready corresponding to the decorative pattern number also becomes problem from equipment cost and exchange aspect in man-hour.

As additive method, in the manufacture method of resin-covered metal sheet, resin melt extrusion on copper coin used the roll-in of embossing decorative pattern the method for transfer pattern before the resin cooling, or heat the metallic plate that has covered resin sheet again, with the method for embossing patterned roll transfer printing.

In these methods, to the resin transfer embossing of molten condition, therefore no matter be that crystallinity polyester or amorphism polyester can both be given the embossed pattern design.But, with the system of extruding during film the situation with the carry-over pinch rolls transfer pattern identical, be subjected to the restriction of decorative pattern, and when the warpage portion of embossing plate roller and metallic plate end etc. contacts, have and make edition impaired danger, therefore need be equipped with several preparation rollers in the storehouse, still be a problem in the equipment cost aspect more.

Summary of the invention

In order to solve described problem, among one of the present invention, not the polyester based resin layer of La Shening by contain a large amount of pigment with mainly undertake the layer giving colored pattern design and give the hidden effect of bottom vision (below be called " A layer ") and, only contain layer (below be called " B layer ") this two-layer formation of the following pigment of 10 weight portions.Promptly, one of the present invention provides a kind of resin-covered metal sheet, it is characterized in that: at least by two-layer main component be polyester resin by tensile layer A layer not and not the B layer side of the laminated thin plate that constitutes of tensile layer B layer be stacked on the metallic plate through bond layer and constitute as bonding plane; The gross thickness of described laminated thin plate is 65 μ m～300 μ m, is used for painted and hidden pigment simultaneously and mainly is added on the A layer; Described A layer has the thickness of 50 μ m～250 μ m; When described B layer has 15 μ m～80 μ m thickness, to the pigment composition addition of described B layer being, is below 10 weight portions with respect to 100 parts by weight resin compositions, and described A layer side surface has been endowed embossing.One of the present invention by because of must add layer (A layer) that the abundant humidity resistance of the pigment layer self of amount has to descend and because of the few humidity resistance of pigment addition preferably layer (a B layer) be laminated into integrated securely, guarantee the humidity resistance of laminated thin plate integral body, further guarantee the humidity resistance of resin-covered metal sheet.Further,, suppress the transit dose of moisture, the security that thin plate that the corrosion of raising metal sheet surface causes and metallic plate are peeled off in time to metal sheet surface by having the few layer of pigment addition.The application of the invention constitutes, even also can give sufficient colored pattern design to the resin-covered metal sheet of the formation that is laminated with the not stretched polyester thin plate that can give embossing, and durability, especially humidity resistance is good.

According to the present invention two, do not contain pigment composition in fact by the B layer, can further improve durability.

According to the present invention three, the molecular weight of resinous principle is in particular range behind the B layer system film by making, even also can keep rerum natura after the deterioration in time.

According to the present invention four, by adding carbodiimide compound with respect to resin 100 weight portions with the ratio of 0.1 weight portion～5 weight portions at the B layer, in the system of extruding during during film or as resin-covered metal sheet, in the time of can suppressing to use by the phenomenon of moisture effects molecular weight and molecular weight, durability is good, and especially humidity resistance is good.

According to the present invention five, the B layer contains and accounts for the above polybutylene terephthalate (PBT) of resinous principle 20 weight % (below be called " PBT ") resin, therefore no matter the crystallinity when the B layer is extruded the system film how, can both be given anti-boiling water dipping property.

According to the present invention six, the B layer contains the above PBT resin of 55 weight %, according to extruding the B layer that the curtain coating condition of system during film can obtain the high state of crystallinity, even do not carrying out crystallization processing etc. in the operation, also can obtain not adhere to the characteristic that the metal part after the heating of machine is given in embossing in the back.Further the A layer is that main body is a formation with amorphism or low-crystalline polyester based resin, and therefore the above temperature of glass transition temperature (Tga) by thin plate being heated to this resin can be given the embossed pattern that utilizes embossing to give machine.

According to the present invention seven, consist of the material that commerciality obtains easily by the resin that makes the A layer, aspect cost, preponderate, and reduce and carry out the shortcoming of crystallization in time, also be difficult to take place what problem even give the situation of embossing behind the long preservation thin plate.

According to the present invention eight, when giving embossed pattern design, can also give the printed patterns design.

According to the present invention nine, by the thin plate heating-up temperature that generally is used for machine that the embossing that the flexible PVC thin plate is given embossing is given is set in this scope, can obtain good embossing and give adaptability.

According to the present invention ten, when giving embossed pattern design, can also give the printed patterns design, by on printed layers, covering specific thicknesses and not adding the polyester based resin layer (below be called " E layer ") of pigment, can make the durability of printed layers good.Further the E layer is that main body constitutes with amorphism or low-crystalline polyester based resin, and therefore the above temperature of glass transition temperature (Tga) by thin plate being heated to this resin can be given the embossed pattern that utilizes embossing to give machine.

According to the present invention 11, consist of the material that commerciality obtains easily by the resin that makes the E layer, aspect cost, preponderate, and reduce and to carry out the shortcoming of crystallization in time, even give under the situation of embossing also being difficult to take place what problem behind the long preservation thin plate.

According to the present invention 12, by the thin plate heating-up temperature that generally is used for machine that the embossing that the flexible PVC thin plate is given embossing is given is set in this scope, can obtain good embossing and give adaptability.

According to the present invention 13, by with extruding legal system film A layer and B layer, reduce the shortcoming of interface peel in time, also can improve productivity.

The design thin plate that the resin-covered metal sheet of at least 2 strata ester resins of layer, substrate resin layer is used is given in the different embossing of rerum natura that the present invention's 14 is stacked, embossing is given layer based on non-crystalline resin, also can be according to calendering legal system film, but therefore small lot effectively obtains the thin plate of various tones.Further, but by give machine transfer printing embossing decorative pattern with embossing, tone not only also can the multiple decorative pattern of small lot transfer printing about the embossing decorative pattern.

The B layer of given thickness plays the function of substrate resin layer, and has a crystallinity, therefore even embossing is given and is given layer monomer to embossing in the machine and be heated to the thin plate temperature that can produce the fusion fracture, as long as below the fusing point Tmb of substrate resin layer, then stacked formation thin plate can not produce problems such as fusion fracture or fold.Thereby, can give and have the stable on heating embossing decorative pattern of higher embossing when giving layer monomer than embossing, the possibility that produces the bad order phenomenon under actual environment for use is little.Here the fusing point Tmb of substrate resin layer be the substrate resin layer according to differential scanning calorimetry (DSC) (DSC) carry out once heat up the time the crystallization melting peak temperature.

Also have, the substrate resin layer is given various tones by extruding the system film production but give layer by embossing, so the substrate resin layer can not add pigment or only by single tone system film, can suppress to become the colour changing loss of extruding system film difficult point.

In the design thin plate that the present invention's 15 resin-covered metal sheet is used, be resin, when extruding the system film, can give well-crystallized by the fireballing polybutylene terephthalate (PBT) of crystallization (PBT) that contains at the substrate resin layer more than the specified quantitative.Thereby, do not need the crystallization of back in the operation to handle, and its fusing point is below 225 ℃, be soft PVC that thin plate layer 230 ℃ of degree of metal sheet surface temperature when being pressed onto metallic plate can obtain sufficient adhesion strength therefore in the past.For the resin-covered metal sheet in 16 inventions of claim the too with the design thin plate.

The present invention 17 in the design thin plate used of resin-covered metal sheet be, send into embossing according to the measured value of differential scanning calorimetry (DSC) (DSC) regulation and give the crystallinity that the substrate resin layer should possess before the machine, even touching embossing thus gives contact-type heating device that machine possesses usually, is heating of metal roller etc., do not have adhesion yet, even and thin plate be heated also can the fusion fracture.

The present invention 18 in the design thin plate used of resin-covered metal sheet be, the resinous principle of giving layer as embossing has the practical experience and the common commercially available amorphism polyester based resin of calendering system film by use, can guarantee stable production, and also favourable aspect cost of material.

The present invention 19 in the design thin plate used of resin-covered metal sheet be, give the surface of folded side layer by layer by what substantially the non-crystalline resin layer is arranged on the substrate resin layer with coetrusion with embossing, further guarantee the interface adhesion strength that thermal welding is stacked more reliably.

The present invention 20 in the design thin plate used of resin-covered metal sheet be to make surface physical property further excellent at aspects such as against weather, anti-wound property, stain resistances.

The present invention 21 in the design thin plate used of resin-covered metal sheet be, by make with thermal welding embossing give the layer and substrate resin build up one layer by layer, compare with stacked all-in-one-piece situations such as giving bond layer separately, can cut down man-hour, and give machine to embossing and supply with embossing and give layer, each monomer thin plate of substrate resin layer, can carry out stacked integrated and embossing simultaneously and give.

The present invention 22 in resin-covered metal sheet, but small lot effectively obtains to possess various color harmony embossing decorative patterns and have the stable on heating resin-covered metal sheet of high embossing.

The manufacture method of the resin-covered metal sheet of the present invention of 23 records according to the present invention, by cooling off the resin-covered metal sheet behind the lamination rapidly, the answer of embossing in the time of can suppressing lamination can obtain to have the embossed pattern design resin-covered metal sheet of the design of the degree of depth.

Description of drawings

Fig. 1 is the ideograph of the resin-covered metal sheet of first basic comprising of the present invention of expression.

Fig. 2 is the ideograph of the stacked resin sheet of second basic comprising of the present invention of expression.

Fig. 3 is the skeleton diagram of expression ordinary soft PVC thin plate with the embossing applicator.

Specific embodiments

First the present invention

Below, first specific embodiments of the present invention is described.

Fig. 1 (a) is the pattern sectional drawing of first resin-covered metal sheet basic comprising of the present invention of expression.Constitute metallic plate through A layer, B layer, bond layer successively from face side.

Except constituting, Fig. 1 (a) also given printing ink layer (C layer) and clear coat (D layer) among Fig. 1 (b).

Except constituting, Fig. 1 (a) also given printing ink layer (C layer) and transparent polyester resin bed (E layer) among Fig. 1 (c).

Fig. 1 (d) is that printed layers is by (c-1) layer and (c-2 layer) two-layer formation, corresponding to the situation of having given pattern printed layers and overall printing layer in Fig. 1 (c) constitutes.

Laminated thin plate thickness of the present invention is got 65 μ m～300 mu m ranges, more precisely should be " film and thin plate " therefore, but is the thin plate that is also referred to as that generally can be called film to thickness for convenience here.

(1) mainly is added with the layer (A layer) that is used for painted and hidden pigment

Below be used for not tensile layer (A layer) painted and hidden pigment, that with the polyester based resin be main component and abbreviate the A layer as mainly being added with sometimes.Also have, the resinous principle that constitutes the A layer is called Resin A sometimes.

The A layer is the polyester based resin layer that does not stretch, and is not meant the situation of not carrying out stretched operation but stretch, but and do not mean that as when extruding the system film because the also non-existent situations such as orientation that the drawing-off of casting roller produces.These are also identical for the B layer.

Paintedly to give design and give the hidden effect of ground vision and added pigment in order to utilize in the A layer.The pigment that uses can be the material that in the past generally was used for coloring resin, but in order just to obtain the hidden effect of sufficient ground at the lamella thickness that generally is used for resin-covered metal sheet, needs to use the white color system pigment of titanium oxide pigments as main body.

Titanium oxide pigments is meant in order to sneak into resin implements general kind and treating capacity surface-treated rutile crystal type, is not meant the Detitanium-ore-type titanium that does not carry out surface-treated titanium oxide or surface treatment effect shortcoming.Certainly, consider, can use to implement titanium oxide pigments that special surface handles etc., but existing situation is, rise with cost and compare, can not obtain corresponding effects from improving the durability aspect.

Based on above-mentioned titanium oxide pigments, use the mix colours tone of white color system expectation of inorganic and organic various color pigments simultaneously.

The preferred thickness of A layer is 50 μ m～250 mu m ranges, if be thinner than this, hidden effect in order to ensure ground, even use titanium oxide pigments also to need to add the extremely pigment of high concentration, and the processability that can cause like this making film deterioration and resin-covered metal sheet descends, and is not preferred therefore.Further consider the above thickness of preferred 70 μ m from the angle that can utilize embossing described later to give the embossed pattern of the various patterns of machine transfer printing.Also have, if thickness surpasses 250 μ m, the hidden effect of ground instead only can raise the cost, is not preferred by saturated therefore.

Even use non-oriented and when having crystalline polyester based resin as A layer main component polyester based resin, by replacing mirror roller with the roller of carving embossing plate to extruding the casting roller of system during film, or be laminated to behind the metallic plate by heating again or appending and be heated to that the above temperature of A layer crystalline melt point makes its fusion and the methods such as transfer printing embossed pattern with the extruding of embossing plate roller, can give embossed pattern, but these two kinds of methods are all restricted to the embossed pattern that can give, and cost of equipment is also high.

Compare with these methods, the embossing that operation is given in off-line (off line) embossing that in the past was used for the flexible PVC thin plate is given machine because of exchange embossing plate roller easily, be suitable for small lot batch manufacture, so when giving embossed pattern, also preferably use this embossing to give machine to the laminated thin plate that is used for resin-covered metal sheet of the present invention.If this moment, the main body of A layer was essentially the polyester based resin of amorphism or low-crystalline, then can be by the above temperature of glass transition temperature (Tga) that is heated to this resin, make the elastic modelling quantity of this layer be reduced to can the transfer printing embossing degree.Further, the A layer is not to use with form of single sheet among the present invention, but with the structure use folded layer by layer with B, therefore, form by the particular B layer, even can make the B layer share the A layer is heated to the above temperature of glass transition temperature (Tga) and also can prevents the web tension functions such as breaking of causing that descend, the adaptability of giving machine that embossing is given easily.

The main body that the amorphism polyester based resin that constitutes the A layer main body preferably uses sour composition is 1 as about 20～about 80mol% of terephthalic acid (TPA) or dimethyl terephthalic acid, pure composition, the 4-cyclohexanedimethanol, the copolyester that remaining about 80～about 20mol% is an ethylene glycol is a resin.Wherein widely used is that about 30mol% of pure composition is 1, the 4-cyclohexanedimethanol, and the resin that remaining about 70mol% is an ethylene glycol is formed, and is preferred from supplying with stability and producing the aspects such as cost advantage that effect brings in batches.The non-crystalline polyester resin of this composition can be enumerated " the EASTER PETG6763 " of a routine EASTMAN chemical company.

But be not limited thereto, said amorphism or low-crystalline mylar comprise at least and giving in the heating process of machine in embossing among the present invention, can form because of carrying out the resin that crystallization not be difficult to give embossing even A layer temperature is heated to more than the glass transition temperature (Tga) also.

From this point, from pure composition be ethylene glycol or, propane diols, butanediol, cyclohexanedimethanol, 1,4-cyclohexanedimethanol, neopentyl glycol etc., the acid composition is terephthalic acid (TPA), M-phthalic acid, adipic acid, 1, select in the resin arbitrarily in the homopolymers of each composition of 4-cyclohexane dicarboxylic acid etc. or the copolymer, the low material of degree of crystallinity absolute value of suitably selecting for use monomer or mixture to have above-mentioned characteristic, the slow-footed material of crystallization etc.

Except pigment composition, can also under the condition that does not influence its character, add various additives in right amount in the A layer.Additive can be enumerated the material that phosphorus system, phenol system and other various antioxidants, heat stabilizer, ultra-violet absorber, light stabilizer, nucleator, metal inert agents, residual polymerization catalyst inert agents, antibacterial mildew inhibitor, antistatic additive, lubricant, fire retardant, filler etc. generally are used for extensive resin material.

The film-forming method of A layer is, when consisting of the amorphism polyester, also can use the resin of A layer calendering system embrane method, but from guaranteeing angle consideration as the durability of laminated thin plate integral body, preferred coextrusion system embrane method and the B layer of adopting firmly is layered in the mould, because can reduce the phenomenon that peel off in time at the interface like this.

(2) for guaranteeing the layer (B layer) of durability

The B layer is the layer of giving in order to ensure the durability of resin-covered metal sheet, and the durability display mechanism was put down in writing as " by the means that solve problem ".

Thereby the B layer at first needs the interpolation concentration of pigment little, does not especially preferably add pigment.If only to the A layer add pigment the hidden effect of ground can to add with respect to 100 parts by weight resin compositions at the B layer when insufficient be pigment below 10 weight portions, but from guarantee as the B layer exist originally meaning guarantee durability that laminated thin plate constitutes, and resin-covered metal sheet that it covered the angle of durability consider, especially preferably do not contain pigment fully.

Further, the B layer is being extruded the state of system behind the film, and preferably the weight average molecular weight that converts with styrene according to GPC (gel permeation chromatography) is in 75000～140000 scopes.

Main deterioration factor was considered to hydrolysis when polyester based resin was used for hygrothermal environment, and embrittlement takes place thus, caused the mechanical properties deterioration, and film etc. can become the state that crackle occurs when bending.When the resin-covered metal sheet state, also can because of the thin layer embrittlement crackle takes place or follow and metallic plate between the decline of adhesion strength phenomenons such as the part thin layer peels off take place, significantly damage the pattern design in appearance, and can't to obtain to cover resin bed at metallic plate be that the anticorrosion ability and the design of the metal surface of purpose given effect.On the other hand, the deterioration that is caused by hydrolysis is that the ester bond in polyester chain partly takes place, and therefore can reduce molecular weight.Making under the film thin plate state the low person of molecular weight in the hygrothermal environment in the past, even in the short-term hygrothermal environment, use the deterioration that also can produce as above-mentioned mechanical properties, even the person then uses in hygrothermal environment can to obtain the higher molecular weight during system film, the durability that before causing mechanical properties decline, can show the long period, equally all can cause molecular weight and molecular weight when in hygrothermal environment, using, but initial molecular weight is high more, also high more through the molecular weight after during same, and the appearance of physical degradation such as film crackle is to begin significantly being lower than certain value part at the absolute value of molecular weight.

Thereby, need carry out following processing for the B layer being made the good layer of humidity resistance.

1. from using the resin raw material aspect, select to be higher than the material of certain degree molecular weight.

2. from the membrane equipment aspect,, make the screw rod design optimization in order to suppress molecular weight and molecular weight.

3. by discharger in position is installed, reduce the hydrolysis when being shaped.

4. do not make the holdup time be longer than required time.

5. study the drying process of raw material, reduce the influence of hygroscopic moisture.

Also have, B layer of the present invention only contains small amounts of pigment, does not perhaps contain pigment fully, therefore, compare with the situation of a large amount of interpolation pigment, the molecular weight in the time of can suppressing to be shaped processing reduces, and therefore obtains easily also to help durability the high material aspect of molecular weight behind the system film.

If B layer of the present invention weight average molecular weight when system film thin plate then as above-mentioned when being used for hygrothermal environment as resin-covered metal sheet, can prevent that hydrolysis earlier from reaching the molecular weight that causes embrittlement, can obtain sufficient durability more than 75000.Also have, if molecular weight below 140000, abundant cutting down cost.Because the molecular weight of employed mylar raw material self need use higher material, because it can not usually obtain continuously, so cost can rise.Also have, even obtained this resin raw material, the influence that the strand during the system film in the forming machine is cut off by mechanicalness is also remarkable, makes the HMW that the film thin plate can't obtain to expect often, not only durability raising effect is saturated, and system film time institute energy requirement also increases.

The resin of B layer of the present invention is formed the preferred composition that obtains above-mentioned molecular weight ranges easily, consider that from this respect raw material preferably uses solid polymer etc. to obtain the PET resin or the PBT resin of the high material of molecular weight easily, can use the independent composition of this resin, perhaps with the product mix of other polyester based resins.

Wherein, especially preferred homopolymerization PBT resin, reason is as follows.

1. get all the higher grade class of initial molecular weight ready as extruding grade (grade).

2. hydrolysis speed is than PET series resin little (with reference to " gathering 1,4-mutual-phenenyl two acid bromide two alcohol ester's heat and hydrolysis properties ", fiber association will, 43 volumes, 7 phases (1987), Tanaka 3,000 Yan Shi of fiber research institute of Dongli Ltd.).

Though 3. be crystalline resin, the elastic modelling quantity of crystal region is lower than the PET series resin, therefore the flexible height of crystallization portion, even cover metallic plate under the higher state of crystallinity, also can show good processability.

Therefore metal sheet surface temperature equal extent when 4. fusing point (Tm) is with flexible PVC thin plate lamination in the past or than its low a little temperature can directly be suitable for the equipment that always is used to make flexible PVC thin plate covered metal plate etc.

Consider from further reduction laminating temperature aspect, preferably by reducing the PBT resin of fusing point with the M-phthalic acid copolymerization, but this PBT resin has the tendency than the homopolymerization PBT humidity resistance difference of same molecular amount, as long as can carry out lamination in the above temperature of homopolymerization PBT fusing point, then consider the preferred homopolymerization PBT resin that uses from the humidity resistance aspect with equipment in the past.

Also have, it is fast that PBT resin and PET resin are compared crystallization speed, therefore, when using the PBT resin that surpasses 20 weight % to form as B layer resin, can give boiling water resistance to resin-covered metal sheet, this be because, even when the B of resin-covered metal sheet layer is amorphism or low-crystalline state, the PBT resin is by boiling water dipping back crystallization at once, and its result also can obtain not take place the thin plate distortion or the elastic modelling quantity of the degree that breaks away from from metallic plate in boiling water.

When the B layer uses the PBT resin that surpasses 55 weight %, according to extruding the B layer that the curtain coating condition of system during film can obtain the high state of crystallinity, even not extruding the crystallization of the back operation of system film handles, also the A layer can be made the polyester layer of described substantial amorphism or low-crystalline, can guarantee laminated thin plate is heated to the tension force that A layer glass transition temperature also can not rupture when above by the B layer, also have, the preheating of giving machine to embossing does not produce with metal roller etc. and adheres to, and can make to be applicable to and to utilize embossing to give the laminated thin plate that machine is given embossed pattern.

As the resinous principle that in the B layer, uses with the PBT mixed with resin, can use and the identical composition of the preferred resinous principle of described A layer, but the resinous principle except PBT is difficult to obtain the high material of raw molecule amount, therefore have the thin plate of the weight average molecular weight of the scope of the invention from easy acquisition, and be applicable to that above-mentioned embossing gives the angle of machine and consider to be preferably the composition that is rich in PBT.

With the amorphism of PBT mixed with resin or the humidity resistance of low-crystalline polyester, not only relevant also relevant with molecular structure with its molecular weight, the structure of the ester bond number in same weight, sour composition, pure composition and whether hydrone to be had a steric hindrance effect etc. all different, can not only lump together according to initial molecular weight, but, can think that initial thin plate molecular weight and humidity resistance has dependency relation for the system of industrial these raw materials that can obtain and PBT mixed with resin.

Can under the condition that does not influence its character, add various additives in right amount at the B layer.Additive can be enumerated the material that phosphorus system, phenol system and other various antioxidants, heat stabilizer, light stabilizer (normal temperature effect type free radical scavenger), nucleator, metal inert agents, residual polymerization catalyst inert agents, antibacterial mildew inhibitor, antistatic additive, lubricant, fire retardant, filler etc. generally are used for extensive resin material.Just, preferably do not add the additive of the permeate water component that can increase B layer thickness direction.

Further, extrude system molecular weight and molecular weight during film as utilizing additive to suppress the B layer, obtain the method for the painted thin plate of scope of the invention molecular weight, perhaps, can add carbodiimide compound as making behind the resin-covered metal sheet method of hydrolysis deterioration under hygrothermal environment.Hydrolysis when this carbodiimide compound can suppress to extrude the system film in the forming machine, its result has the effect of the painted thin plate of molecular weight in the easy acquisition claim of the present invention, and the carbodiimide compound that remains in the thin plate that does not consume in the forming machine can play the effect that is suppressed at the hydrolysis when using in the hygrothermal environment.

Carbodiimide compound can have the material of following general formula basic structure for example.

—(N＝C＝N—R—) _n—

In the following formula, n represents the integer more than 1.R represents other organic system combining units.

The R of these carbodiimide compounds part can be aliphatic, alicyclic, aromatic any one.Can enumerate poly-4 specifically, 4-diphenyl methane carbodiimide, polyparaphenylene carbodiimide, poly-metaphenylene carbodiimide, polymethyl benzene base carbodiimide, poly-diisopropyl phenylene carbodiimide, poly-methyl diisopropyl phenylene carbodiimide, poly-triisopropyl phenylene carbodiimide etc., and their monomer.This carbodiimide can use separately also can make up two or more uses.

With respect to 100 parts by weight resin components, carbodiimide compound preferably adds 0.1 weight portion～5 weight portions, more preferably 0.5 weight portion～5 weight portions.If preferably more than 0.1 weight portion, more preferably more than 0.5 weight portion, then can obtain sufficient hydrolytic resistance and improve effect.And, if below 5 weight portions, it is saturated or extrude the situation of system film generation variety of issue to avoid suppressing the effect of molecular weight and molecular weight, degradation situation under the bad order that also can avoid carbodiimide compound to ooze out causing for the thin plate behind the system film or the mechanical properties.Also have, can also avoid the B layer to cooperate the situation of cost costliness.

Additive with anti-hydrolysis effect can also have the block copolymer of multifunction group epoxy base and graft copolymer etc. for example.These also can an amount of interpolation in the scope of the not required humidity resistance of deterioration B layer and other performances (the curved processability of folding etc.).Because these additives, the water-disintegrable improved thing of polyester based resin is known.

Certainly, also can cooperate additive in the A layer with same anti-hydrolysis effect, but these have reactive additive and can react with the hydroxyl on the surface of the titanium oxide that adds as pigment, therefore, be difficult to the effect that obtains to add, but also become the factor of pigment particles aggegation easily, so, the situation of effect when adding the B layer to.

The B layer thickness is preferably in the scope of 15 μ m～80 μ m.By making them more than 15 μ m, can obtain to keep effect, and can fully suppress moisture and see through to metal sheet surface as the sufficient durability of laminated thin plate integral body.Also have, by making them below 80 μ m, it is saturated to avoid durability to keep effect, and controlled gross thickness when being made as the laminated thin plate that is used for resin-covered metal sheet, thereby can avoid being difficult to the relative attenuation of A layer thickness obtaining the situations such as sufficient hidden effect that produced by pigment.

The gross thickness of the thin plate of stacked A layer and B layer is preferably at 65 μ m～300 mu m ranges.If more than 65 μ m, described A layer function and B layer function easily can get both.Also have, if below 300 μ m, can directly use the processing mold of secondary formings such as the punching press that in the past is used for the flexible PVC covered metal plate, bending, pull and stretch, the cost aspect is favourable.

(3) printed layers (C layer)

Also the C layer can be set at the A laminar surface, give the printed patterns design.Printed layers can photogravure, lithographic printing, screen painting and other known methods are given.Purpose is to give bag accent, wood grain accent or printed patterns designs such as geometry pattern, abstract design.Can be the part printing, also can be comprehensive overall printing, also can implement part printing and overall printing layer both sides.From guaranteeing that printed layers durability (the coming off of printed layers, variable color, fade) angle considers, preferably on printed layers, give clear coat or transparent resin layer.

(4) clear coat (D layer)

Giving of coating can be carried out before laminated thin plate is given machine by embossing, also can after carry out, but therefore the good operability of coating production line when giving the thin plate of the smooth state before the embossing, preferably implements printing and coating at the A layer in advance.

Giving coating can implement according to various usual methods, the resin of coating D form can enumerate as silanol condensation type such as polysiloxane series, acrylic polysiloxane series or, materials such as cyanate cross-linking type such as PVF vinyl ether copolymers, acrylic polyalcohol, polyurethane polyol, PEPA, but be not limited thereto, so long as can obtain adaptation with the A layer, and the heating of metal of giving in the operation with embossing has non-adhesive, then do not do special restriction, can use.Also have, also can be by constituting coating D more than two-layer, top layer is for having the cohesionless layer of metal, also can sandwich function with this layer and bond layer of printed layers C or A layer layer.Be added with ultra-violet absorber, silicon oxide particle, antistatic additive, semitransparent pigment, dyestuff etc. according to purpose in this coating.

The D layer thickness if be thinner than this, is easy to generate problems such as being difficult to evenly coating preferably at 1～10 mu m range, is not preferred therefore.Also have, if be thicker than this, the secondary workability that adaptability and resin-covered metal sheet are given in embossing worsens easily, is not preferred therefore.

(5) transparent resin bed (E layer)

Can on the C layer, further give based on thickness at the substantive amorphism of 25 μ m～100 mu m ranges or the E layer of low-crystalline mylar.At this moment, printed layers can show the design with degree of depth, forms all the other compositions and the identical not tensile layer of the preferred resin composition of A layer except not containing pigment simultaneously, therefore can also give the embossed pattern that utilizes embossing to give machine.It must be identical resin composition that the A layer does not need with the E layer.

The E layer need be given printing back on the A layer stacked, therefore, if thickness is thinner than this, can make stacked before operability during the individual layer thin plate worsen very much, be not preferred therefore.If opposite thickness is thicker than this, the flavescence phenomenon that causes is penetrated in illumination will be remarkable, and the deterioration of the processability of resin-covered metal sheet, is not preferred therefore.

With A layer or B layer in the same manner, can also add various additives at the E layer, the ultra-violet absorber that especially preferred interpolation can prevent variable color that printed layers light deterioration causes, fade etc.Also have, also can under printed layers is had an X-rayed not difficult condition, add mica powder or holographic paper tinsel and give design.

As the method that E is laminated to layer by layer above the printed layers C layer, can adopt various bonding agents, it is that resin etc. is host that this bonding agent can use with polyester based resin or polyethers, with curing such as isocyanate-based crosslinking agent, generally be called the material of dry method lamination with bonding agent.Also have, also can form the C layer by the printing-ink with thermal welding, perhaps give coating layer with thermal welding etc. on top layer in printing process, utilizing embossing to give thin plate heating process in the machine, to carry out thermal welding stacked etc.

The gross thickness of laminated thin plate also preferably is no more than 300 μ m when giving the E layer.

(6) metallic plate

Metallic plate as object of the present invention can use various steel plates or aluminium sheets such as hot rolled steel plate, cold-rolled steel sheet, hot-dip galvanized steel sheet, plated steel sheet, tin plate, corrosion resistant plate, also can apply common chemical conversion processing back use.The thickness of substrate metal plate is different because of purposes of resin-covered metal sheet etc., but can select in 0.1mm～10mm scope.

By being laminated on the substrate metal plate, can obtain resin-covered metal sheet of the present invention by A layer and the two-layer at least laminated thin plate that constitutes of B layer.The heat-curable adhesive layer (below be called " F layer ") that is used for the lamination operation can be enumerated various known substances such as epoxide resin adhesive, urethane adhesive.

To metallic plate use contrary roller coating machine (reverse coater), touch coating machine (kiss coater), etc. the coating apparatus that generally uses, on the metal covering that posts stacked all-in-one-piece thin plate, bonding agent is coated with into dried bonding agent thickness and becomes 2～10 μ m degree.

Then, use infrared heater and/or hot-blast heater, drying and heating coated face remain on arbitrary temp to the surface temperature of metallic plate, use the roll laminating machine immediately simultaneously, the cover layer stacked plate, and by cooling off the acquisition resin-covered metal sheet.

Second the present invention

Below based on second the present invention of the explanation of example shown in the accompanying drawing.

Fig. 2 (1a) is the ideograph of the resin-covered metal sheet of second basic comprising of the present invention with the design thin plate.Resin-covered metal sheet with the basic comprising of design thin plate for giving layer A by embossing and substrate resin layer B constitutes.

Fig. 2 (1b) is beyond Fig. 2 (1a) constitutes, and further gives in embossing and is provided with the layer C that is made of non-crystalline polyester resin in fact between layer A and the substrate resin layer B.

Fig. 2 (1c) is beyond Fig. 2 (1a) constitutes, and further is provided with the coating D that heating of metal is showed non-cementability on the surface that layer A given in embossing.

One example of Fig. 2 (1d) expression resin-covered metal sheet, the resin-covered metal sheet that constitutes shown in Fig. 2 (1a) is layered on the metallic plate F through heat-curable adhesive E with the design thin plate.Also having, also can be Fig. 2 (1b) and Fig. 2 (1c)) shown in the resin-covered metal sheet of formation similarly be layered on the metallic plate F with the design thin plate.

Fig. 3 represents that an example of machine was given in normally used embossing in order to give embossed pattern at the flexible PVC thin plate in the past.

Embossing is given layer A and is formed by the different separately polyester resin of rerum natura with substrate resin layer B.The polyester resin that layer is given in following handle formation embossing calls " polyester resin A " (or abbreviating resin " A " as), and the polyester resin that forms the substrate resin layer is called " polyester resin B " (or abbreviating resin " B " as).

1) forms the resin that layer A given in embossing

Give the resinous principle of layer so long as can roll substantive noncrystalline polyester resin of system film usually as embossing, then do not do special restriction, can use.Here said amorphism polyester resin is meant, measure mylar that can't see clear and definite crystallization behavior according to differential scanning calorimetry (DSC) (DSC), though comprise in addition showing crystallinity but crystallization speed is extremely slow, therefore substantially being taken as is the material of amorphism polyester resin." the EASTER PETG6763 " of the EASTMAN chemical company that wherein fluctuation of many, the raw material stable supplying of the practical experience of calendering system film less, the cost of material aspect is also favourable is a preferred example.Just, the present invention is not limited thereto.For example can also use the calendering that contains EASTMAN chemical company with " TSUMAMI " series of PETG level or show crystallinity under given conditions but under usual conditions, be used as " PCTG5445 " etc. of EASTMAN chemical company of non-crystalline resin and the main body of sour composition is 1 as about 20～80mol.% of terephthalic acid (TPA) or dimethyl terephthalic acid, pure composition, 4-cyclohexanedimethanol and remain the mylar that about 80～20mol.% is an ethylene glycol.If the ratio of components of pure composition surpasses this scope, then crystallinity is remarkable, is not preferred therefore.

Further, can use neopentyl glycol copolymerization PET, substantive noncrystalline composition.

Give in the layer in order to give design and to give the hidden effect of bottom sense of vision and add pigment in embossing.Used pigment can be the general material that in the past was used for coloring resin, and its addition also can be the general addition that is used for above-mentioned purpose.For example, during white color system is painted, can regulate tone with colored inorganic, organic pigment with the high titanium oxide pigments of hidden effect as substrate.

Perhaps, also add pigment at the substrate resin layer and carry out when painted, reduce the low colouring agent of hidden effect that organic systems such as the semitransparent pigment of pigment concentration of layer or dyestuff are given in embossing, cooperate the design that forms color with the tone of substrate resin layer by adding.Further, also can give layer in embossing this moment adds holographic paper tinsel or painted mica and waits and give design.

Also have, can suitably add and improve the required additive of calendering system film.These additives can be enumerated as for the various lubricants that improve from the release property of stack or load when alleviating the system film, for the wire super high molecular weight acrylic resin that improves fusion tension force or the processing aids such as easy dispersion treatment polytetrafluoroethylene (PTFE) of having implemented to be launched into the fibrillation shape, gelation promoter, for improving inclination (bank) shape, improving additive that ripple adds etc.

Further, embossing is given and can suitably add above-mentioned additive in addition in the layer under the condition that does not influence its character.This additive can be enumerated various antioxidants such as phosphorus system, phenol system, heat stabilizer, ultra-violet absorber, light stabilizer, impact improver, the metal inert agents, residual polymerization catalyzed inert agents, antibacterial mildew inhibitor, antistatic additive, fire retardant, filler etc. generally are used for the material of resin material, and terminal carboxylic acid sealer such as carbodiimide system or epoxy system or anti hydrolysis agent etc. are particularly useful for the material of mylar.

Embossing is given the thickness of layer preferably at 50 μ m～300 mu m ranges.If more than 50 μ m, then calendering system film is good, obtains uniform thin plate easily.And needn't add high concentration pigment in order to obtain the hidden effect of bottom, avoid adding degradation problem under the processability that the pigment of high concentration causes easily.If also have below 300 μ m, adding when then embossing is given pined for, and can avoid occuring as being heated to sufficient temperature and needing excess energy etc. to be unfavorable for the situation of cost and efficient.Also have, can avoid taking place the saturated situation of effect the various performances of design thin plate requirement.Be determined at the version degree of depth of wanting the embossing plate given in the above-mentioned thickness range, give a layer desired thickness with the decision embossing.Embossing of the present invention is as mentioned above given layer thickness and is got 50 μ m～300 mu m ranges, therefore, should be recorded as " film and thin plate ", but is the thin plate that is also referred to as that generally can be called film to thickness for convenience here.Also identical for the substrate resin layer.

Embossing is given layer and is laminated by making embrane method with calendering, but the goods of the various tones of small lot high efficiency production.

2) resin of formation substrate resin layer B

Embossing is given in the machine when giving embossing decorative pattern heating thin plate, if having only embossing to give layer then situations such as fusion fracture, fold, the width of cloth that contracts take place, by having the substrate resin layer, plays the supporting layer effect that prevents these phenomenons with respect to this.Thereby, the required performance of substrate resin layer be not for also adhering to contacting through the metallic roll of heating etc., and make embossing give layer monomer the problems referred to above not occur, situations such as fusion fracture, fold, the width of cloth that contracts can not take place yet in the temperature higher than the temperature that can give embossing.Further, to carry out thermal welding stacked if can give layer with embossing, then can carry out stacked integrated operation simultaneously when the heating thin plate is given in the machine in embossing.Also have, during as the resin-covered metal sheet purposes, preferably under the temperature conditions of lamination when flexible PVC was resin-covered metal sheet in the past, obtain firm bonding force.

Consider from function aspects as supporting layer, need be the polyester resin of the state of the above crystallization of certain degree, the measured value when more specifically saying so according to once the heating up of differential scanning calorimetry (DSC) (DSC) satisfies the thin plate of relational expression [0.5＜(Δ Hm-Δ Hc)/Δ Hm].Even constitute, when its crystallinity is hanged down, also can the heating of metal roller that machine is given in embossing be adhered to because resin B is made up of crystallinity.

Also have, when the design thin plate was covered the metallic plate use, the fusing point of preferred substrates resin bed (Tmb) was 180 ℃～240 ℃ scopes, and the substrate resin layer is the thin plate that does not stretch.This is owing to use the laminating apparatus that used when the flexible PVC thin plate layer being pressed onto metallic plate in the past, directly is suitable for and identical in the past laminating temperature condition.Get above-mentioned melting range by the substrate resin layer, the metal sheet surface temperature in the time of can be lamination is set for and is higher than substrate resin layer fusing point, near the fusion bonding interface of substrate resin layer and can obtain firm bonding force.By making substrate resin layer fusing point, also can obtain firm bonding force in lamination in the past, and avoid the application at the metallic plate back side to handle phenomenons such as deterioration easily below 240 ℃.Also have, by being set in more than 180 ℃, when metallic plate is carried out lamination, can guarantee this advantage of bonding force with lower laminating temperature though lost, but give the function excellence of machine supporting layer as embossing, feed embossing with monomer and give the situation of machine and compare with embossing being given layer, can improve the thin plate temperature when giving embossing.If the substrate resin layer uses oriented film, before reaching substrate resin layer fusing point, will cause remarkable contraction when carrying out lamination, the resin bed at resin-covered metal sheet causes fold etc. easily, is not preferred therefore.

Polyester resin as forming resin B can use various crystallinity polyester resins.PETG (below be called " PET ") is that resin etc. is slow because of crystallization speed, in order to obtain the preferred crystallinity of the present invention, need implement crystallization separately after extruding the system film to handle, so operation increases.Further, PET be resin after carrying out crystallization, therefore its fusing point height during with condition and metallic plate lamination in the past, can't obtain sufficient adhesion strength, and is not preferred.

With respect to this, polybutylene terephthalate (PBT) (below be called " PBT ") is that resin or polytrimethylene-terephthalate (below be called " PTT ") are that the crystallization speed of resin is fast.Thereby the casting roller temperature when extruding the system film by suitable setting can be given the substrate resin layer with required crystallinity when extruding the system film, considers especially preferably to use from this angle.

Further, the fusing point of these resins is, when forming the so-called homopolymerization PBT that constitutes or homopolymerization PTT by sour composition and pure composition single separately is about 225 ℃, can obtain firm bonding force during with above-mentioned condition in the past and metallic plate lamination, considers it also is preferred from this aspect.From considering with the adhesive strength aspect of copper coin, be that copolymerization such as M-phthalic acid copolymerization PET in the resin are formed by PET, can obtain to have the material of above-mentioned preferred range fusing point.But this moment, crystallization speed was slower than homopolymerization PET, and the required time of crystallization treatment process increases, and is not preferred therefore.

According to the condition of laminating apparatus, in the time of need obtaining firm bonding force in the temperature lower than the fusing point of homopolymerization PBT resin or homopolymerization PTT resin, can use by waiting the PBT that reduces fusing point with the M-phthalic acid copolymerization is resin.At this moment, preferred copolymerization ratio is, can obtain (Δ Hm-Δ Hc)/Δ Hm greater than 0.5 value in the thin plate film making process.

Also have, the substrate resin layer can also be based on homopolymerization PBT resin or homopolymerization PTT resin, mix and use non-crystalline resin, but proceed to the resin B that when extruding system film do not stick to heating of metal roller in order to obtain degree of crystallization this moment, and the mixing of resin B preferably contains 60 weight % above homopolymerization PBT resins or homopolymerization PTT resin in forming.

Ratio by making crystalline resin is given preferred crystallinity easily in extruding film making process more than 60 weight %.By the non-crystalline resin of undermixing 40 weight %, form degree of crystallinity to reduce crystallization to greatest extent the time by its of the crystallization heat of fusion (Δ Hm) of differential scanning calorimetry (DSC) (DSC) expression.Like this, can reduce the heat that the crystallization fusion when being laminated to metallic plate is consumed, further increase, obtain firm bonding force easily by the amorphous domain volume.

Also can the various desired additives of identical suitable interpolation with Resin A for the substrate resin layer.The substrate resin layer is to make according to extruding the system embrane method, by making the transparent thin board that does not add pigment or being coloured to specific single look, can prevent raw material and leeway that colour changing brings.

The thickness of substrate resin layer is preferably at 20 μ m～300 mu m ranges.By more than 20 μ m, in the time of can fully guaranteeing to give machine zone of heating stacked plate with embossing as the effect of supporting layer.Also have,, can avoid when giving the effect of supporting layer saturated, only can increase condition of cost as embossing by below 300 μ m.

The system film of substrate resin layer can carry out as blow moulding or T modulus method with the known film-forming method of extruding.For the purpose of thermal welding of guaranteeing to give layer, can be and the constituting of the layer coextrusion that constitutes by the amorphism polyester resin in fact with embossing.

Resin as the layer that is made of the amorphism polyester resin is in fact formed, can use and can be used in embossing and give the identical material of amorphism polyester resin of layer resin composition.It can be to give layer identical composition with embossing, also can be different compositions.Embossing is given in the thin plate heating process of machine, and hot welding layer laminates to be spent when giving layer with the substrate resin layer, and layer is given in embossing becomes thermoplastic state.When bringing into play its effect, the substrate resin layer need keep high elastic modulus.According to equipment, embossing takes place sometimes give layer and the hypodynamic situation of the driving fit of substrate resin layer.Utilize coextrusion and when giving in fact the substrate resin layer of the layer that is made of the amorphism polyester resin, the surface of substrate resin layer side (layer that is made of the amorphism polyester resin in fact) also can be softened by heating in use.Obtain the firm closing force of embossing being given layer like this, easily.

The layer that is made of the amorphism polyester resin is the layer with bond layer function in fact, so its thickness is preferably at 3 μ m～30 mu m ranges.

The gross thickness of laminated thin plate (A+B or A+C+B) is preferably below 500 μ m, more preferably below 300 μ m.By below 500 μ m, more preferably below 300 μ m, can make as the secondary operations adaptability such as punch process of resin-covered metal sheet fully good.Also have, can use the forming machine that in the past was used for the soft PVC resin-covered metal sheet, consider it also is preferred from making the forming machine aspect again.

3) the stacked integrated and embossing of thin plate is given

The example that machine 10 is given in the common embossing of having represented among Fig. 3 in the past to use in order to give embossed pattern at the flexible PVC thin plate.It is configured to utilize behind the metallic roll 1 preheating thin plate 2 of heating, utilizes contactless heater 3 further to improve the thin plate temperature, is passed into then between embossing plate roller 4 and the compression roller 5, and the embossing decorative pattern is transferred to thin plate.

Supply with simultaneously by the embossing of calendering legal system film for this equipment and to give layer and by the substrate resin layer of extruding the legal system film substrate resin layer of the layer coextrusion that constitutes by the amorphism polyester resin in fact (or with), method as the one example can be given an example, to stacked these thin plates of the supply unit of heating of metal roller, utilize the heat of heating of metal roller to make these two kinds of thin plates carry out stacked integrated.

Can implement with flexible PVC is identical in the past about giving of embossing decorative pattern.At this moment, the situation of giving layer monomer with embossing is different, even the thin plate heating-up temperature that embossing is given in the machine is set in more than 160 ℃, below (Tmb-20) ℃, also can not produce the phenomenon to the adhesion or the thin plate fusion fracture of heating of metal roller.Thereby can obtain embossing and give the high embossing hear resistance that layer monomer can't obtain.

4) metal non-adhesive coating D's gives

Can give coating D according to various purposes on laminated thin plate (A+B or A+C+B) surface, as improving against weather, perhaps improve anti-wound property, improve stain resistance, improve solvent resistance and give design with degree of depth etc. by giving ultraviolet-absorbing.The giving of coating D can feed embossing in laminated thin plate carries out before giving machine, also can after carry out.But therefore the good operability of coating production line when giving the thin plate of the smooth state before the embossing, is preferably given layer in embossing in advance and is implemented coating.At this moment, coating needs to have the non-cementability with heating of metal except above-mentioned purpose.

Giving coating can implement according to various known method, the resin of coating D form can enumerate as silanol condensation type such as polysiloxane series, acrylic polysiloxane series or, materials such as cyanate cross-linking type such as PVF vinyl ether copolymers, acrylic polyalcohol.But the present invention is not limited thereto, so long as can obtain to give the adaptation of layer with embossing, and have the non-cementability with heating of metal, then not doing special restriction, can use.Also have, also can be by constituting coating D more than two-layer, top layer is for having the cohesionless layer of metal, also can clip function with this layer and bond layer of Resin A layer.Can be added with ultra-violet absorber, silica (silica) particle, antistatic additive, semitransparent pigment, dyestuff etc. according to purpose in this coating.

The thickness of coating D is preferably at 1～10 mu m range, by evenly coating easily more than 1 μ m.Also have, give adaptability by below 10 μ m, obtaining fully good embossing.

5) metallic plate F

Metallic plate among the present invention can use various steel plates such as hot rolling copper coin, rolled copper, molten zinc plating copper coin, electrogalvanizing copper coin, zinc-plated copper coin, corrosion resistant plate, aluminium sheet, and aluminium class alloy sheets also can apply common chemical conversion processing back use.The thickness of substrate metal plate is different because of purposes of resin-covered metal sheet etc., but can select in 0.1mm～10mm scope.

6) manufacture method of resin-covered metal sheet

The following describes the manufacture method of resin-covered metal sheet.Utilizing the embossing applicator to give the laminated thin plate of the embossing decorative pattern bonding agent that (A+B or A+B+C) uses when being laminated to the substrate metal plate, can enumerating epoxy is that bonding agent, urethane adhesive, polyester are the heat-curable adhesive that bonding agent etc. generally uses.The method that obtains resin-covered metal sheet is, use contrary roller coating machine, touch the coating apparatus that coating machine etc. generally uses, metallic plate is built up at laminating layer on the metal covering of thin plate of one and heat-curable adhesives such as above-mentioned epoxy system, polyurethane series, polyester system to be coated with into dried bonding agent thickness to become 2～10 μ m degree.

Then, use the dry and heating coated face of infrared heater and/or hot-blast heater, the surface temperature of metallic plate is remained on arbitrary temp, use the roll laminating machine simultaneously immediately, the substrate resin layer side that covers into laminated thin plate becomes bonding plane, and obtains resin-covered metal sheet by cooling.Be preferably placed at fusing point (Tm) with the substrate resin layer of metallic plate bonding plane side among the present invention 180 ℃～240 ℃ scopes.At this moment, it is identical to make the surface temperature of metallic plate and flexible PVC thin plate layer in the past cover the situation of covering metallic plate, to obtain firm bonding force.

According to the present invention, can obtain embossing hear resistance resin-covered metal sheet preferably.Preferably carry out cooling rapidly such as water cooling behind the lamination immediately, the embossing that the thin plate heating causes when alleviating lamination is replied.

Embodiment

First the present invention

For further concrete and describe first the present invention in detail, represent embodiment below, but first the present invention is not subjected to any qualification of these examples.In addition, the bioassay standard of the rerum natura of resin-covered metal sheet shown in embodiment and the comparative example, test method are as follows.

(1) weight average molecular weight of mylar

The gel permeation chromatograph HLC-8120GPC that makes in eastern ソ-(strain) upward installs the GPC-800CP of the chromatographic column Shim-Pack series of (strain) Shimadzu Seisakusho Ltd. manufacturing, use hexafluoroisopropanol/chloroform=1/20 (vol/vol) mixed solvent during the modulation sample, with sample solution concentration 0.476wt/vol%, solution injection rate 10 μ l, the mobile phase solvent uses chloroform, measure under 40 ℃ solvent flow rate 1.2ml/ minute, solvent temperature, be scaled polystyrene, calculate the weight average molecular weight of polyester resin.The weight average molecular weight of used polystyrene standard is 2000000,430000,110000,35000,10000,4000,600.Measure extruding the B layer of system behind the film.

(2) durability (humidity resistance) test

The resin-covered metal sheet of 60mm * 60mm is left standstill after two months in the climatic chamber of 80 ℃ * 98%RH, according to the visual observations appearance change.The situation that does not have fully to change is designated as (zero), and resin bed has a little crackle or has situation about expanding a little to be designated as (△), and resin bed has remarkable crackle or remarkable expansion arranged and produce situation about peeling off between laminated thin plate and metallic plate and is designated as (*).

(3) adaptability is given in embossing: anti-adhesiveness

When giving machine and give embossing with embossing shown in Figure 3, the situation that thin plate is sticked on the heated roller (warm-up mill) is designated as (*), and inadhesive situation is designated as (zero).

(4) adaptability is given in embossing: breaking property of refractory

When giving machine and give embossing, in heater heating thin plate process, the situation of thin plate fusing is designated as (*), situation about not fusing is designated as (zero) with embossing shown in Figure 3.

(5) adaptability is given in embossing: transfer printing

Visual observations is given thin plate after machine is given embossing with embossing shown in Figure 3, the transfer printing of embossing decorative pattern is got beautiful situation be designated as (zero), the shallow a little situation of transfer printing is designated as (△) in contrast to this, and transfer printing is poor, the embossing decorative pattern is shallow or be designated as (*) with the irrelevant just surperficial situation that becomes coarse of embossing decorative pattern.

(6) boiling water resistance test

The resin-covered metal sheet of 60mm * 60mm was flooded in boiling water 3 hours, the surface state of this resin sheet of visual observations, the situation that does not have fully to change is designated as (zero), and the situation that the surface becomes coarse a little is designated as (△), and the situation that distortion such as significantly expansion take place resin bed is designated as (*).

(7) processability

Resin-covered metal sheet is impacted the driving fit bend test, and the surface state of the fancy veneer of visual observations bending machining portion is designated as (zero) to the situation that does not almost have to change, and takes place a little that the situation of crackle is designated as (△), and the situation that crackle takes place is designated as (*).In addition, impacting the driving fit bend test is following carrying out.Make the sample of 50mm * 150mm separately from the length direction and the width of covered metal plate, keep more than 1 hour at 23 ℃, use folding test machine bending to 180 ° (inner bend radius 2mm) then, the cylindrical hammer of diameter 75mm, quality 5Kg is fallen on this sample from the height of 50cm.

A) making of laminate film

" B layer " composition of in table 1, having represented embodiment a1～a7 and comparative example a1～a6.

Table 1

As shown in table 1, embodiment a1～a7 and comparative example a1～a6 use the twin shaft of two the φ 65mm extruder that mixes, and utilize the coextrusion of feed head (feed block) mode, obtain to have the double-deck laminated thin plate of the B layer that resin as shown in table 1 forms.The gross thickness of laminated thin plate is 120 μ m, has represented the B layer thickness in the table 1.The weight average molecular weight of also having represented the B layer behind the system film in the table 1.The composition that mixes that consists of PBT resin (NOVADURAN 5020S:20 weight portion) and PETG resin (EASTER 6763:80 weight portion) of A layer, titanium oxide pigments 24 weight portions (the resinous principle amount is 100 o'clock).This is all identical except the comparative example a7～a13 of individual layer thin plate situation.

Table 2 has been represented the composition of comparative example a7～a13 individual layer thin plate.

Table 2

As shown in table 2, comparative example a7～a13 is the single thin film that only is made of the many layers of pigment addition, only uses the twin shaft of a φ 65mm to mix and extrudes machine-processed film.Gross thickness is 120 μ m.The system film all is curtain coating (casting) system embrane method of using the T mould.

B) coating (D layer) gives

Table 3 has been represented embodiment a8, a9, and the composition of comparative example a14～a19.

Table 3

Table 4 has been represented embodiment a10～a15, and the composition of comparative example a20, a21.

Table 4

About table 3 illustrated embodiment a8, a9 and comparative example a14～a19, and table 4 illustrated embodiment a13～a15, give printed layers and coating at laminated thin plate A layer side surface.Print process is common photogravure coating, after the A laminar surface applies overall printing with white color system printing ink, carries out the printing of part abstract patterns.Further, the clear coat that constitutes by the acrylic polyalcohol of cyanate cross-linking type with thickness shown in the table 4 coating thereon.

In addition, these coatings are given the B layer composition of goods shown in table 3 and table 4, and the material in the table 3 is discontented with unabridged version invention claim 6, therefore, does not utilize embossing to give the embossing adaptability of machine.The B layer thickness all is 30 μ m.Also have, the composition of A layer is all identical with embodiment a1～a7, comparative example a1～a13, and thickness is 90 μ m.Coating layer thickness is illustrated in table 3, table 4.

C) transparent thin film layer (E layer) gives

As shown in table 3, about embodiment a8, a9 and comparative example a14～a19, give printed layers and transparent thin film layer at laminated thin plate A layer side surface.Print process is common photogravure coating, after the A laminar surface applies overall printing with white color system printing ink, carries out the printing of part abstract patterns.Further, giving polyester with printing production line thereon is the adhesive resin layer, according to the stacked transparent thin film layer that is provided with of thermal welding.The mixing that consists of PBT resin (NOVADURAN 5020S:20 weight portion) and PETG resin (EASTER 6763:80 weight portion) of transparent thin film layer is formed, inorganic pigment such as oxygen-free titanium pigment in fact, and thickness is 50 μ m.The material of record satisfies claim 6 of the present invention because of the B layer in the table 4, therefore, has the adaptability of machine that embossing is given.

These each layer resins are formed the concrete following material that uses.

PBT:NOVADURAN 5008 (manufacturing of engineering plastics company of Mitsubishi), the MW=68000 of raw material

PBT:NOVADURAN 5020S (manufacturing of engineering plastics company of Mitsubishi), the MW=113000 of raw material

About 31mol.% of the pure composition of PETG:EASTER 6763 (manufacturing of EASTMAN chemical company) is by 1, the amorphism PET that the 4-cyclohexanedimethanol replaces, the MW=756000 of raw material

7% of the sour composition of co-PET:BK-2180 (manufacturing of Mitsubishi Chemical polyester company) is the copolymerization PET of M-phthalic acid, the MW=65800 of raw material

PET:RT-580 (Japanese UNIPET company make), the MW=134000 of raw material

The company of spinning clearly CARBODILITE HCM-8V:(day makes), carbodiimide is an anti hydrolysis agent

D) embossed pattern gives

The continuity method embossing of also generally using with flexible PVC thin plate is as shown in Figure 3 given machine 10 and is given embossed pattern.The summary of this device constitutes, at first utilize the contact-type mode of heating preheating thin plate 2 that uses METAL HEATING PROCESS roller 1, then utilize and use the non-contact type mode of heating of infrared heater 3 that thin plate is heated to arbitrary temp, utilize embossing plate roller 4 that the embossed pattern transcription is printed on the thin plate.

About giving the whole thin plate of embossing, be that the temperature of 180 ℃ and embossing plate roller is 60 ℃ and implements embossing and give with the heating-up temperature of thin plate.

E) making of resin-covered metal sheet

Be bonding agent then at the general polyester of using as the polyvinyl chloride covered metal plate of metal covering coating, making dried bonding agent thickness is 2～4 μ m degree, then utilize the dry and heating coated face of hot-blast heater and infrared heater, the surface temperature of setting the preceding zinc-plated copper coin (thickness 0.45mm) of lamination is 235 ℃, use roll laminating machine cover layer stacked plate immediately, and, estimate above-mentioned every index by natural air cooling making resin covering copper coin.The kind of bonding agent, coating condition are all identical in whole embodiment and comparative example.

F) evaluation of printed patterns design resin-covered metal sheet

Carry out above-mentioned evaluation for gained printed patterns design resin-covered metal sheet.The evaluation result of having represented embodiment a1～a7, comparative example a1～a13 in the table 5.

Table 5

Table 6 has been represented embodiment a8, a9, and the evaluation result of comparative example a14～a19.

Table 6

	Durability (humidity resistance)	Processability	Anti-boiling water dipping property
				Embodiment a8	○	○	○
Embodiment a9	○	○	○
				Comparative example a14	△	○	○
Comparative example a15	△	○	○
				Comparative example a16	×	○	○
Comparative example a17	×	○	○
				Comparative example a18	×	○	○
Comparative example a19	×	○	○

Table 7 has been represented embodiment a10～a15, and the evaluation result of comparative example a20, a21.

Table 7

Can obtain to draw a conclusion from this result.

Embodiment a1～a7 and comparative example a1～a13 (table 5)

Comparative example a7～a13 is utilizing the painted single-layer polyester thin layer of titanium oxide pigments to be pressed onto example on the metallic plate, but the durability result is all poor.

Comparative example a7～a9 has the weight average molecular weight that the B layer of claim 3 of the present invention need possess, and expands but many bubble shapes have taken place in the sample after the hot resistance test.May be because the rising of the permeate water component of the lamella thickness direction that the interpolation titanium oxide pigments causes has promoted the corrosion of metal sheet surface, cause that the part between thin plate and the metallic plate is peeled off.

Confirm among comparative example a10～a13 that the many places crackle takes place resin bed, and also as if reduce with the bonding force of metallic plate.Thin layer is kept bigger intensity among comparative example a7～a9, and therefore at bonding force sloping portion generation bubble, with respect to this, the deterioration of resin bed self is also remarkable among comparative example a10～a13, therefore thinks crackle must take place.

Also have, among comparative example a7～a9, resin is formed the B layer compositing range that is in claim 6 of the present invention, therefore feed not produce when machine is given in embossing to adhere to or fusing, but because of crystallinity is high can't the transfer printing embossing.On the other hand, the resin bed of being made up of individual layer among comparative example a10～a13 is that low-crystalline is formed, and therefore produces the adhesion of giving the machine warm-up mill to embossing, is difficult to thin plate is passed into the embossing plate roller.

Among comparative example a1～a6, thin plate is by the A layer and the B layer is two-layer constitutes, but the weight average molecular weight of B layer is lower than the scope of the invention among comparative example a3～a6, still can't obtain good humidity resistance.Thickness is thinner than the required thickness of B layer of the present invention among the comparative example 1a, and the pigment addition to the B layer among the comparative example a2 is many.The result of this moment also is that humidity resistance is poor.

With respect to this, resin bed made among embodiment of the invention a1～a7 that the two-layer pigment that limits with the layer of metallic plate bonding plane side adds to obtain favorable durability (humidity resistance).Also have, the resin of B layer is formed among the embodiment a1～a4 consistent with claim 6 of the present invention, utilizes embossing to give machine and gives embossing to thin plate, can obtain to have the resin-covered metal sheet of good embossing outward appearance.Humidity resistance is good among the embodiment a7, but therefore the B layer slow-footed PET resin that is crystallization, can't carry out crystallization, the adaptability that can't give machine that embossing is given when extruding the system film.

Embodiment a8, a9 and comparative example a14～a19 (table 6)

Use and not have the adaptive composition of giving machine to embossing and form as the B layer, and utilize printing and coating to give design, among the comparative example a15 resin form identical with the B layer of embodiment a6, so but extrude the weight average molecular weight of making behind the film and be lower than embodiment a6 because of adding titanium oxide pigments.Its result cracks after the humidity resistance test owing to the deterioration of resin bed self.About adding carbodiimide is the comparative example a14 of anti hydrolysis agent, also is that addition is few, can't obtain effect.

Comparative example a16～a19 is the situation of adding the titanium oxide pigments that surpasses the scope of the invention at the B layer, and these can't obtain thin plate is made the effect of two-layer formation.

Comparative example a17, and a19 be that the carbodiimide that has added scope shown in the claim 4 of the present invention is the situation of anti hydrolysis agent, but additive effect reduction when adding the layer identical with titanium oxide pigments to can't obtain the sufficient effect that suppresses molecular weight and molecular weight when extruding the system film.

With respect to this, the pigment addition of B layer and is under the situation of anti hydrolysis agent using carbodiimide in the scope of the invention among embodiment a8 and the a9, can suppress molecular weight and molecular weight when the system film, can obtain good humidity resistance simultaneously.

Embodiment a10～a15, and comparative example a20, a21 (table 7)

Be coated with printed layers and coating or printed layers and transparent resin layer on the laminated thin plate, arbitrarily A layer, B layer all use the scope of the invention under the situation, so humidity resistance is no problem.

Second the present invention

For further concrete and describe second the present invention in detail, represent embodiment below, but second the present invention is not subjected to any qualification of these embodiment.In addition, the bioassay standard of the rerum natura of thin plate shown in embodiment and the comparative example and resin-covered metal sheet, test method are as follows.

(1) crystallization melting peak temperature (Tm)

The DSC-7 that adopts PerkinElemer to make measures the 10mg sample according to JIS-K7121 " computational methods of the transition temperature assay method-melt temperature of plastics " under 10 ℃ of/minute firing rates.Crystallization fusion summit temperature when once heating up is designated as Tm.And obtain crystallization fusion heat Δ Hm simultaneously.Also having, is to measure before machine is given in the feeding embossing about using the substrate resin layer of extruding the making of system embrane method.

(2) crystallization peak temperature (Tc)

The DSC-7 that adopts PerkinElemer to make measures the 10mg sample according to JIS-K7121 " computational methods of plastics transition temperature assay method-crystallized temperature " under 10 ℃ of/minute firing rates.Crystallization summit temperature when once heating up is designated as Tc.

And obtain crystallization heat Δ Hc when once heating up simultaneously.For identical during with the above-mentioned Tm of mensuration in the sample of sample.

(3) adaptability is given in embossing: anti-adhesiveness

When giving machine 10 and give embossing with embossing shown in Figure 3, thin plate is sticked to heated roller (metallic roll 1) go up and can't peel the situation of coming and be designated as (*), the situation that can't carry out steady production because of adhering to is designated as (△), and inadhesive situation is designated as (zero).

(4) adaptability is given in embossing: breaking property of refractory

When giving machine 10 and give embossing with embossing shown in Figure 3, in heater 3 heating thin plate processes, the situation of thin plate fusing is designated as (*), situation about not fusing is designated as (zero), fold is not arranged or have the situation of the width of cloth that significantly contracts to be designated as (△) though have to rupture.

(5) adaptability is given in embossing: transfer printing

Visual observations is given thin plate after machine 10 is given embossing with embossing shown in Figure 3, the transfer printing of embossing decorative pattern is got beautiful situation be designated as (zero), the shallow a little situation of transfer printing is designated as (△) in contrast to this, and transfer printing is poor, the embossing decorative pattern is shallow or be designated as (*) with the irrelevant just surperficial situation that becomes coarse of embossing decorative pattern.

(6) embossing hear resistance: heat-resisting quantity

Lamination give the metallic plate that machine 10 is given the thin plate of embossing with embossing shown in Figure 3, in 105 ℃ heated air circulation type baking oven, left standstill 3 hours, visual observations then, the situation that does not have fully to change of comparing with the embossing shape before the input baking oven is designated as (zero), the situation that the embossing answer takes place in contrast to this a little is designated as (△), and embossing is replied significantly or the complete obiteration of embossing decorative pattern is that shaggy situation is designated as (*).

A) the resin-covered metal sheet making of design thin plate (A+B or A+C+B)

Give the resin of layer forms as embossing, use " the EASTERPET G6763 " of EASTMAN chemical company, and cooperate the big association of 0.75 weight portion (when the resinous principle amount is 100 weight portions) change into company fatty acid ester base lubricant " PO-8 ", 0.5 weight portion RAYON company of Mitsubishi acrylic acid series lubricant " Metablen L-1000 ", to use the PETG base green of Tokyo printing ink company as pigment be masterbatch, cooperate 16 weight portions in pigment concentration, layer is given in the embossing that utilizes calendering system embrane method to make thickness 120 μ m.

As substrate resin layer (substrate resin layer or C+ substrate resin layer), make the laminated thin plate (A+B or A+B+C) of resin composition as shown in table 8 and thickness.Utilize to use that the The tape casting of T mould makes extrude system film thin plate and have in fact the layer that constitutes by noncrystalline mylar time be the coextrusion of adopting feed head mode, the thickness of the layer that is made of noncrystalline mylar is 10 μ m in fact.

About the thin plate of embodiment b9,, carry out 160 ℃ * 30 seconds back heat treated with the noncontact heating with importing in the heating furnace with infrared heater after the traction of casting roller.(Δ Hm-Δ the Hc)/Δ Hm of the substrate resin layer after the back heat treated is 0.76.

Table 8

Also have, each raw material that uses in the table 8 is as follows.

NOVADURAN 5020S: homopolymerization PBT resin, the manufacturing of engineering plastics company of Mitsubishi (glass transition temperature: 45 ℃, crystallization melting peak temperature: 223 ℃)

Co-PET BK-2180: M-phthalic acid copolymerization PET, Mitsubishi Chemical Ind's manufacturing (glass transition temperature: 76 ℃, crystallization melting peak temperature: 246 ℃)

CORTERRA CP509200: the homopolymerization resin, the manufacturing of SHELL company (glass transition temperature: 49 ℃, crystallization melting peak temperature: 225 ℃)

EASTER 6763: about 31% usefulness 1 of the ethylene glycol of PETG part, the amorphism polyester resin that the 4-cyclohexanedimethanol replaces, the manufacturing of EASTMAN chemical company (glass transition temperature: 81 ℃, crystallization melting peak temperature: do not observe)

PCTG 5445: about 70% usefulness 1 of the ethylene glycol of PETG part, the amorphism polyester resin that the 4-cyclohexanedimethanol replaces, the manufacturing of EASTMAN chemical company (glass transition temperature: 88 ℃, crystallization melting peak temperature: do not observe)

Table 9

	Have or not the A layer	Have or not the C layer	B layer kind	B layer thickness (μ m)	The after-baking of system film
						Embodiment b1	Have	Do not have	B-1	40	Do not have
Embodiment b2	Have	Do not have	B-2	40	Do not have
						Embodiment b3	Have	Have	B-2	40	Do not have
Embodiment b4	Have	Have	B-2	20	Do not have
						Embodiment b5	Have	Do not have	B-3	40	Do not have
Embodiment b6	Have	Do not have	B-2	100	Do not have
						Embodiment b7	Have	Do not have	B-7	40	Do not have
Embodiment b8	Have	Do not have	B-8	40	Do not have
						Embodiment b9	Have	Do not have	B-5	40	Have
Comparative example b1	Do not have	Do not have	B-1	40	Do not have
						Comparative example b2	Do not have	Do not have	B-3	40	Do not have
Comparative example b3	Have	Do not have	B-4	40	Do not have
						Comparative example b4	Have	Do not have	B-5	40	Do not have
Comparative example b5	Have	Do not have	B-6	40	Do not have
						Comparative example b6	Have	Do not have	Do not have	—	—
Comparative example b7	Have	Do not have	B-2	15	Do not have
						Comparative example b8	Have	Have	B-2	15	Do not have

B) embossed pattern gives

The continuity method embossing that utilization is also generally used at the soft PVC thin plate is given machine 10 (with reference to Fig. 3) and is given embossed pattern.Heated roller is set in 100 ℃, about embodiment b1～b9, and comparative example b1～b8, adopts heater that the thin plate before the contact embossing patterned roll is heated to 165 ℃.Also have, the temperature of embossing plate roller is 70 ℃, is the colored roller of surface average roughness Ra=10 μ m.

About embodiment b10～b13, and comparative example b9～b14, heated roller (metallic roll 1) is set in 100 ℃, change thin plate temperature by the heater heating.This moment embossing plate roller 4 temperature and embossing plate pattern and embodiment b1～b9, to reach comparative example b1～b8 identical.Also have, substrate resin layer kind and thickness thereof are identical when having the substrate resin layer.

C) making of resin-covered metal sheet

Be the polyester of generally using and using that heat-curable adhesive is applied to metal covering then as the polyvinyl chloride covered metal plate, make dried bonding agent thickness at 2～4 μ m degree (bond layer (E)), then with hot-blast heater and infrared heater drying and heating coated face, (metallic plate (F): surface temperature thickness 0.45mm) is set in 235 ℃ galvanized steel plain sheet, cover the polyester resin thin plate with the roll laminating machine immediately, and resin-covered metal sheet is made in cooling.

D) the resin-covered metal sheet evaluation of design thin plate (A+B) and resin-covered metal sheet

Estimate above-mentioned each index.The table 10 that the results are shown in embodiment b1～b9, comparative example b1～b8.Produce the sample that adheres to about the heated roller of embossing being given machine in the table 10 and do not carry out the evaluation of back.Also have, with heater heating back thin plate produce remarkable fold, phenomenons such as the width of cloth that contracts, fusion fracture do not carry out the stable on heating evaluation of embossing behind the lamination.

Table 10

Comparative example b3, b4 and b5 are the situations that substrate resin layer [(Δ Hm-Δ Hc)/Δ Hm] is lower than claim scope of the present invention, and the heated roller that laminated thin plate is given machine to embossing has produced adhesion.Thereby can't give embossed pattern to thin plate.Wherein the adhesion that takes place of the relatively large comparative example b3 of this numerical value is the lightest, can peel off from heated roller.But because the thin plate elastic modelling quantity that heater heating causes descends and the adhesion of cylinder is combined, thin plate ruptures.

Comparative example b6 does not use the substrate resin layer, give in the machine situation that layer is given in the embossing that only feeds calendering system film in embossing, alleviated adhesion by the lubricant that adds more amount, but elastic modelling quantity descends significantly during with heater heating thin plate, and the fusion fracture still takes place to heated roller.

Comparative example b1 and b2 give the situation that only feeds the substrate resin layer that meets the scope of the invention in the machine in embossing, though do not take place to the adhesion of heated roller or the fusion fracture of heating the thin plate that causes by heater, but the crystallinity height can't carry out most important embossing and give.

Though comparative example b7 has the crystallinity that meets substrate resin layer scope of the present invention, thickness is thinner than the situation of preferable range, though prevented the adhesion to heated roller, the thin plate undercapacity when heating with heater and fusion fracture takes place.When layer that coextrusion is made of noncrystalline polyester resin in fact, extrude gauge of sheet and can also can see identical result from the comparative example b8 that is thicker than comparative example b7, therefore can to know in order preventing and to rupture when heating that of the present invention have crystalline substrate resin layer and need have more than the specific thicknesses by heater.

Embodiment b9 is to use the composition of the composition identical with comparative example b4 as the substrate resin layer, and extrude the after-applied heat treated situation of system film, utilize heat treatment to promote the crystallization of substrate resin layer, do not produce the thin plate fracture when heating, obtained good embossing transfer printing to the adhesion of heated roller with heater.Though embodiment b9 does not meet claim 15 or 16 but meet the situation of claim 14 and 17, though be in the low state of crystallinity of substrate resin layer when extruding the system film, if before embossing is given, heat-treat the adaptability that to give as substrate resin layer of the present invention.

Embodiment b1～b8 is the composition of substrate resin layer and the situation that thickness is in preferable range of the present invention, has the preferred crystallinity of the present invention when extruding the system film, need not carry out crystallization and handle in the postorder operation, just can obtain good embossing and give adaptability, the hear resistance of embossing is also good.

Table 11

	B layer kind	B layer thickness (μ m)	Thin plate temperature before the embossing (℃)
				Embodiment b10	B-2	50	165
Embodiment b11	B-2	50	175
				Embodiment b12	B-2	50	185
Embodiment b13	B-2	50	195
				Comparative example b9	B-2	50	145
Comparative example b10	B-2	50	155
				Comparative example b11	B-2	50	210
Comparative example b12	Do not have	—	145
				Comparative example b13	Do not have	—	155
Comparative example b14	Do not have	—	165

Table 12

Embodiment b10～b13 shown in above-mentioned table 11 and the table 12, and comparative example b9～b14 the substrate resin layer is existed and non-existent situation changes the thin plate temperature that feeds before the embossing patterned roll.The minimum comparative example b9 of thin plate temperature that has before substrate resin layer and embossing are given is an embossing hear resistance deficiency.With respect to this, the embossing hear resistance has improvement slightly among the comparative example b10 of thin plate temperature though improved, and insufficient.

With respect to this, the embodiment b10～b13 that further improves the thin plate temperature has then obtained sufficient embossing hear resistance.Just, the thin plate temperature approaches among the embodiment b13 of set upper limit temperature (Tmb-20) in the claim 22 ℃, can see the thin plate width of cloth that contracts a little when heating with heater.

Have the substrate resin layer, and the thin plate temperature is than the fusion fracture that has produced thin plate among the taller comparative example b11 of defined terms in the claim 22.

3 layers the situation that do not have of comparative example b12～b14 is, because of embossing is given layer by calendering legal system film, and contain the more amount lubricant, therefore there is not problem fully to 100 ℃ of heated rollers adhesions, but the thin plate temperature when heating with heater rises, therefore thin plate generation fold and fusion fracture can't give embossing embodiment b10～accessing under the required thin plate temperature of satisfied embossing hear resistance of b13 acquisition.

Utilize possibility on the industry

Resin-covered metal sheet of the present invention and resin-covered metal sheet are two-layer with the design thin plate by making the polyester resin layer, make pigment addition with the resin bed of metallic plate contact surface side below particular value, and make molecular weight at particular range, can be made into the good resin-covered metal sheet of durability (humidity resistance), generation melting fracture or fold can be reduced when giving the embossed pattern design to thin plate, low-cost production can be realized stablizing. Further, form and B layer composition by regulation A layer, can use in the past and give machine for the embossing of the flexible PVC thin plate being given embossing, can obtain to have the resin-covered metal sheet of good embossing outward appearance.

Claims (14)

1. resin-covered metal sheet is characterized in that: at least by two-layer main component be the not tensile layer A layer of polyester resin and not the B layer side of the laminated thin plate that constitutes of tensile layer B layer be stacked on the metallic plate through bond layer and constitute as bonding plane; The gross thickness of described laminated thin plate is 65 μ m～300 μ m, is used for painted and hidden pigment simultaneously and mainly is added on the A layer; Described A layer has the thickness of 50 μ m～250 μ m; When described B layer has 15 μ m～80 μ m thickness, to the pigment composition addition of described B layer being, is below 10 weight portions with respect to 100 parts by weight resin compositions, and described A layer side surface has been endowed embossing.

2. as the resin-covered metal sheet of claim 1 record, it is characterized in that: described B layer does not contain pigment composition in fact.

3. as the resin-covered metal sheet of any record in claim 1 or 2, it is characterized in that: the weight average molecular weight after the converting with styrene according to gel permeation chromatography (GPC) of the described B layer of system behind the film is in 75000～140000 scope.

4. as the resin-covered metal sheet of claim 1 or 2 records, it is characterized in that: when the resin Composition of described B layer was 100 weight portions, described B layer was added with the carbodiimide compound of 0.1 weight portion～5 weight portions.

5. as the resin-covered metal sheet of claim 1 or 2 records, it is characterized in that: described B layer contains the polybutylene terephthalate (PBT) resin above resinous principle 20 weight %.

6. as the resin-covered metal sheet of claim 1 record, it is characterized in that: described B layer contains the polybutylene terephthalate (PBT) resin above resinous principle 55 weight %, and the main body of described A layer is the mylar of amorphism or low-crystalline in fact.

7. as the resin-covered metal sheet of claim 6 record, it is characterized in that: the amorphism in fact of described A layer or the mylar of low-crystalline are, the main body of acid composition is terephthalic acid (TPA) or dimethyl terephthalic acid, and 20～80mol.% of pure composition is 1, the 4-cyclohexanedimethanol, residue 80～20mol% is an ethylene glycol.

8. as the resin-covered metal sheet of claim 7 record, it is characterized in that: in the described A layer with described B layer by layer the opposed surface of folded side give printed layers (C layer), further give the clear coat (D layer) of 2 μ m～20 mu m range thickness on its surface.

9. as the resin-covered metal sheet of any record in the claim 6～8, it is characterized in that: will under described B layer is in the state of crystallization, carry out the stacked incorporate thin plate that constitutes by A layer and B layer or be heated to more than the glass transition temperature (Tga) of described A layer by the thin plate that D layer, C layer, A layer, B layer constitute and after the following temperature of fusing point (Tmb) of described B layer, give embossing with the embossing plate roller to described A layer side surface, through bonding agent described B layer side is layered on the metallic plate as bonding plane then.

10. as the resin-covered metal sheet of claim 1 record, it is characterized in that: in described A layer, give described C layer with the opposed surface of the folded layer by layer side of described B, further give on its surface main body for amorphism or low-crystalline in fact mylar and do not add pigment and thickness at the transparent resin layer (E layer) of 25 μ m～100 mu m ranges.

11. resin-covered metal sheet as claim 10 record, it is characterized in that: the amorphism in fact of described E layer or the mylar of low-crystalline are, the main body of acid composition is terephthalic acid (TPA) or dimethyl terephthalic acid, and 20～80mol% of pure composition is 1, the 4-cyclohexanedimethanol, residue 80～20mol% is an ethylene glycol.

12. resin-covered metal sheet as any record in claim 10 and 11, it is characterized in that: carry out the stacked incorporate thin plate that constitutes by E layer, C layer, A layer, B layer under the crystallization state and be heated in the glass transition temperature (Tga and Tge) of described A layer and described E layer arbitrary high that more than side's glass transition temperature and after the following temperature of the fusing point of described B layer (Tmb) being at described B layer, give embossing with the embossing plate roller to described A layer side surface, through bonding agent described B layer side is layered on the metallic plate as bonding plane then.

13. as the resin-covered metal sheet of claim 1 or 2 records, it is characterized in that: described A layer and described B layer are to be undertaken integrated by coextrusion system embrane method.

14. an interior of building ornament materials, the resin-covered metal sheet of any record in the use claim 1～13.

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