JP2971515B2 - Stainless steel / resin laminate sheet and products using it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a stainless-resin laminate sheet in which a hot-melt adhesive layer for adhesion is adhered to the surface of a stainless steel thin plate, and a product using this sheet. About.

[Prior Art] Conventionally, a surface of a base made of a synthetic resin is coated with a metal. As a method of applying a metal coating to the surface of such a synthetic resin, there has been a method of applying metal plating to the surface of a resin base. However, such a method has problems such as a complicated plating process, high cost, and difficulty in application to a large substrate.

On the other hand, there is a method of bonding a thin metal sheet to the surface of a synthetic resin base. Such a device is characterized in that it is only necessary to attach a metal sheet to the surface of a molded resin substrate by bonding, and that the operation is simple and that the substrate can be easily attached to a large substrate. However, in general, the bonding strength between a metal and a synthetic resin is relatively low, and problems such as peeling are likely to occur. For this reason, most of such materials generally use an aluminum sheet which is easy to bond as a metal. However, this aluminum has a disadvantage that it is easy to bond, but is soft and easily scratched.

On the other hand, stainless steel is advantageous in that it is hard and hard to be damaged, has extremely high corrosion resistance, has a high-grade metallic luster, and is easily colored. However, this stainless steel has poor adhesion due to the formation of a strong oxide film on its surface, and it has been difficult to bond this stainless steel sheet to the surface of a synthetic resin base. In addition, in order to bond the stainless steel sheet to the synthetic resin base, the pretreatment step and the like are complicated and inefficient.

In order to solve such a problem, a first adhesive layer is applied to the surface of a stainless steel sheet, and a second adhesive layer is applied on the first adhesive layer. Resin laminate sheets were developed. Such sheets are disclosed in Japanese Patent Application Nos. 1-286959 and 1-286960, both of which are the same applicant as the present applicant.

Such a sheet uses, as the first adhesive layer, one having a high adhesiveness to the stainless steel sheet,
In addition, as the second adhesive layer, a synthetic resin material having adhesiveness to the first adhesive layer and having general-purpose adhesiveness to various synthetic resin materials forming the base is used.

However, such a sheet is manufactured in the form of a long sheet, and each user cuts and presses the sheet into a predetermined shape, and heat-welds the processed sheet to the surface of the base. Alternatively, the processed sheet is placed in a mold, a resin is injected into the mold, and the sheet is integrally heat-sealed to the substrate by heat during injection molding.

Therefore, it is difficult to strictly regulate the conditions of the heat welding in the step of manufacturing the final product by integrally bonding the sheet to the base. The second adhesive layer is
Since it has general-purpose adhesiveness to various resin materials, a certain degree of bonding conditions, for example, high temperature and high pressure are required to obtain sufficient bonding strength. However, in the final step of bonding this sheet to the substrate,
As described above, it is difficult to satisfy such bonding conditions. For example, in a case where a processed sheet is placed in a mold and the sheet is adhered to a substrate at the same time as injection molding, the temperature and pressure of the injected resin depend on the type of the resin forming the substrate and the pressure. The conditions are limited by the shape of the base and the like, and the limited conditions do not always match the bonding conditions of the sheet. Therefore, there are problems such as when such a sheet cannot be used, or in order to obtain a sufficient adhesive strength between the sheet and the substrate, it is necessary to change the conditions of the molding step of the substrate.

Further, in the final step of bonding the sheet to the substrate, the control of the bonding conditions is likely to be inaccurate, and the bonding strength with the substrate may be reduced.

[Problems to be Solved by the Invention] The present invention has been made based on the above circumstances, and can be easily and firmly adhered to a substrate such as a synthetic resin.
Moreover, the present invention provides a stainless steel / resin laminate sheet having a relatively loose bonding condition and a product utilizing the characteristics of the sheet.

[Means for Solving the Problem and Action Thereof] The laminate sheet of the present invention covers at least one surface of a stainless steel thin plate with a first adhesive layer, and further has a first adhesive layer on the first adhesive layer. The second adhesive layer is coated, and the third adhesive layer is further coated on the second adhesive layer, and is provided with three adhesive layers. The first adhesive layer is a hot-melt adhesive containing a polyolefin-based polymer and a copolymer of an aliphatic unsaturated carboxylic acid or an anhydride thereof, and a second hot-melt adhesive. The layer is an adhesive layer obtained by mixing a plurality of types of thermoplastic resins, and has good adhesiveness with the first adhesive layer, and has general-purpose adhesiveness with various resin materials. The third adhesive layer is made of a thermoplastic resin material compatible with the resin material forming the substrate to be bonded.

Such a laminate sheet uses the above-mentioned material for the first adhesive layer that adheres to a stainless steel thin plate, and has a strong adhesive force to stainless steel. A second adhesive layer is coated on the first adhesive layer, and the first adhesive layer and the third adhesive layer are firmly fixed by the second adhesive layer. Glued. The third adhesive layer is formed of a thermoplastic resin compatible with the resin material of the base, has an extremely good adhesiveness with the base, has a low bonding condition with the base, and can be used in any case. Adhesion to the substrate can be ensured, and reliable adhesion can be achieved even if the management of the adhesion conditions is incorrect in this adhesion step.

Such a laminate sheet is firmly integrated as a whole, and it is easy to cut and press this laminate sheet. Further, since the adhesive layer also provides lubrication with the mold, there is no need to use a lubricant at the time of press molding, and the operation is easy. Also, this third
It is preferable to use the same type of resin material as the resin material of the substrate to be bonded. As described above, if the same type of resin material is used, the adhesion to the base can be more easily achieved.

Embodiment An embodiment of the present invention will be described below with reference to the drawings. First
The figure shows the implementation of the stainless steel / resin laminate sheet. The stainless-resin laminate sheet 11 has a first hot-melt adhesive layer 13 adhered to one surface of a stainless steel sheet 12 made of a stainless steel thin plate. Is further coated with a second hot-melt type adhesive layer 14. Further, the second adhesive layer 14
A third adhesive layer 15 is applied on the substrate.

This stainless sheet 12 has a thickness of 0.01
Those having a size of about mm to 0.5 mm are used. In addition, according to the specifications, the surface is glossy surface, satin finish, hairline finish, and other surface finishes, and if necessary, for example, by adjusting the thickness of the oxide film on the surface, coloring by light interference Finishing is done.

The first adhesive layer 13 is for bonding to the stainless steel sheet 12, and is a graft copolymer of a polyolefin-based polymer and an aliphatic unsaturated carboxylic acid or an anhydride thereof, or a graft copolymer thereof. It is composed of a hot-melt adhesive resin composed of a mixture of a graft copolymer and a polyolefin-based polymer. This adhesive has an extremely strong adhesive force to the stainless steel material, so that the stainless steel sheet 12 is sufficiently bonded to the stainless steel material for practical use.

When the graft copolymer and the polyolefin polymer are mixed, the content of the graft copolymer in the mixture is preferably 0.5% by weight or more. Further, the kind of the aliphatic unsaturated carboxylic acid or its anhydride to be graft-copolymerized with the polyolefin-based polymer is, from the viewpoint of the ease of the graft copolymerization,
It is preferable to select from acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride and the like. The graft ratio of the graft copolymer is selected in accordance with the type of unsaturated carboxylic acid to be graft-copolymerized with the polyolefin-based polymer, but is usually preferably in the range of 0.01 to 5.0%.

The second adhesive layer 14 is for firmly bonding the first adhesive layer 13 and the third adhesive layer 15 to each other. That is, the first purpose of the first adhesive layer 13 is to have an adhesive property with the stainless steel sheet 12 and an insufficient adhesive property with other synthetic resin materials. Therefore, the second adhesive layer 14 is formed on the first adhesive layer 13, and the third adhesive layer 15 and the first adhesive layer 15 are interposed via the second adhesive layer 14. By bonding 13, the stainless steel sheet 12 and the first to third adhesive layers 13, 14, and 15 are firmly and integrally bonded to each other.

The kind of the adhesive forming the second adhesive layer 14 is variously selected according to the kind of the synthetic resin material forming the third adhesive layer 15, the required adhesive strength, and the like. Also,
The selection is made in accordance with the workability required when the laminate sheet is press-formed or thermally welded to the base. Generally, the adhesive constituting the second adhesive layer 14 preferably has sufficient adhesiveness and workability in common to various synthetic resin materials generally used.

In consideration of these points, the adhesive used for the second adhesive layer 14 includes three components of a thermoplastic polyester resin, an ethylene copolymer, and another type of thermoplastic resin. A melt-mixed adhesive resin composition is preferred. The thermoplastic polyester resin includes 40 to 100 mol% of terephthalic acid as a dicarboxylic acid component and 0 to 60 mol% of other aromatic dicarboxylic acids, and 1,4-butanediol 40 as a low molecular weight glycol component. -100 mol% and 0-60 mol% of diethylene glycol or 1,6-hexanediol, and 0-10 mol% of polytetramethylene glycol having a molecular weight of 600-6000 with respect to all dicarboxylic acids.
It is preferably a thermoplastic polyester resin having a reduced viscosity of 0.5 to 100 ° C and a viscosity of 0.5 or more.

Also, the component of this thermoplastic copolyester resin is
30 to 90%, and the ethylene copolymer contains one or more functional groups selected from an epoxy group, a carboxylic acid group or a dicarboxylic anhydride group,
The total amount of the components of the ethylene copolymer and the thermoplastic resin is 70 to 10% by weight, and the components of the ethylene copolymer in the total amount of the ethylene copolymer and the thermoplastic resin are included. More preferably, the proportion is from 5 to 100% by weight.

Further, as the other thermoplastic resin, any one of a vinyl aromatic hydrocarbon polymer or copolymer, a (meth) acrylate polymer or copolymer, an ethylene polymer, and a polyolefin elastomer is used. Or one or more of them.

The third adhesive layer 15 is made of a thermoplastic resin material compatible with a synthetic resin material forming a substrate to be bonded, preferably a resin material of the same kind as the material forming the substrate. You. For example, when the resin material constituting the base is a vinyl chloride resin, the third adhesive layer 15
It is preferable to use the same type of vinyl chloride resin material.

Next, a method and an apparatus for manufacturing such a laminate sheet 11 will be described with reference to FIG.

Reference numeral 24 in FIG. 2 denotes a roll around which the stainless steel sheet 12 is wound. The roll 24 supplies the belt-shaped stainless steel sheet 12. The stainless sheet 12 is guided by a guide roller 19, heated to a predetermined temperature by a heater 22, and then sent between a pair of thermocompression rollers 21. Reference numeral 17 denotes a roll for supplying a resin material film 13 'for forming the adhesive layer 13. This film 13 'is made of the first adhesive layer 13
Is formed of a resin material having a thickness of, for example, 0.05 mm. Reference numeral 18 denotes the second adhesive layer.
A roll for supplying a film 14 ′ of a resin material forming 14. This film 14 'is formed of the second adhesive layer 14
Is formed of a resin material having a thickness of, for example, 0.05 mm. A roll 25 supplies a film 15 'of a resin material forming the third adhesive layer 15. The film 15 'is a film made of a resin material forming the third adhesive layer 15, and has a thickness of, for example, 0.05 mm.

Then, the films 13 ', 14', 15 'supplied from these rolls 17, 18, 25 are supplied between a pair of thermocompression rollers 21, overlapped with the stainless steel sheet 12, and thermocompressed to each other. The above first sheet is placed on the stainless steel sheet 12.
Or third adhesive layers 13, 14, 15 are formed. In this case, the pressing pressure of the pressing roller 21 is 1.5 to 2.0 kg / cm ² , and the pressing temperature is 130 to 150 ° C. And this laminate sheet
11 is further heated by the heater 23,
It is taken up by the take-up roll 16 via 20.

The laminate sheet 11 of such an embodiment has, for example, an adhesive strength between the stainless steel sheet 12 and the first adhesive layer 13.
It reaches 6.0 kg / cm or more, and peeling between them is completely prevented. The adhesive strength between the second adhesive layer 14 and the third adhesive layer 15 is 2.8 kg / cm when the third adhesive layer 15 is polycarbonate, and 2.8 kg / cm when the third adhesive layer 15 is ABS. 3.4kg
/ cm, 1.0kg / cm for polyethylene, 2.6kg / cm for hard vinyl chloride, 3.0k for soft vinyl chloride
g / cm.

In addition, the laminated body sheet 11 is not necessarily limited to the above, and can be changed according to various specifications. For example, the adhesive layer is not limited to one side and may be applied to both sides. The adhesive layer does not need to be applied to the entire surface of the stainless steel sheet, but may be applied to a part of the surface.

As described above, this laminated sheet 11 is a stainless steel sheet.
12 and the adhesive layers 13, 14, 15 are tightly integrated,
The laminate sheet 11 can be easily cut, bent, pressed, etc., and the laminate sheet has a thermoplastic resin material compatible with the synthetic resin material of the substrate to be bonded,
Preferably, since the third adhesive layer 15 made of the same resin material as the resin material of the base is adhered, the third adhesive layer 15 can be easily and firmly bonded to the base, and the bonding conditions are mild. This laminated sheet can be easily and firmly adhered to a substrate even in a production line or the like where it is difficult to control accurately.

FIG. 3 shows another method and apparatus for manufacturing the laminated sheet 11. In this manufacturing apparatus, the films 13 'and 14' forming the first adhesive layer 13 and the second adhesive layer 14 are applied by the pressure roller 21, and then the third pressure roller 26 Film forming an adhesive layer 15 of
15 'is thermocompressed. 27 and 28 are heaters. This is a film for forming first and second adhesive layers.
The conditions for thermocompression bonding of the films 13 'and 14' and the conditions for thermocompression bonding of the film 15 'forming the third adhesive layer can be set as different conditions. Since various resin materials are used for the third adhesive layer 15 in accordance with the type of the resin material of the base to be bonded, when the resin material of the third adhesive layer 15 is changed, The conditions for the thermocompression bonding of the film 15 'can be easily changed.

Of course, the production method and production apparatus for the laminated sheet are not limited to those described above. For example, the first
Alternatively, the films 13 'and 14' forming the second adhesive layer may be thermocompression-bonded to each other in another step in advance, and the integrated film may be supplied and thermocompression-bonded on the stainless steel sheet 12. Further, in some cases, the three films 13 ', 14', and 15 'forming the first to third adhesive layers are thermocompression-bonded together in a separate step, and the three films are integrated. The supplied film may be supplied and thermocompression-bonded onto the stainless steel sheet 12.

In addition, various products using the laminated sheet can be provided by utilizing the property of the laminated sheet that can be easily thermally bonded to the base.

For example, FIGS. 4 and 5 show a molding material for an automobile, for example, a side molding 30 using the laminated sheet. The side molding includes, for example, an elongated band-shaped molding body 31 made of a vinyl chloride resin material, and a laminated sheet 11 obtained by cutting the laminated sheet 11 into an elongated band shape is thermally welded to the surface of the molding body 31. Have been. In this case, the substrate, that is, the same kind of vinyl chloride resin as the molding body 31 is used for the third adhesive layer 15 of the laminate sheet 11. This molding is manufactured in a long form, cut into an appropriate length, and attached to the side of the vehicle body.
In this case, the laminate sheet 11 is firmly
Therefore, even if the side molding 31 is cut or bent, the stainless sheet 12
Does not peel off.

In addition, as shown in FIG. 6, for example, the side molding 30 supplies the band-shaped laminated sheet 11 supplied from the roll 34 to a nozzle 33 of an extruder 32 for extruding and molding the molding main body 31, The laminated body sheet 11 is extruded together with the resin, and the molding body 31 is formed. At the same time, the laminated body sheet 11 is adhered to the molding body to manufacture. As shown in FIG. 7, the laminated sheet 11 supplied from the roll 34 is superimposed on the molding body 31 extruded from the extruder 32, and these are pressed and thermally welded by a pressure roller 35. It may be.

In addition, as this molding material, in addition to the side molding described above, a food top molding, a front wind molding, a roof drip molding, a door belt molding, a quarter wind molding, a back wind molding,
There are a luggage molding, a wheel arch molding, a step molding, and the like, and the configuration, manufacturing method, and the like of these are substantially the same as those of the above-described side molding.

In addition, the laminated body sheet of the present invention is not limited to the above-mentioned ones, but can be applied to various products.

[Effects] As described above, the stainless steel sheet and the adhesive layer of the laminate sheet of the present invention are firmly joined and integrated, so that even if the laminate sheet is cut, bent or pressed, Is not peeled off, and the laminated sheet processed in this manner can be easily bonded to a substrate, and various excellent products can be provided by utilizing this property. Further, since the laminate sheet uses a thermoplastic resin material, preferably the same kind of resin material, which is compatible with the resin material forming the substrate to be bonded as the third adhesive layer, It is very easy to adhere to the laminate sheet, and it can be securely adhered even if the control of the adhesion condition is somewhat inaccurate. The effect of this laminate sheet is large, for example, the applicable range is wide.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of the stainless steel / resin laminate sheet of the present invention, FIG. 2 is a schematic view showing a manufacturing method and apparatus, and FIG. 3 is a schematic view showing another manufacturing method and apparatus. 4 and 5 show the molding material of the present invention, FIG. 4 is a perspective view, FIG. 5 is a sectional view taken along the line VV in FIG. 3, and FIGS. It is the schematic which shows the manufacturing method and apparatus of a molding material. 11 ... Laminated sheet, 12 ... Stainless steel sheet, 13 ...
First adhesive layer, 14 second adhesive layer, 15 third adhesive layer, 30 molding material, 31 molding body

Claims (3)

(57) [Claims] 1. A sheet of stainless steel, a first adhesive layer applied to at least one surface of the sheet, and a second adhesive layer applied on the first adhesive layer. A third adhesive layer applied on the second adhesive layer, wherein the first adhesive layer comprises a polyolefin-based polymer and an aliphatic unsaturated carboxylic acid or an anhydride thereof. It is formed from a hot-melt adhesive containing a graft copolymer,
The second adhesive layer is formed of a hot-melt adhesive obtained by mixing a plurality of types of thermoplastic resins, and the third adhesive layer is formed of a synthetic resin material forming a substrate to be bonded. A stainless steel / resin laminate sheet comprising a hot melt adhesive made of a thermoplastic synthetic resin compatible with the stainless steel / resin. 2. The stainless steel / resin laminate sheet according to claim 1, wherein said third adhesive layer is formed of the same kind of resin material as a resin material forming a substrate to be bonded. . 3. The stainless steel / resin laminate sheet according to claim 1, wherein the third adhesive layer of the stainless steel / resin laminate sheet is thermally bonded to a surface of a synthetic resin substrate. Product used.