JP3203313B2 - Polyolefin resin sheet and resin-coated decorative metal sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin sheet and a resin-coated decorative metal sheet suitable for use as members of building materials, home appliances, furniture and the like.

[0002]

2. Description of the Related Art Conventionally, as a resin-coated decorative metal plate, for example, various resin-coated decorative metal plates for interior / exterior and home electric appliances and furniture used as building materials, a vinyl chloride resin sheet is used in view of processing characteristics and price. Coatings have been most commonly used. However, the vinyl chloride resin has a problem that hydrogen chloride gas is generated at the time of combustion and the incinerator is easily damaged during disposal treatment such as incineration. Therefore, in recent years, a resin-coated decorative metal plate that does not use such a vinyl chloride-based resin sheet has been demanded.

Under such circumstances, various metal plates covered with a polyolefin-based resin sheet which are relatively inexpensive and have relatively few problems due to gas generated during combustion have been studied. Such polyolefin resins such as polyethylene and polypropylene do not have polar parts such as functional groups in the molecular structure, and have extremely poor adhesion to metal plates such as steel plates due to high crystallinity. There's a problem. Conventionally, various methods have been studied to solve this problem.

[0004] For example, a method of performing a surface treatment such as a solvent treatment, a flame treatment, a heated air treatment, an oxidation treatment or the like on a polyolefin bonding surface, or mechanically roughening a metal surface to be bonded,
Or a method of surface oxidation treatment, polyolefin is acrylic acid, methacrylic acid, maleic acid, maleic anhydride,
A method using a polyolefin modified with an unsaturated carboxylic acid such as methyl acrylate, an anhydride thereof, or an ester thereof has been proposed.

[0005] However, in any of the methods, the steps become complicated, sufficient adhesive strength to a metal plate cannot be obtained, and furthermore, such as bending workability and punching workability as a resin-coated decorative metal plate. There were problems such as poor secondary workability or high cost.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyolefin resin sheet and a resin-coated decorative metal which are inexpensive and have excellent secondary workability such as adhesion to a metal plate, bending workability and punching workability. To provide a board.

[0007]

DISCLOSURE OF THE INVENTION The present invention has found a polyolefin resin sheet and a resin-coated decorative metal plate which have solved the above-mentioned problems. The gist of the present invention is as follows. A composition comprising 2 to 10 parts by weight of the component (c) with respect to 100 parts by weight of the polymer comprising the mixture of the component (b), wherein the ratio of the components (a) and (b) is (%) by weight. / (B) = polyolefin resin sheet in the range of 95 to 75/5 to 25, and the sheet was subjected to corona discharge treatment and contained one or more functional groups reactive with component (c). A decorative metal plate coated with a polyolefin resin, which is bonded to a metal plate via an adhesive.

(A) component: crystalline polypropylene resin (b) component: the following (i) hard segment in a polymerization reactor
And (ii) the soft segment is multi-stage in two or more stages
Polymerized polyolefin-based thermoplastic elastomer- based thermoplastic elastomer (i) propylene homopolymer block and / or copolymer block of propylene and α-olefin (ii) ethylene homopolymer block and / or ethylene Copolymer block with α-olefin (c) component; polyethylene copolymer modified with unsaturated carboxylic acid or anhydride thereof

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The crystalline polypropylene resin as the component (a) constituting the present invention is a propylene homopolymer, a block copolymer of propylene with an α-olefin such as ethylene, butene, hexene or the like, or a random copolymer thereof. ,
Alternatively, it is arbitrarily selected from a mixture thereof, but a random copolymer is preferable from the viewpoints of film forming properties of the sheet and secondary workability such as bending workability as a resin-coated decorative metal plate.

Next, a polyolefin-based thermoplastic elastomer (hereinafter referred to as "TPO") which is the component (b) constituting the present invention.
) In the polymerization reactor, the following (i) hard segment
And (ii) the soft segment is multi-stage in two or more stages
It is a copolymer obtained by polymerization.

(I) As the hard segment, a propylene homopolymer block or a copolymer block of propylene and an α-olefin, for example, propylene /
Binary or ternary copolymer blocks such as ethylene, propylene / 1-butene, and propylene / ethylene / 1-butene are exemplified.

Further, (ii) the soft segment may be an ethylene homopolymer block or a copolymer block of ethylene and an α-olefin, for example, ethylene / propylene, ethylene / 1-butene, ethylene / propylene / 1- Binary or ternary copolymer blocks such as butene are exemplified.

The TPO used in the present invention is generally an implanted TPO or Reactor-produ.
This is a type called cedTPO, and the feature of the production method is that a multi-stage polymerization of a hard segment and a soft segment is performed in two or more stages in the same polymerization reactor. This makes it possible to produce a plurality of types of polymers continuously and at low cost, and to obtain a copolymer such as an intramolecular blend that is completely different from TPO produced by ordinary mechanical blending. can get.

In a polymer blend by ordinary mechanical mixing, since a high molecular weight elastomer component has a high melt viscosity, it is difficult to obtain a composition having a morphology in which the elastomer component is finely dispersed. By using, a composition having a morphology in which hard segments and soft segments are finely dispersed can be obtained. Further, since the TPO has good compatibility with the components (a) and (c), a composition having a morphology that is finely dispersed to some extent can be obtained even when blended with each other. Specific examples of such a TPO include:
It is commercially available from Tokuyama Corporation under the trade name "PER" and from Himont Corporation under the trade name "Cataroy".

The unsaturated carboxylic acid or the anhydride thereof used in the polyethylene copolymer modified with the unsaturated carboxylic acid or the anhydride thereof as the component (c) constituting the present invention is acrylic acid. , Methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, itaconic acid, itaconic anhydride or an ester compound of a monoepoxy compound of these derivatives and the above acids,
A reaction product of a polymer having a group capable of reacting with these acids in the molecule and an acid is exemplified.

In order to produce a polyethylene-based copolymer modified with an unsaturated carboxylic acid or an anhydride thereof, these modified monomers are copolymerized in advance in the step of polymerizing ethylene, or these modified monomers are added to the polymerized polyethylene. Monomers can also be graft copolymerized. In the modification, these modified monomers are used alone or in combination, and the content is 0.01 to 20% by weight, preferably 0.1 to 10% by weight.
Copolymerization or graft copolymerization is carried out in the range of weight%. If the content is less than 0.01% by weight, it is difficult to exert a sufficient adhesiveness improving effect, while if it exceeds 20% by weight, problems such as difficulty in production and poor heat stability during extrusion occur. easy.

Among the above-mentioned polyethylene copolymers modified with unsaturated carboxylic acids or anhydrides, preferred copolymers are ethylene-acrylic acid copolymers.
Ethylene-methacrylic acid copolymer, ionomer, acrylic acid-modified polyethylene, maleic anhydride-modified polyethylene, maleic acid-modified polyethylene, and the like.Examples include ethylene-acrylic acid copolymer in terms of handling, heat stability during extrusion, cost, and the like. Polymers and ethylene-methacrylic acid copolymers are particularly preferred. Further, these copolymers may be used alone or in combination.

Further, the polyolefin resin sheet of the present invention is a composition comprising 2 to 10 parts by weight of the component (c) with respect to 100 parts by weight of the polymer comprising the mixture of the components (a) and (b). And (a) / (b) = 95 to 75/5 to 25% by weight of the components (a) and (b).
Must be in the range of

In the above relationship, if the component (c) is less than 2 parts by weight, sufficient adhesive strength to a metal plate is not exhibited, and
When the amount exceeds the weight part, the heat resistance of the polyolefin resin sheet as a whole decreases, and at the time of secondary processing such as bending processing, the resin sheet is cracked or cracked, and the whitening of the sheet of the processed part becomes more conspicuous, Further, it is not preferable in terms of cost.

If the content of the component (b) is less than 5% by weight in the ratio of the components (a) and (b), the flexibility and impact resistance of the entire sheet cannot be improved, and the sheet is folded into a resin-coated decorative metal plate. During processing, particularly at low temperature and high speed, there is a problem that the decorative sheet is cracked or cracked, and whitening is easily noticeable. On the other hand, the component (b) is 25% by weight.
In the composition region exceeding, the sheet becomes too flexible, the surface hardness is reduced, and the scratch resistance is liable to be inferior.In addition, when the resin-coated decorative metal plate is subjected to punching, the resin sheet may be galling or after the punching. There is a problem that a whisker-like resin piece may remain on the end surface of the resin sheet.

In the polyolefin resin sheet of the present invention, other resins, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, nucleating agents, coloring agents, antibacterial and antibacterial agents are used to such an extent that their properties are not impaired. Various additives such as a fungicide, an antistatic agent, a lubricant, a flame retardant, and a filler may be appropriately compounded. In addition, printing, embossing, or the like can be appropriately performed on the surface of the polyolefin-based resin sheet in order to enhance the design.

In the resin-coated decorative metal plate of the present invention, the above-mentioned polyolefin resin sheet needs to be bonded to the metal plate using a specific adhesive. As the adhesive, a polyester-based and / or isocyanate-based adhesive containing one or more kinds of functional groups reactive with the component (c) in the composition is used. In particular, the isocyanate group rapidly reacts with polar groups such as -OH and -COOH, and can react with the polar group contained in the polyolefin resin sheet used in the present invention. Adhesion can be ensured.

The polyester resin used herein is a thermoplastic polyester resin and refers to a saturated polyester resin obtained by condensation of a dicarboxylic acid and a polyhydric alcohol. Further, as the isocyanate compound, a tolylene diisocyanate compound, a diphenylmethane diisocyanate compound, tris (isocyanate phenyl)
Thiophosphate compounds and the like.

Further, in order to secure the adhesive strength at the sheet / adhesive interface, the above-mentioned adhesive has a reaction with a sheet-side polar group such as an epoxy group, a methylol group, an alkoxyl group, an aziridinyl group and a carbodiimide group in addition to the isocyanate compound. A compound having a functional group may be added.

The adhesive having such a composition is generally used for a polyvinyl chloride-coated metal sheet. When the above-mentioned polyolefin resin sheet is used, the adhesive is specially prepared in a production line of the polyvinyl chloride-coated metal sheet. In addition, the manufacturing equipment can be used as it is without preparing the adhesive for the polyolefin and changing the equipment such as new installation or remodeling of the adhesive supply equipment and the adhesive coating equipment. Further, since there is no primer treatment step, complicated step management is not required.

Next, the method for producing the resin-coated decorative metal sheet of the present invention will be described. A polyolefin-based resin sheet having the above-mentioned composition range is formed in advance, and a corona discharge treatment is applied to an adhesive surface of the sheet with a metal plate, and an adhesive containing one or more functional groups reactive with the component (c). Adhering to metal plate with agent.

As a method for forming the polyolefin resin sheet, a known method, for example, an extrusion casting method using a T-die or an inflation method can be adopted, and it is not particularly limited. An extrusion casting method using a T-die is preferred from the viewpoints of stability and productivity. The molding temperature in the extrusion casting method using a T die is appropriately adjusted depending on the flow characteristics and film forming properties of the composition,
Approximately melting point or higher and 260 ° C or lower, preferably 180 ° C to 23 ° C
What is necessary is just to carry out in the range of 0 degreeC.

The thickness of the polyolefin resin sheet is usually 50 to 500 μm. Sheet thickness is 50μ
If it is less than m, the performance as a protective layer and the suitability for embossing with respect to the metal plate tend to be poor, and if it exceeds 500 μm, the suitability for secondary processing such as punching as a resin-coated decorative metal plate tends to be poor.

In the resin-coated decorative metal plate of the present invention,
Before bonding the polyolefin resin sheet to the metal plate, it is necessary to perform a corona discharge treatment on the bonding surface of the sheet with the metal plate. When the corona discharge treatment is not performed at all, the adhesive strength to the metal plate hardly appears. The conditions of the corona discharge treatment are not particularly limited, but usually 10 to 10
It is performed under the condition of about 0 W / m ² / min.

Next, as a method of adhering the polyolefin resin sheet and the metal plate, the polyester-isocyanate adhesive is applied to the metal plate by using a commonly used coating equipment such as a reverse coater or a kiss coater. Apply to the metal surface on which the resin sheet is to be bonded so that the thickness of the adhesive after drying is about 2 to 4 μm, and then dry and heat the coated surface with an infrared heater and a hot-air heating furnace to obtain a metal plate surface temperature. Is maintained at a temperature equal to or higher than the melting point of the polyolefin-based resin sheet, the polyolefin-based resin sheet that has been subjected to corona discharge treatment using a roll laminator is immediately coated and cooled to obtain a polyolefin-based resin-coated decorative metal plate.

As the metal sheet of the present invention, various steel sheets such as a hot-rolled steel sheet, a cold-rolled steel sheet, a hot-dip galvanized steel sheet, an electro-galvanized steel sheet, a tin-plated steel sheet, and a stainless steel sheet, and an aluminum sheet can be used. You may use it after doing.

[0032]

EXAMPLES The present invention will now be described more specifically and in detail with reference to the following Examples, which should not be construed as limiting the invention thereto. The measurement standards and test methods for the physical properties of the resin-coated decorative metal sheet shown in the examples and comparative examples are as follows.

(1) Peeling strength under normal conditions The peeling strength was measured in accordance with JIS K6744.
Width). (2) Erichsen test The test was carried out in accordance with JIS K 6744, and the coating resin layer was not peeled off (O), and the peeled resin layer was (X).
Displayed as

(3) Peel strength after boiling water The sample was immersed in boiling water for 1 hour, and the above normal peel strength was measured.

(4) Peel strength after heating The sample was subjected to a hot air heating treatment at 150 ° C. for 1 hour, and then the above normal peel strength was measured.

(5) Bending workability A bending test was performed on the resin-coated decorative metal plate, and the surface condition of the resin sheet in the bent portion was visually judged. If there was almost no change (O), slight cracking occurred. The sample was indicated by (△), and the sample with cracks was indicated by (×). The bending test was performed as follows. 50 mm × 15 from the length and width directions of the resin-coated decorative metal plate
After preparing a 0 mm sample and holding it at 0 ° C for 1 hour or more,
180 ° using a bending tester (inner bending radius 2 mm)
Folded.

(6) Difficulty in whitening Similar to the bending property in (5), a bending test is performed on the coated metal plate, and the surface state of the resin sheet in the bent portion is visually determined, and the whitening phenomenon is hardly noticeable. The sample was marked with (○), the one with a slight whitening phenomenon was marked (△), and the one with a considerable whitening phenomenon marked (x).

(7) Punching workability A 300 mm × 300 mm resin-coated decorative metal plate is formed on a 300 mm × 300 mm resin-coated metal plate from a resin sheet surface with an opening shape of 100 mm × 20.
Punching and bending were performed so as to have a width of 0 mm (corner part R10) and a width of bending of 10 mm, and the surface state of the resin sheet in the processed part was visually determined. ), Those with slight galling or beard were marked (△), and those with noticeable galling or beard were marked (x).

Example 1 (a) Novatec PP EG7 (a melt index (hereinafter abbreviated as "MI") manufactured by Nippon Polychem Co., Ltd.) as a crystalline polypropylene resin: 1.7 g / 10
Min) of 85 parts by weight and (b) TPO as “P.E.R.
T310J "[manufactured by Tokuyama Corporation, MI: 1.5 g / 1
0 min] 15 parts by weight and (c) an ethylene-acrylic acid copolymer resin "Novatech EAA A210K" (manufactured by Nippon Polychem Co., Ltd., acrylic acid content: 7% by weight, MI: 3 g / 10 min], and kneading the composition consisting of 5 parts by weight with a white colorant so as to be homogeneous using a twin-screw kneading extruder equipped with a T die.
A polyolefin-based resin sheet having a thickness of 150 μm was formed.

Next, after a corona discharge treatment was performed on the surface of the obtained sheet to be bonded to the metal plate under the condition of 50 W / m ² / min, a polyester-based adhesive for a commercially available polyvinyl chloride-coated metal plate was used. Is applied to the metal surface on which the polyolefin-based resin sheet is to be bonded so that the thickness of the adhesive after drying is about 2 to 4 μm, and then the coated surface is dried and heated by an infrared heater and a hot-air heating furnace. While maintaining the surface temperature (thickness: 0.5 mm) above the melting point of the polyolefin-based resin sheet, the polyolefin-based resin sheet that has been subjected to corona discharge treatment using a roll laminator is immediately coated and cooled, so that the polyolefin-based resin coating is obtained. A decorative steel plate was prepared, and the above items were evaluated.

The obtained resin-coated decorative steel sheet had sufficient adhesion to the galvanized steel sheet in all of the normal peel strength, the peel strength after boiling water, and the peel strength after heating, and did not peel even in the Erichsen test. Good results were also obtained in the evaluation of bending workability, whitening resistance, and punching workability. The results are summarized in Table 1.

Example 2 In Example 1, as shown in Table 1, the composition of the polyolefin resin sheet was as follows: (a) 80 parts by weight of a crystalline polypropylene resin;
(B) A resin-coated decorative steel sheet was obtained in exactly the same manner except that TPO was changed to 20 parts by weight.

The obtained resin-coated decorative steel sheet had sufficient adhesion to the galvanized steel sheet in all of the normal peel strength, the peel strength after boiling water, and the peel strength after heating, and did not peel even in the Erichsen test. Good results were also obtained in the evaluation of bending workability, whitening resistance, and punching workability.

Example 3 In Example 1, as shown in Table 1, the composition of the polyolefin resin sheet was as follows: (a) 95 parts by weight of a crystalline polypropylene resin;
(B) A resin-coated steel sheet was obtained in exactly the same manner except that TPO was changed to 5 parts by weight.

The obtained resin-coated decorative steel sheet had sufficient adhesion to the galvanized steel sheet in all of the normal peel strength, the peel strength after boiling water, and the peel strength after heating, and did not peel even in the Erichsen test. However, in the evaluation of the bending workability, some cracks occurred in the resin sheet in the bent portion.

Example 4 In Example 1, as shown in Table 1, the composition of the polyolefin resin sheet was as follows: (a) 75 parts by weight of a crystalline polypropylene resin;
(B) A resin-coated decorative steel sheet was obtained in exactly the same manner except that the TPO was changed to 25 parts by weight.

The obtained resin-coated decorative steel sheet had sufficient adhesion to the galvanized steel sheet in all of the normal peel strength, the peel strength after boiling water, and the peel strength after heating, and did not peel even in the Erichsen test. However, in the evaluation of the punching workability, the resin sheet in the processed portion had some galling and whiskers.

Example 5 The procedure of Example 1 was repeated except that the composition of the polyolefin resin sheet was changed to 2 parts by weight of the modified polyethylene copolymer (c) as shown in Table 1. A resin-coated decorative steel plate was obtained.

The obtained resin-coated decorative steel sheet had a partly normal peel strength of 3.8 kg / 20 mm and had slightly poor adhesion, and no peeling occurred in the Erichsen test. Good results were also obtained in the evaluation of bending workability, whitening resistance, and punching workability.

Example 6 The procedure of Example 1 was repeated except that the composition of the polyolefin resin sheet was changed to 10 parts by weight of the modified polyethylene copolymer as shown in Table 1. A resin-coated decorative steel plate was obtained.

The obtained resin-coated decorative steel sheet had sufficient adhesion to the galvanized steel sheet in all of the normal peel strength, the peel strength after boiling water, and the peel strength after heating, and did not peel even in the Erichsen test. However, it was slightly inferior in the evaluation of the whitening resistance and the punching workability.

Comparative Example 1 The procedure of Example 1 was repeated except that the composition of the polyolefin resin sheet was changed to 100 parts by weight of (a) the crystalline polypropylene resin as shown in Table 2. A coated decorative steel plate was obtained.

The obtained resin-coated decorative steel sheet had sufficient adhesion to the galvanized steel sheet in all of the normal peel strength, the peel strength after boiling water, and the peel strength after heating, and did not peel even in the Erichsen test. However, in the bending workability evaluation, cracks occurred in the resin sheet in the bent portion.

Comparative Example 2 In Example 1, as shown in Table 2, the composition of the polyolefin resin sheet was as follows: (a) 70 parts by weight of a crystalline polypropylene resin;
(B) A resin-coated decorative steel plate was obtained in exactly the same manner except that TPO was changed to 30 parts by weight.

The obtained resin-coated decorative steel sheet had sufficient adhesion to the galvanized steel sheet in all of the normal peel strength, the peel strength after boiling water, and the peel strength after heating, and did not peel even in the Erichsen test. However, in the evaluation of the punching workability, many gallings and whiskers occurred on the decorative sheet in the processed portion.

Comparative Example 3 A resin-coated decorative steel sheet was obtained in the same manner as in Example 1, except that the corona discharge treatment was not performed.

The obtained resin-coated metal sheet had a normal peel strength of 0.05 kgf / 20 mm or less, had little adhesion to a steel sheet, and did not function as a resin-coated decorative steel sheet at all.

Comparative Example 4 The procedure of Example 1 was repeated except that the composition of the polyolefin resin sheet was changed to 1 part by weight of the modified polyethylene copolymer (c) as shown in Table 2. A resin-coated decorative steel plate was obtained.

The obtained resin-coated decorative steel sheet had a normal peel strength of 2.5 kgf / 20 mm width and had insufficient adhesion to a galvanized steel sheet, and peeling occurred even in the Erichsen test.

Comparative Example 5 The procedure of Example 1 was repeated except that the composition of the polyolefin resin sheet was changed to 15 parts by weight of (c) the modified polyethylene copolymer as shown in Table 2. A resin-coated steel sheet was obtained.

The obtained resin-coated decorative steel sheet had a normal peel strength of 5.5 kgf / 20 mm and had sufficient adhesion to the steel sheet, and did not peel even in the Erichsen test. However, the peel strength after boiling water and after heating was measured. Was significantly reduced, and the bending workability and the whitening resistance were remarkably inferior.

Comparative Example 6 A resin-coated steel sheet was obtained in the same manner as in Example 1, except that no adhesive was applied to the steel sheet. The obtained resin-coated decorative steel sheet had a normal peel strength of 0.05 kgf / 20 mm width or less, had little sufficient adhesion to the steel sheet, and did not function as a resin-coated decorative steel sheet at all.

[0063]

[Table 1]

[0064]

[Table 2]

As can be seen from Table 1, Examples 1 to 6 show that the composition range of the polyolefin resin sheet used for the resin-coated decorative metal sheet is within the specified range of the present invention, and that the sheet subjected to the corona discharge treatment is excellent. It can be seen that they exhibit good adhesion to secondary metal plates and secondary workability. These performances are almost at the same level as a conventional resin-coated steel sheet using a semi-rigid vinyl chloride resin (for example, a semi-rigid vinyl chloride resin sheet is used instead of a polyolefin resin sheet in Example 1 and the other parts have exactly the same configuration Normal peel strength of the product 5.2kgf
/ 20mm width, peel strength after boiling water 4.7kgf / 20mm
Width and peel strength after heating were 4.5 kgf / 20 mm width).

On the other hand, when the composition range of the polyolefin resin sheet is out of the specified range as shown in Comparative Examples 1 to 5 from Table 2 or when the corona discharge treatment is not performed, the adhesion to the metal plate and the bending process are performed. One of the properties, the whitening resistance, and the punching workability was poor, and it was found that it was difficult to obtain a resin-coated decorative metal plate having a sufficiently excellent balance of each property.

[0067]

As described above, according to the present invention, a polyolefin-based resin sheet and a resin-coated cosmetic which are inexpensive and excellent in secondary workability such as adhesion to a metal plate, bending workability, and punching workability are provided. A metal plate can be provided.

Claims (3)

(57) [Claims] 1. Component (c) is added in an amount of 2 to 100 parts by weight of a polymer comprising a mixture of the following components (a) and (b).
It consists of a composition in which 10 parts by weight are blended, and the ratio of the components (a) and (b) is 95% to 75/5 by weight% (a) / (b).
25. A polyolefin resin sheet in the range of 25. (A) component; crystalline polypropylene resin (b) component; the following (i) hard segment in a polymerization reactor:
And (ii) the soft segment is multi-stage in two or more stages
Polymerized polyolefin-based thermoplastic elastomer (i) propylene homopolymer block and / or copolymer block of propylene and α-olefin (ii) ethylene homopolymer block and / or ethylene and α-olefin (C) component: a polyethylene copolymer modified with an unsaturated carboxylic acid or an anhydride thereof 2. Component (c) is added in an amount of 2 to 100 parts by weight of a polymer comprising a mixture of the following components (a) and (b).
It consists of a composition in which 10 parts by weight are blended, and the ratio of the components (a) and (b) is 95% to 75/5 by weight% (a) / (b).
Using a polyolefin resin sheet in the range of 25,
This sheet is subjected to a corona discharge treatment and a polyether containing one or more functional groups reactive with the component (c).
A decorative metal plate coated with a polyolefin resin, which is bonded to a metal plate via a stell-based and / or isocyanate-based adhesive . (A) component; crystalline polypropylene resin (b) component; the following (i) hard segment in a polymerization reactor:
And (ii) the soft segment is multi-stage in two or more stages
Polymerized polyolefin-based thermoplastic elastomer (i) propylene homopolymer block and / or copolymer block of propylene and α-olefin (ii) ethylene homopolymer block and / or ethylene and α-olefin (C) component: a polyethylene copolymer modified with an unsaturated carboxylic acid or an anhydride thereof 3. The polyolefin resin sheet according to claim 1, wherein the polyethylene copolymer (c) is an ethylene-acrylic acid copolymer or an ethylene-methacrylic acid copolymer. Or a resin-coated decorative metal plate.