JP2011202024A - Resin film, decorative metal plate coated with the resin film and building material for ship interior finishing to use the decorative metal plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film having excellent embossing processability comparable or superior to conventional soft polyvinyl chloride resins and having good adhesiveness to a metal plate, a luxurious decorative metal plate coated with the resin film, and a building material for ship interior finishing obtained by using the decorative metal plate.SOLUTION: There is provided a resin film for ship interior finishing, having an average surface roughness Ra of 0.1-400 μm, composed mainly of a polyester component and subjected to embossing work. There are also provided the decorative metal plate coated with the resin film, and the building material for ship interior finishing obtained by using the decorative metal plate.

Description

  The present invention relates to a resin film excellent in embossability equivalent to or higher than that of a conventional soft vinyl chloride resin and having good adhesion to a metal plate. The present invention also relates to a high-grade decorative metal plate coated with the resin film and a ship interior building material using the decorative metal plate.

  Conventionally, a decorative metal plate obtained by laminating a resin film on a metal plate has been widely used for building materials for ship interiors. The resin film used for the decorative metal plate for these building materials needs to have excellent adhesion to the metal plate as the base. This is because if the adhesion between the resin film and the underlying metal plate is poor, water or the like enters from that portion, and after a certain period of time, the water corrodes the underlying metal plate and the laminated resin film peels off. This is because the problem of end. Moreover, water resistance is also required for building materials for ship interiors depending on the use mode.

  Furthermore, in order to increase the commercial value as a building material application, it is also necessary to add surface aesthetics, that is, a high-class feeling. For this reason, embossed patterns have been widely applied to the surface of decorative metal plates. I came. Accordingly, it is also important for building materials that the embossability of the resin film is good. This is because the embossed pattern of a certain depth remains on the resin film to give the decorative metal plate a high-class feeling. Conventionally, a soft vinyl chloride resin or the like has been widely used as a resin film mainly from the viewpoint of easy embossing and low cost (Patent Document 1).

JP 2005-281699 A

  However, soft vinyl chloride resins are softened by adding and mixing phthalic acids such as DBP (dibutyl phthalate) and DOP (dioctyl phthalate) as plasticizers to facilitate molding. However, there is a problem that harmful substances such as hydrogen chloride gas and dioxin may be generated during combustion.

  In addition, there are films using olefin resin polyethylene, polypropylene resin, etc. instead of vinyl chloride resin. When these resin films are used, the embossability is good, but on the metal plate. In the case of laminating and bending such as processing, there is a problem that the processed portion becomes white and the aesthetics are impaired.

  An object of the present invention is to solve the above-mentioned problems, and to provide a resin film excellent in embossability that is equal to or higher than that of a conventional soft vinyl chloride resin. Moreover, providing a resin film with good adhesion to the metal plate, providing a high-grade decorative metal plate coated with the resin film, and providing a building material for ship interior using the decorative metal plate. For the purpose.

The present invention has the following features.
(1) The resin film for ship interior of the present invention is characterized in that the surface roughness is 0.1 to 400 μm in average surface roughness Ra, and a polyester component as a main component is embossed.
(2) In the above (1), the polyester component is polybutylene terephthalate.
(3) The crystalline copolymer polyester resin film for ship interior of the present invention is a film having a component concentration gradient in the thickness direction, and a polyvalent acid component or a polyhydric alcohol component in a resin component in a portion in contact with a metal plate. A part of is replaced with other components.
(4) The polyester resin film for laminating a metal plate for ship interior of the present invention is a resin film composed of a plurality of layers,
The layer in contact with the metal plate is a crystalline copolyester resin film in which a part of the polyhydric acid component or polyhydric alcohol component in the resin component is replaced with another component,
The thickness of the layer in contact with the metal plate / the thickness of the layer not in contact with the metal plate = 1/20 to 1,
It is characterized by being.
(5) The resin film for ship interior of the present invention is the resin film according to any one of (1) to (4), wherein the ionomer resin component is added in an amount of 1 to 50 weights in the resin component in the portion in contact with the metal plate. % Containing resin film.
(6) The decorative metal plate for ship interior of the present invention is characterized in that the resin film according to any one of (1) to (5) is laminated on a metal plate.
(7) The building material for ship interior according to the present invention is formed using the decorative metal plate described in (6) above.

  INDUSTRIAL APPLICABILITY The present invention can provide a resin film excellent in embossability that is equal to or higher than that of a conventional soft vinyl chloride resin and having good adhesion to a metal plate. Moreover, a high-grade decorative metal plate coated with the resin film can be provided, and a ship interior building material using the decorative metal plate can be provided.

It is an example of the measurement curve in DSC (differential scanning calorimetry).

  Hereinafter, embodiments of the present invention will be described.

  The first aspect of the method for producing a decorative metal plate of the present invention is that a resin film having predetermined characteristics is laminated on the metal plate, and then the metal plate and the resin film are simultaneously passed through the engraving roll at a predetermined speed. The embossed pattern is formed on the resin film. Moreover, the 2nd form laminates the resin film which formed the embossed pattern beforehand using the engraving roll on a metal plate.

(Metal plate)
In the present invention, examples of the metal plate on which the resin film is laminated include a steel plate, an aluminum plate, and a copper plate, but are not particularly limited thereto. As the steel plate, a plain steel cold-rolled steel plate having a thickness of 0.10 to 1.2 mm is preferable. In particular, a plain steel cold-rolled steel sheet having a thickness of about 0.1 to 0.5 mm is more preferable. Among cold-rolled steel sheets, low-carbon or ultra-low-carbon aluminum killed steel sheets are preferably used, but non-aging steels added with Nb, Ti, etc., chromium-containing steel sheets containing 3 to 18% by weight of chromium, and various compositions Stainless steel plates can also be used. The surface of these cold-rolled steel sheets may be surface-treated.

  Surface treatment methods include plating and painting. Examples of the type of plating include zinc plating, zinc-aluminum alloy plating, zinc-cobalt-molybdenum plating, tin plating, nickel plating, nickel-phosphorus plating, nickel-cobalt plating, and nickel-tin plating. As the type of coating, various types of coating methods such as roll coating can be applied by spraying various paints according to their properties.

Moreover, in order to make the adhesiveness of a resin film and a metal plate favorable, it is also preferable to perform the adhesiveness improvement process of the metal plate surface. As such a surface treatment method of the metal plate, it is preferable to attach chromium hydrated oxide to the surface of the metal plate by about 1 to 40 mg / m ² as a chromium amount, for example, by an electrolytic method, a dipping method, or the like. In addition, the surface treatment for adhesiveness improvement can also use another well-known means.

(Resin film)
As a kind of the resin film laminated on the metal plate, polybutylene terephthalate (PBT) resin, polyethylene terephthalate (PET) resin, polycarbonate (PC) resin or the like is preferably used. Also, blend resin of PBT resin and PET resin, blend resin in various proportions with PBT resin or PET resin and other resins, blend resin of PBT resin and PC resin, blend resin with PBT resin and ionomer (IO) resin Alternatively, a blend resin of these three or more resins is used. Moreover, the resin film of a copolymer with PBT resin or PET resin and a compound, for example, a copolymer with isophthalic acid, adipic acid, etc. is mentioned.

  Furthermore, as a resin film, the multilayer laminated film which laminated | stacked the resin film of two or more layers can also be used. When using a multilayer laminated film, the kind of resin film excellent in adhesiveness can be disposed on the surface in contact with the metal plate.

  In the case of using a blend resin in which two or more kinds of resins are mixed, the adhesiveness can be improved while the characteristics inherent to the resin to be mixed are kept by blending the resin having good adhesion. However, since the blend resin is mechanically mixed with resins having different properties, there are many cases where a non-uniform state is generated, and there is a problem that the state of close contact with the metal plate is likely to vary. As a solution for this, it is also possible to use a resin in which some of the components in the resin are replaced with other components.

  In the present invention, from such a viewpoint, various experimental results are examined, and a crystalline copolyester resin in which a part of the polyvalent acid component or polyhydric alcohol component in the PET resin in the resin film is substituted with another component is provided. It has been found that by using it, a remarkable improvement effect is observed in the adhesion with the metal plate.

  Here, the polyvalent acid component in the PET resin refers to a terephthalic acid moiety. The polyhydric alcohol component refers to an ethylene glycol moiety. “Substitution with other components” means substitution with an acid component or an alcohol component, and the acid component is an aliphatic dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid or alicyclic It refers to a dicarboxylic acid or an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, 2,6 naphthalenedicarboxylic acid, or a combination of two or more.

  Examples of the alcohol component include aromatic diols such as bisphenol A, or aliphatic diols such as diethylene glycol, 1,4 butanediol, 1,6 hexanediol, and alicyclic diols such as 1,4 cyclohexanedimethanol. It refers to a single or a combination of two or more.

  Such substitution of the acid component or alcohol component is performed using the specific raw material during polycondensation, and the substitution component ratio is preferably 5 to 30 mol%. If it is less than 5 mol% or more than 30 mol%, not only the intended properties such as improvement in adhesion cannot be achieved, but also the property inherent in the resin is deteriorated. Since it newly occurs, it is not preferable.

  The “crystalline copolymer polyester resin partially substituted with other components” specifically refers to, for example, an isophthalic acid copolymer PBT resin.

  Moreover, when using the resin film which consists of a multilayer, the thickness of the resin film (lower layer film) which contacts a metal plate is below the thickness of the resin film (upper layer film) which does not contact a metal plate directly Is preferred. In particular, the thickness of the lower film / the thickness of the upper film is preferably adjusted to about 1/20 to 1. This is because, in the case of using a multilayer resin film, it is necessary to use a resin having excellent adhesion to the metal plate surface for the portion in contact with the metal plate. It is not necessary to do. On the other hand, it is preferable that the upper film is thicker than at least the lower film from the viewpoint that the embossed pattern formed deeper can give a high-class feeling to the resin surface.

  When using the resin film which consists of a multilayer, when IO resin component is contained in a part of resin component in the resin film of the part which contacts a metal plate at least, adhesiveness with a metal plate will improve further. In this case, the content of the IO resin component is preferably 1 to 50% by weight of the total resin component.

  The reason for limiting the content of the IO resin component in this way is as follows. That is, the IO resin film is particularly excellent in adhesion to metal, but on the other hand, its content is limited because it is inferior to other resins in terms of strength. When the content is less than 1% by weight, the excellent effect of improving the adhesiveness of the IO resin cannot be exhibited. When the content exceeds 50% by weight, the adhesiveness is improved, but the strength and heat resistance are improved. This is because the deterioration of property and the decrease in transparency (white turbidity) are more noticeable. Although the thickness of a resin film is not specifically limited, For example, about 0.02-0.30 mm, Furthermore, about 0.08-0.15 mm is preferable from an economical viewpoint. Also in the case of a multilayer film in which resin films are laminated at different thickness ratios, it is preferable from the economical viewpoint to adjust the total thickness within this thickness range.

  In addition, when using only one type of resin film, it is preferable to use PBT resin. PBT resin can easily form a semi-permanent embossed pattern, is less likely to deteriorate even when left in water for a long period of time, and has a high-grade feeling compared to other resin films. In addition, when used as a building material for ship interiors, it can be used without being deteriorated for a long time even if it is directly splashed with water.

  The above-mentioned resin film can be coated on a metal plate before embossing. As a method of coating the resin film on the metal plate, for example, in the case of PBT resin, an adhesion method such as ultrasonic welding or spin weld can be used. Alternatively, an epoxy-based, polyester-based, cyanoacrylate-based adhesive or the like may be used, but it is simply bonded by a method of crimping onto a metal plate that has been heated above the melting point of the resin (thermocompression bonding method). Also good. When the resin film and the metal plate are bonded by the thermocompression bonding method, it is preferable to treat the surface of the metal plate in advance so that a strong adhesion can be obtained. As the surface treatment method, methods such as electrolytic chrome treatment and adhesion primer treatment can be employed.

(Embossing)
The embossing method is, for example, a method in which a heat-melted resin is extruded from a T die onto a casting roll embossed to form a film having an embossed eye on one side, and a multilayer film is directly engraved roll (emboss roll) A method of passing through, a method of heating a brown film and passing it between engraving rolls, a method of embossing with a vacuum force through a rotating screen roll, a hot needle process of passing a multilayer film through a perforator There are various methods such as compression using an engraving roll. In the case of the first embodiment of the present invention, it is preferable that the resin film supplied from the T-die is embossed after being heat-bonded to a separately supplied metal plate.

  In this case, the surface temperature of the engraving roll can be set and adjusted by a method in which a certain amount of coolant such as water flows in a pipe provided in the roll.

  As the embossed pattern shape, various patterns such as a random mat, a square shape, a diamond shape, a deep drawing shape, and a grain pattern (referred to as SG pattern) can be used according to the needs of the product.

  For the measurement of the average surface roughness Ra (μm) after embossing of the resin film, a film that has been embossed at the time of film formation, produced according to the second embodiment of the production method described above, is used. That is, the heat-melted resin is extruded from a T die onto an engraving casting roll to form a film having embossed eyes on one side. The average surface roughness is also measured in the same manner for the resin film laminated metal plate produced by the first embodiment of the above production method.

  The engraving roll used was provided with irregularities having an average surface roughness Ra of 1 μm, 11 μm, 35 μm, 110 μm, 320 μm, and 480 μm.

(Measurement of average surface roughness)
The average surface roughness was measured as follows. The average surface roughness Ra (μm) of the resin film surface was measured in accordance with JIS B0601 using a SURFCOM surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). In addition, this measurement was performed about five resin test pieces, the surface roughness of four different places was measured about each test piece, the average value was calculated, and it was set as surface roughness Ra (micrometer).

(DuPont impact test)
The DuPont impact test is a test aimed at water resistance. Since the embossing gives a certain strain to the surface layer of the resin film, if this state is maintained for a long time, the resin surface is easily deteriorated by immersion in water. Therefore, after being immersed in water for a certain period of time, a certain impact was applied, and the case where the resin film was not destroyed at this time was regarded as having good impact resistance.

The DuPont impact test was conducted as follows. That is, a metal plate having a constant length and width and a thickness of 0.50 mm is heated to a temperature equal to or higher than the melting point of the resin film to be coated, and has the same dimensions as the plate and a thickness of 0.1 mm. A test piece was obtained by heat-pressing the resin film. The test piece was passed at a constant speed through an engraved roll of grain (SG eyes) provided with irregularities having an average surface roughness Ra = 11 μm. This test piece was cut into a size of 60 × 60 mm and then left in demineralized water at 38 ± 2 ° C. for 1 month. After one month, the specimen was taken out from the desalted water, dried at room temperature, and compliant with JIS K5400 using a DuPont impact tester (size of impact part: 0.5 inch diameter, load: 1 kg, high Measured visually and evaluated as follows.
Score 5 = No cracking of the film Score 4 = Fine cracks occur in part of the film Score 3 = Small cracks occur in the entire embossed part of the film Score 2 = Large cracks occur in the entire embossed part of the film Score 1 = Entire film There was no problem in use for the resin films determined to be 5 and 4 by the above-mentioned score with remarkable cracking. In addition, this test measured about 10 test pieces each. Moreover, the judgment person was changed and it judged by the several judgment person, and made the average value the DuPont impact test score.

(DSC (differential scanning calorimetry))
DSC measurement was performed under the following conditions. A differential scanning calorimeter DSC-7 (manufactured by Perkin Elmer) was used as a measuring device. About 5 mg of a sample was precisely weighed with a semi-micro balance, and the temperature was raised at 20 ° C./min while flowing nitrogen gas, at 20 ° C./min. After the temperature was lowered, the endothermic peak temperature (Tmp) and the exothermic peak temperature (Tc2) were determined from the temperature rise and temperature fall curves as shown in FIG. That is, using a differential scanning calorimeter, Tmp was obtained from the endothermic peak of the temperature rise curve when a precisely weighed sample of about 5 mg was heated to a molten state at 20 ° C./min in a nitrogen gas atmosphere. After holding in the state for 3 minutes, Tc2 was determined from the exothermic peak in the temperature drop curve when the temperature was lowered to room temperature at 20 ° C./min.

(Evaluation of resin and metal plate adhesion)
In a state where the surface temperature of the 0.5 mm thick galvanized steel sheet was heated to within Tmp + 10 ° C. of the resin, a 0.100 mm thick resin film was brought into contact and pressure-bonded using a roll to produce a resin bonded steel sheet. A 60 × 60 mm square specimen was cut out from this steel plate, and a 5 mm wide well-cut was cut into the steel plate surface using a cutter knife from above the resin. About this specimen, an 8 mm overhang was performed using an Eriksen test machine, and the girder part was forcibly peeled off, and the score = 5 when not peeled, and the score = 1 when peeled easily 5 points The adhesion was evaluated by an evaluation method.

  Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1
Example 1 is an example of using a homopolymer single-layer resin film, and a PBT resin was used. An aluminum killed cold-rolled steel sheet having a thickness of 0.50 mm and a carbon content of 0.03% by weight was prepared, and this steel sheet was subjected to galvanizing treatment to a thickness of 0.002 mm, and this galvanized steel sheet was heated to 229 ° C., A laminated steel plate was produced by thermocompression bonding of a 0.100 mm thick PBT resin film having an intrinsic viscosity of 1.4 on the surface. Next, the laminated steel sheet is heated and held at the set temperature, and the engraving roll adjusted to 30 ° C. having a grain-shaped (SG pattern) pattern with irregularities having an average surface roughness Ra = 11 μm is provided. In use, the steel plate and the resin were simultaneously pressed and embossed and then quenched into water and cooled. The average surface roughness Ra for evaluating the embossability of the resin film on the steel sheet thus treated was 7.0 μm, the DuPont impact test score was 5, and the adhesion score of a specimen prepared in the same manner was 3. It was.

(Examples 2-3, Comparative Example 1)
Examples 2-3 and Comparative Example 1 are usage examples of a homopolymer monolayer resin film, and Examples 2 and 3 used PBT resins having different intrinsic viscosities. In Comparative Example 1, a PET resin was used. A laminated steel sheet was produced under the same conditions as in Example 1, and the embossing was performed while adjusting and setting the surface temperature of the engraving (cooling) roll having a roughness of average surface roughness Ra = 11 μm (SG eyes) to 30 ° C. Processing was performed. The adhesion test was performed using the average surface roughness Ra of the resin film on the steel sheet thus treated, the DuPont impact test, and a specimen prepared in the same manner.

(Examples 4-6, Comparative Examples 2-3)
Examples 4 to 6 and Comparative Examples 2 to 3 are usage examples of blend resins, Example 4 is an equal blend of PBT resin and PET resin, and Example 5 is an equal blend of PBT resin and PC resin. 6 used a 95/5 blend of PET resin and IO resin, Comparative Example 2 used an equal blend of PET resin and PC resin, and Comparative Example 3 used a 70/30 blend of PET resin and IO resin. The processing conditions and the evaluation test were performed under the same conditions as in Example 1.

(Examples 7 to 9)
Examples 7 to 9 are examples of using a copolymer resin in which an acid component or an alcohol component in a polyester resin is substituted with another component, and Example 7 is a case where terephthalic acid as an acid component is substituted with 10 mol% of isophthalic acid. Example, Example 8 is an example in which 10 mol% of adipic acid is substituted, and Example 9 is an example in which ethylene glycol as an alcohol component is substituted with 10 mol% of cyclohexanedimethanol. The processing conditions and the evaluation test were performed under the same conditions as in Example 1.

(Examples 10-12, Comparative Examples 5-6)
Examples 10 to 12 and Comparative Examples 5 to 6 are examples using a multilayer resin, of which Example 10 and Example 11 are resins of Example 7, which are PET copolymer resins containing 10 mol% of isophthalic acid. Example 10 is a use example of a two-layer film of PBT resin film and Example 10 has a thickness ratio of 4: 1, that is, a PET copolymer resin film is used as an adhesive layer, and the thickness of the PET copolymer resin film is 0. In this example, the thickness of the non-adhesive PBT resin film is 0.080 mm. Example 11 is an example in which the thickness ratio is 9: 1, that is, the thickness of the PET copolymer resin film is 0.010 mm, and the thickness of the PBT resin film which is a non-adhesive layer is 0.090 mm. Comparative Example 5 is an example in which the thickness of the adhesive layer is extremely thin, the thickness of the PET copolymer resin film is 0.004 mm, and the thickness of the PBT resin film that is a non-adhesive layer is 0.096 mm. In the thickened example, the adhesion with the metal plate of Comparative Example 5 is significantly inferior. Example 12 and Comparative Example 6 are examples in which a blend resin containing IO having good adhesiveness is used for the adhesive layer, but Example 12 is the resin of Comparative Example 3 and the IO resin content is 30%. On the other hand, in Comparative Example 6, since the IO resin component is excessively mixed at 70%, the evaluation of the DuPont impact test, which is an index of strength, is remarkably lowered, and further, the transparency is lowered (white turbidity) is noticeable. It was.

(Examples 13 to 24)
Examples 13 to 24 are examples in which embossing was performed using engraving rolls having different average surface roughness Ra (μm), and an aluminum-killed cold-rolled steel sheet having a thickness of 0.5 mm and a carbon content of 0.03% was prepared. The steel sheet was then galvanized to a thickness of 0.002 mm, the galvanized steel sheet was heated, and a resin film was thermocompression bonded onto the steel sheet surface to produce a laminated steel sheet. Next, after heating the laminated steel sheet, the above-mentioned average surface roughness Ra is 1 μm, 11 μm, 35 μm, 110 μm, 320 μm, 480 μm provided with irregularities, and the engraving roll set and adjusted to 30 ° C. Simultaneously crimped and embossed, then quenched into water and cooled. Table 3 shows the average surface roughness Ra of the resin film on the steel sheet thus treated, the DuPont impact test score, and the adhesion score of the prepared specimen. Of these, Examples 13 to 18 are PBT resin films having an intrinsic viscosity of 1.4, which are resins of Example 1, and have thicknesses of 0.100 mm, 0.200 mm, and 0.500 mm as shown in Table 3. Examples 19 to 24 are resin films of a 95/5 blend of PET resin and IO resin, which are the resins of Example 6, and have three thicknesses as in Examples 13 to 18. This is an example using this. Regarding the thickness of the resin film, in Examples 13 to 15 and Examples 19 to 21, the thickness was 0.100 mm, in Examples 16 and 22, the thickness was 0.200 mm, and Examples 17 to 18 and In Examples 23 to 24, the thickness was adjusted to 0.500 mm. Tables 1 to 3 summarize the processing conditions and evaluation test results of the examples and comparative examples described above.

  The present invention provides a resin film excellent in embossing property equivalent to or higher than that of a conventional soft vinyl chloride resin and having good adhesion to a metal plate. Moreover, since the high-grade decorative metal plate which coat | covered the resin film is provided and the building material for ship interiors using the decorative metal plate is provided, industrial applicability is very high.

Claims (7)

A resin film for ship interior that has an average surface roughness Ra of 0.1 to 400 μm and is embossed with a polyester component as a main component. The resin film for ship interior according to claim 1, wherein the polyester component is polybutylene terephthalate. Crystalline copolyester for ship interiors, which is a film having a component concentration gradient in the thickness direction and in which a part of the polyvalent acid component or polyhydric alcohol component in the resin component in contact with the metal plate is replaced with another component Resin film. A resin film comprising a plurality of layers, wherein the layer in contact with the metal plate is a crystalline copolyester resin film in which a part of the polyhydric acid component or polyhydric alcohol component in the resin component is substituted with another component. A polyester resin film for laminating metal plates for ship interior, wherein the thickness of the layer in contact with the metal plate / the thickness of the layer not in contact with the metal plate = 1 / 20-1. The resin film for ship interior according to any one of claims 1 to 4, wherein the resin film is a resin film containing 1 to 50% by weight of an ionomer resin component in a resin component in a portion in contact with a metal plate. A decorative metal plate for ship interior, wherein the resin film according to any one of claims 1 to 5 is laminated on a metal plate. The ship interior building material shape | molded using the decorative metal plate of Claim 6.