JP4885484B2 - Laminated sheet for design coating and laminated sheet coated metal sheet - Google Patents

Description

  The present invention relates to a laminated sheet for designable coating, and a laminated sheet-coated metal plate coated with the laminated sheet. In particular, it is excellent in scratch resistance and workability, and suppresses deterioration in secondary workability after long-term storage caused by deterioration in break elongation and bending whitening over time, and is coated on a thick metal plate. More particularly, the present invention relates to a laminated covering metal plate that can be suitably used for elevator interior materials such as elevator car walls, elevator car doors, and the like, and a laminated sheet for producing the metal plate. Moreover, the metal sheet for covering laminated sheets of the present invention can be suitably used for home appliance housing use, building interior material use, and steel furniture use. Furthermore, the laminated sheet for designable coating of the present invention is intended to enhance the designability by coating on a wooden board, an inorganic fiber board, a thermoplastic resin board, a thermosetting resin board, etc. in addition to coating a metal plate. Can be suitably used.

Conventionally, as a material suitable for the above-mentioned use, a soft vinyl chloride resin sheet provided with an embossed design (hereinafter sometimes referred to as “soft PVC sheet”), a synthetic resin molded product, plywood, wood fiber board, metal The thing which coat | covered the board etc. has been used. As a characteristic of this soft PVC sheet,
(1) Since it is excellent in embossing suitability, a coating material rich in design can be obtained.
(2) The balance between workability, which is generally a contradiction element, and scratch resistance on the surface is relatively good.
(3) It is easy to obtain a resin film having excellent durability because it has excellent compatibility with various additives and has been studied for improvement in physical properties with additives for many years.
Etc. can be mentioned.

  As a method of continuously embossing the long sheet of soft PVC, the film-formed sheet is softened by reheating and pressed with a roll engraved with an embossed pattern (hereinafter referred to as “embossed plate roll”). A method of transferring a pattern continuously is generally used. As a method for heating the sheet, there are a contact type in which the sheet is brought into contact with a heated metal roll and a non-contact type in which the sheet is heated without being brought into contact with the roll by an infrared heater or a hot air heater. In an actual production line, there may be only one of them, but in general, both are often used together. Moreover, the equipment which has these series of processes is called "embossing machine".

  Such an embossing machine generally incorporates a design that makes it very easy to exchange and remove the embossing plate roll. Moreover, since the diameter of the embossing plate roll is smaller than the casting roll of the extrusion film forming equipment, the embossing pattern can be easily and economically changed by preparing various embossing plate rolls. . Therefore, it can be said that the embossing method using the embossing machine is suitable for manufacturing a small lot.

  Moreover, after printing on the surface of the colored soft PVC sheet, a transparent soft PVC sheet is laminated and integrated, and the laminated sheet is continuously passed through an embossing machine. There is a soft PVC laminate sheet having In this case, using the sheet preheating in the embossing machine, two layers of sheets can be laminated and integrated by heat fusion, and since a special process for lamination is not required, the productivity is good. The cost was also excellent.

  However, in recent years, the use of the above flexible PVC sheet has been limited due to problems such as VOC (Volatile Organic Components), endocrine disrupting action, and problems of generating hydrogen chloride gas and other chlorine-containing gases during combustion. Has come to receive. Then, the alternative material of the flexible PVC sheet which has the above outstanding characteristics is examined.

  Among these, from the viewpoint of cost, a sheet made of polyolefin resin was first examined. However, a polyolefin resin has a problem that a bent portion is whitened when it is bent as a resin-coated metal plate. In order to solve this problem, the use of a formulation that lowers the crystallinity results in low surface hardness, and scratch resistance is a problem in applications such as elevator inner layer materials that are frequently touched by people.

  Patent Document 1 proposes a configuration in which a layer made of a transparent polycarbonate resin is laminated on a colored base material layer made of a polyethylene resin.

  Patent Document 2 proposes a method for preventing deterioration of processability over time by adding a specific MBS-based crosslinked rubber to an amorphous polyester-based resin. It is said that a remarkable effect is recognized against the decrease.

  As an alternative to the soft PVC sheet, an acrylic resin that can be formed into a calender has been studied. Patent Document 3 proposes to use, as a transparent surface layer and a colored base material layer, an acrylic sheet that has been softened by adding a cross-linked elastic component so that bending can be performed.

Patent Document 4 proposes to coat a base resin sheet made of acrylic resin with a transparent resin layer made of polyester resin.
: JP 2003-145702 A : JP 2002-121367 A : JP 2004-142164 A : JP 2000-094596 A

  However, the object of the invention of Patent Document 1 is to ensure surface hardness and impact resistance, and does not take into account the prevention of bending whitening of the processed portion when the resin-coated metal plate is bent. Further, when a polyolefin-based resin is used as the base material layer, there is no heat-fusibility between the surface layer and the polycarbonate-based resin, and thus special contrivance is required for adhesive lamination. In addition, regarding adhesive lamination with a metal plate, adhesive strength cannot be obtained only with an adhesive used for laminating a conventional soft PVC sheet.

  On the other hand, a sheet made of a non-crystalline polyester resin capable of producing a sheet with a calendar facility that has been used for film formation of a conventional soft PVC sheet has been studied, and a resin coating excellent in surface hardness and workability It is developed as a sheet for metal plates. However, non-oriented amorphous polyester has a problem that mechanical properties such as elongation at break gradually decrease when stored at a temperature lower than the glass transition temperature (Tg) of the resin after thermoforming. The decrease in physical properties is attributed to the progress of so-called enthalpy relaxation. In other words, when a non-crystalline polyester resin sheet was coated on a relatively thick metal plate like an elevator interior material to make a resin-coated metal plate, it was stored for a while after being bent without any problems. If the bending process is performed later in the same manner, problems such as the sheet being broken at the bent part or being visually recognized as whitening due to a large number of fine cracks are generated. Since the cause of the deterioration of workability over time is relaxation of enthalpy, the workability is restored by heating once above the glass transition temperature (Tg) of the coating resin in the previous step of subjecting the resin-coated metal plate to bending, Because it increases, it is not acceptable to processing manufacturers. In addition, a sheet composed of a single layer of an amorphous polyester resin is poor in suitability for embossing machines, which have been used for embossing soft PVC sheets off-line, and has sufficient heat resistance for embossing. It was difficult to transfer the embossed pattern having the property. This is because, when laminating to a relatively thick metal plate, even if rapid cooling with water cooling is performed, the temperature of the metal plate does not cool immediately, so that the embossed pattern becomes shallow due to the preheating. This means that there is a return and it is cheap, and there was a problem with this point when it was used for elevator interior use.

  Moreover, although patent document 2 is carrying out the disclosure regarding the improvement of the workability fall resulting from the enthalpy relaxation of an amorphous polyester-type resin, since it is not a thing for a resin coating metal plate, with respect to prevention of bending whitening Is not effective. It seems that void whitening due to the addition of the crosslinked rubber is influential. Also, suitability for embossing machines is not improved.

  Furthermore, in the configuration disclosed in Patent Document 3, it is difficult to achieve both surface hardness and workability as a resin-coated metal plate. If the surface hardness is high in order to ensure scratch resistance, the workability is improved. A problem arises and the opposite problem occurs in order to ensure processability. In addition, the acrylic resin containing a large amount of cross-linked elastic body component is elastically recovered from the applied strain at the same time that it is peeled off from the plate roll even when pressed with the embossing plate roll of the embossing machine, so that beautiful emboss transfer There was a problem that it was difficult to get.

  In addition, the object of the invention of Patent Document 4 is to obtain a laminated sheet with good vacuum formability, and since a relatively hard acrylic resin is used, workability as a resin-coated metal plate is sufficient. There was also a problem that it could not be.

  Therefore, the present invention can provide a good embossed pattern using an embossing machine that has been used conventionally, and can provide various colored sheets efficiently by a calendar film forming method. Provided is a laminated sheet for coating, and a laminated sheet-coated metal sheet produced by coating this laminated sheet and having workability that is the same as that immediately after laminating even after being folded after long-term storage. Let it be an issue.

  The present invention will be described below. In order to facilitate understanding of the present invention, reference numerals in the accompanying drawings are appended in parentheses, but the present invention is not limited to the illustrated embodiment.

  The first aspect of the present invention is a first resin layer (10) mainly composed of an acrylic resin containing a core-shell type acrylic cross-linked elastic component, and the dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, A diol component comprising 50 to 75 mol% of 1.4-cyclohexanedimethanol and a second resin layer (20) mainly composed of an aromatic polyester resin composed of 25 to 50 mol% of ethylene glycol; The tensile break elongation at 23 ° C. of the first resin layer is 120 to 350%, and the tensile break elongation at 23 ° C. after leaving the second resin layer in an environment of 40 ° C. × 90% RH for 30 days is 120%. It is the laminated sheet (110) for designable coatings characterized by the above.

  Here, in the present invention, “main component” means that the corresponding resin is 50% by mass or more, preferably 75% by mass or more, based on the resin component of the layer containing each resin (100% by mass). (In the present specification, the same applies hereinafter).

  Moreover, the numerical rule regarding the “tensile elongation at break” in the present invention shall be applied to both the flow direction (MD) during film formation and the direction (TD) perpendicular to the measurement direction (TD). The same applies hereinafter).

  The “laminate sheet” of the present invention includes both a range generally referred to as “film” and a range referred to as “sheet” with respect to the thickness. Hereinafter, in the present invention, for convenience, a single name “sheet” is used (the same applies hereinafter).

  The second aspect of the present invention includes a first resin layer (10) mainly composed of an acrylic resin containing a core / shell type acrylic cross-linked elastic body component, an aromatic polycarbonate resin, or a polyester resin and an aromatic resin. A second resin layer (20) mainly composed of a blend composition with a polycarbonate-based resin, the first resin layer has a tensile elongation at break at 23 ° C. of 120 to 350%, and the second resin layer A laminate sheet for design coating (110), characterized by having a tensile elongation at break at 23 ° C of 120% or more after standing in an environment of 40 ° C x 90% RH for 30 days.

  About the said blend composition, while the polyester-type resin is a dicarboxylic acid component of this resin, a terephthalic acid or a dimethyl terephthalic acid, and a diol component is 50-75 mol% 1.4-cyclohexanedimethanol, 25-50 An aromatic polyester resin composed of mol% ethylene glycol is preferred.

  In the blend composition, the aromatic polycarbonate resin is also preferably 25% by mass or more based on the total amount of the blend composition.

  Further, the polyester resin in the blend composition is such that the dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, and the diol component is 25 to 50 mol% of 1.4-cyclohexanedimethanol, and 50 to 75 mol%. While being an aromatic polyester resin composed of ethylene glycol, the blend composition may be a blend composition of less than 55% by weight of aromatic polyester resin and 45% by weight or more of aromatic polycarbonate resin.

  Furthermore, it is preferable that the first resin layer (10) has a colorant and the second resin layer (20) is transparent.

  In the said laminated sheet for designable coatings (120), you may have a printing layer (30) between the 1st resin layer (10) and the 2nd resin layer (20).

  The laminated sheet for designable coating (130) may have an uneven shape formed by an embossed plate on the surface of the second resin layer (20).

  In the third aspect of the present invention, the first resin layer (10) side of the laminated sheet for design coating having an uneven shape formed by an embossed plate on the surface of the second resin layer (20) is bonded to the surface. And a laminated sheet-covered metal plate (150) laminated on the metal plate (60) with an adhesive.

  4th this invention is an elevator interior material using said laminated sheet covering metal plate (150).

  5th this invention is a steel furniture member using said laminated sheet coating metal plate (150).

  6th this invention is a household appliances housing | casing member using said laminated sheet covering metal plate (150).

  7th this invention is a building interior material using said laminated sheet covering metal plate (150).

  In the 1st present invention and the 2nd present invention, since the 1st resin layer (10) has acrylic resin as the main ingredients, it is excellent in coloring nature. Moreover, the 1st resin layer (10) is excellent in adhesiveness with the 2nd resin layer (20) and a metal plate (60). In addition, since the acrylic resin is relatively easy to form a calendar, laminated sheets of various colors can be easily obtained in a small lot.

  Furthermore, in the first aspect of the present invention, the second resin layer (20) is a layer mainly composed of a polyester resin having a specific composition range, and the laminated sheet of the present invention is excellent in surface hardness and embossing machine. The transferability of the embossed pattern is also good. Therefore, it is possible to obtain a laminated sheet that can transfer not only the color but also the embossed pattern with a small lot and various patterns. Furthermore, even if the laminated sheet of the present invention is coated on a metal plate and stored for a long period of time and then bent, the resin layer is not cracked or whitened due to fine cracks due to a decrease in workability over time.

  In the second aspect of the present invention, the second resin layer (20) is mainly composed of a layer mainly composed of a blend composition of a polyester resin having a specific composition range and an aromatic polycarbonate resin, or an aromatic polycarbonate resin. By setting it as the layer used as a component, the glass transition temperature of resin which comprises a 2nd resin layer can be made high. As a result, the embossing heat resistance of the embossed pattern imparted to the layer can be increased. Therefore, the embossed pattern can be further improved in survivability even when laminated on a relatively thick metal plate which takes time to cool from the heating temperature of the metal plate during lamination.

  In the third aspect of the present invention, it is possible to obtain a laminated sheet-coated metal sheet having an embossed design that has good workability and scratch resistance and does not cause a decrease in bending workability even after long-term storage. .

  In the fourth to seventh aspects of the present invention, it is possible to obtain a processed product having good performance produced using a metal plate having the above performance.

  The laminated sheet for design coating of the present invention and the laminated sheet-coated metal plate will be described below with reference to FIGS. 1 (a) to 1 (e) as appropriate.

  Fig.1 (a) is sectional drawing which shows typically the lamination sheet 110 of the basic composition of this invention. The laminated sheet 110 includes a first resin layer 10 mainly composed of an acrylic resin and an aromatic polyester resin having a specific composition range, or a blend composition of an aromatic polycarbonate resin and a polyester resin having a specific composition range. Alternatively, it is formed by at least two layers of the second resin layer 20 mainly composed of an aromatic polycarbonate resin. 1B is a cross-sectional view of a laminated sheet 120 having a configuration in which a printing layer 30 is provided between the first resin layer 10 and the second resin layer 20 in addition to the configuration of FIG. It is a schematic diagram which shows. FIG.1 (c) shows the cross section of the lamination sheet 130 with which the embossed 2nd resin layer 20A by which the embossing pattern was provided to the 2nd resin layer 20 side surface of the lamination sheet 120 of FIG.1 (b) is arrange | positioned. It is a schematic diagram shown. Moreover, FIG.1 (d) is the laminated sheet 140 which provided the adhesive bond layer 40 or the adhesive resin layer 40 between the 1st resin layer 10 and the 2nd resin layer 20 in the structure of Fig.1 (a). It is a schematic diagram which shows the cross section. Furthermore, FIG.1 (e) is a model which shows the cross section of the lamination sheet coating | coated metal plate 150 in which the lamination sheet 130 of the structure shown in FIG.1 (c) is laminated | stacked on the metal plate 60 via the adhesive bond layer 50. FIG. FIG. Hereinafter, each of these layers will be described in detail.

<First resin layer 10>
The first resin layer 10 is mainly composed of an acrylic resin containing a core / shell type acrylic cross-linked elastic body component, and can be easily obtained by a calendering method.

  The first resin layer 10 has a tensile elongation at break at 23 ° C. of 120 to 350% in both the flow direction (MD) during sheet formation and the direction (TD) perpendicular to the flow direction (MD). If the tensile elongation at break is too small, regardless of the composition of the second resin layer 20, when the laminated sheet is coated on a relatively thick metal plate and the laminated sheet-coated metal plate is subjected to bending processing, It becomes easy to produce workability defects, such as a crack of a lamination sheet. Further, if the tensile elongation at break is too large, the flexibility of the first resin layer 10 is too high, which causes a problem in the handleability of the first resin layer 10 alone. Moreover, even if the second resin layer 20 described below is laminated with a practical thickness, it is difficult to impart sufficient scratch resistance to the laminated sheet.

Here, the “acrylic resin” refers to the general formula (1)
_{^{CH 2 = CR 1 -COOR 2 (}} 1)
The thing which contains as a main component the polymer obtained by superposing | polymerizing the single composition of the acryl-type monomer shown by or multiple composition.

In the general formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents an alkyl group or a cycloalkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms.

  As the acrylic resin in the first resin layer 10, for example, an acrylic resin whose rupture elongation is improved by random copolymerization of butyl acrylate and the like with methyl methacrylate and the like, excellent compatibility with the acrylic resin, An acrylic resin to which the plasticizer having an action of lowering the glass transition temperature Tg of the acrylic resin is added, or an acrylic whose elongation at break is improved by adding a polymer component having a certain degree of compatibility with the acrylic resin. A resin or the like can be used. Among these, acrylic resins mainly composed of methyl methacrylate having a glass transition temperature Tg of 85 ° C. or higher can be preferably used. When the glass transition temperature Tg is lower than this, a problem is likely to occur in the film forming property in the calendar film forming.

  As a plasticizer having an action of lowering the glass transition temperature of the acrylic resin, a phthalic acid plasticizer (for example, dioctyl phthalate (DOP)), an acrylic resin having a molecular weight of 1000 to 20000 obtained by continuous bulk polymerization A polymer plasticizer (for example, “Alfon UP” manufactured by Toa Gosei Co., Ltd.) or the like can be used.

  In addition, as a polymer component having a certain degree of compatibility with the above acrylic resin, polyvinylidene fluoride resin, polyethylene oxide, or the like can be used.

  As the crosslinked elastic body component added to the acrylic resin, those generally used as impact modifiers such as ABS and MBS can be used. In the present invention, since it is necessary to add a relatively large amount of a crosslinked elastic body component, it is excellent in compatibility with an acrylic resin serving as a matrix resin and hardly causes whitening in bending. It is preferable to use “component”.

  The “acrylic resin-based cross-linked elastic component” is obtained by graft polymerization of an acrylic composition phase for obtaining compatibility with a matrix by multistage polymerization on a cross-linked acrylic rubber phase.

  Examples of the acrylic resin used in the crosslinked acrylic rubber phase include acrylic acid esters having an alkyl group with 1 to 8 carbon atoms. In order to improve the processability at low temperature, it is preferable that the main component is an acrylic resin having a glass transition temperature lower than 0 ° C., and has 4 to 8 carbon atoms such as butyl acrylate and 2-ethylhexyl acrylate. Are preferred.

  Other vinyl monomer components that can be copolymerized include methacrylic acid esters such as methyl methacrylate and butyl methacrylate, aromatic vinyl compounds such as styrene, and vinyl cyanide compounds such as acrylonitrile. Also good.

  The crosslinkable / copolymerizable monomer for imparting a crosslinked structure to the acrylic rubber phase may be any monomer having at least two polymerizable double bonds in one molecule, such as ethylene glycol dimethacrylate, Use of unsaturated carboxylic acid diesters of glycols such as 1.3-butylene glycol dimethacrylate, 1.4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, and polyvinylbenzene such as divinylbenzene and trivinylbenzene. Can do.

  The acrylic rubber phase is graft-polymerized with a monomer mainly composed of a methacrylic ester resin for the purpose of improving the compatibility with the matrix resin.

  Examples of the methacrylic acid ester that is the main monomer for graft polymerization include alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. Examples of the acrylic ester as the copolymer component include acrylic ester components such as methyl acrylate, ethyl acrylate, and butyl acrylate, aromatic vinyl compounds such as styrene, and vinylcyan compounds such as acrylonitrile. Etc.

  The acrylic resin-based crosslinked elastic body component having the above basic structure is referred to as a core / shell type acrylic, and various types are commercially available as an acrylic impact modifier or a processing aid.

  The acrylic resin containing the core-shell type acrylic cross-linked elastic body component is of various grades with designations such as “soft acrylic”, “soft acrylic”, “flexible acrylic”, or “calendar acrylic”. Are commercially available, and these can also be suitably used in the present invention. However, the cross-linked elastic component that can be used in the present invention is not limited to the acrylic cross-linked elastic component, and MBS-based cross-linked elastic is not limited to the extent that bending whitening, weather resistance, heat resistance, etc. are not a problem. Body components and the like may be used in combination.

  Such an acrylic resin has a high melt tension because it contains a relatively large amount of the crosslinked elastic body component. Therefore, there is little possibility that the melt tension is insufficient during the calendar film formation and the film is drawn down to make it difficult to form the film.

  Moreover, by including a crosslinked elastic body component, the releasability of the first resin layer 10 from the metal roll is improved, and there is little risk of sticking to the calendar roll without special measures for the lubricant or the like. Therefore, the acrylic resin in the first resin layer 10 is an acrylic resin containing a core-shell type copolymer composition, which is suitable for forming the first resin layer 10 by the calendering method. The first resin layer of various colors can be efficiently produced in a small lot by a calendering method.

  Moreover, since the releasability from the heated metal roll is also good in the embossing machine, it can be excellent in embossing suitability.

  Further, when the acrylic resin containing the above-mentioned core / shell type acrylic cross-linked elastic body component is used, the elongation at break is large, so that when it is used for the first resin layer 10 of the present invention, the necessary tensile force is required. It is easy to obtain elongation at break, and good workability can be imparted to the resin-coated metal plate.

  The first resin layer 10 is provided with a colorant for the purpose of imparting design properties by various colors, providing a visual concealing effect for the base material on which the laminated sheet such as the metal plate 60 is coated, and improving the coloring of the printing layer 30. Can be added. The colorant may be a pigment or a dye, and those generally used for the above purpose can be used. Regarding the addition amount, an amount generally added for the above purpose may be used. For example, the addition amount of the pigment is 0.2 to 40% by mass based on the mass of the entire first resin layer 10 (100% by mass). Regarding the concealing property, the required pigment addition amount (%) increases as the thickness of the first resin layer 10 decreases. Moreover, the addition amount of dye is 0.1-2 mass% on the basis (100 mass%) of the mass of the 1st resin layer 10 whole. Further, the colorant may be one kind or a mixture of several kinds.

  As a preferred colorant, for example, a titanium oxide pigment that has a high concealing effect in white coloration and has a small influence on the processability of a laminated sheet can be used as a base because the particle size is fine. Furthermore, a small amount of chromatic organic or inorganic pigments or dyes may be added to adjust the color. In this case, since the 1st resin layer 10 is a layer which has acrylic resin as a main component, the dispersibility of a coloring agent is excellent and the color development property of the 1st resin layer 10 becomes favorable. Thereby, the lamination sheet of this invention excellent in the designability can be obtained.

  Regarding the visual hiding effect of the background, the degree of importance differs depending on the application, and it cannot be specified unconditionally. As a guideline, for resin-coated metal sheets for interior building materials, JIS K5600-4-1: 1999 (Paint General Test Method-Part 4: Visual characteristics of coating film-Section 1: Hiding power (light colored paint) In many cases, it is required that the concealment ratio measured in accordance with (1)) is 0.98 or more. Therefore, also in the laminated sheet of the present invention, the concealment rate is preferably 0.98 or more. Moreover, since the design of the color and pattern which a base | substrate has is reflected depending on a use, the coloring concealment property of the 1st resin layer 10 can also be reduced dare.

  In addition, various additives may be added to the first resin layer 10 in appropriate amounts as long as the properties are not impaired. Additives include various antioxidants such as phosphorus and phenol, process stabilizers such as lactone and phenol acrylate, thermal stabilizers, ultraviolet absorbers, hindered amine radical scavengers, impact modifiers, various processing aids. And additives generally added to resin materials, such as an agent, a metal deactivator, an antibacterial / antifungal agent, an antistatic agent, a flame retardant, a pigment dispersibility improver, and a filler / bulking agent.

  There is no restriction | limiting in particular about the film forming method of the 1st resin layer 10, You may form by extrusion film forming methods, such as a calender film forming method, a T-die film forming method, and an inflation method, a solvent casting method, etc. Among these, it is particularly preferable to form a film by a calendar film forming method excellent in small lot compatibility. From this point of view, there is an advantage of the present invention in which the first resin layer 10 is composed mainly of an acrylic resin containing a specific component.

  The thickness of the first resin layer 10 is preferably 40 μm or more. If the thickness is too thin, it is necessary to add a large amount of colorant to conceal the base, and as a result, the workability of the first resin layer 10 may be reduced. In addition, in order to obtain a high concealing effect while reducing the thickness of the first resin layer 10, it is necessary to add a special colorant, which increases the manufacturing cost. Furthermore, in consideration of film formation stability when the first resin layer 10 is formed by a calendar method, the thickness of the first resin layer 10 is more preferably 70 μm or more.

  Moreover, it is preferable that the thickness of the 1st resin layer 10 is 280 micrometers or less. If the thickness is too thick, the design effect, the visual hiding effect, and the protective effect on the metal plate 60 are saturated, but the workability may be reduced. Moreover, in order to make the thickness of the laminated sheet of this invention into the preferable range shown below, it is preferable that the 1st resin layer 10 is the thickness within said range.

<Second resin layer 20>
The second resin layer 20 can impart scratch resistance to the laminated sheet of the present invention by being laminated on the relatively flexible first resin layer 10. Further, since the first resin layer 10 is inferior in embossing suitability (transferability) due to containing a large amount of the acrylic resin-based crosslinked elastic body component, by laminating the second resin layer 20, The laminated sheet can be made excellent in embossing suitability. In addition, by specifying the composition of the second resin layer 20, it is possible to prevent deterioration in workability even if the resin-coated metal plate is subjected to bending after being stored for a long period of time. Furthermore, there is an effect of protecting the printing layer 30 described below.

  In the first aspect of the present invention, the second resin layer 20 that achieves the above object has a dicarboxylic acid component of terephthalic acid or dimethyl terephthalic acid, and a diol component of 50-75 mol% of 1.4-cyclohexanedi. The main component is an aromatic polyester resin composed of methanol and 25 to 50 mol% ethylene glycol. By blending the above components, a low crystalline aromatic polyester resin can be obtained. If the ratio of 1.4-cyclohexanedimethanol in the diol component is less than this, the physical property deterioration due to enthalpy relaxation becomes remarkable, which is not preferable. If it exceeds this range, the characteristics of the crystalline resin will become prominent, and crystallization may progress during heating by an embossing machine, making embossing difficult, and workability as a resin-coated metal plate may be reduced. There is a risk.

  Here, “low crystallinity” means an amorphous polyester resin generally used in the prior art (for example, “Easter PETG6763” manufactured by Eastman Chemical Company), in which the dicarboxylic acid component is terephthalic acid. And the diol component is composed of about 30 mol% of 1.4-cyclohexanedimethanol and about 70 mol% of ethylene glycol). Is. For the second resin layer 20 in the laminated sheet for designable coating according to the present invention, the low crystalline resin is preferably used without orientation.

  The low crystalline polyester resin that can be used for the second resin layer 20 of the present invention is a calendered film having a temperature condition that has been used for conventional soft PVC sheet filming because of its crystallinity. Although it is difficult to produce a sheet with equipment, it is possible to form a film as an amorphous sheet according to an ordinary extrusion film forming method. Further, in the heating process until the embossed pattern is transferred by the embossing machine, the crystallization to such an extent that emboss transfer becomes difficult does not proceed. Further, even when heating when laminating to a metal plate, the workability does not deteriorate due to the progress of crystallization.

  As the polyester resin in the above composition range, Eastman Chemical whose dicarboxylic acid component is terephthalic acid and whose diol component is about 65 mol% of 1.4-cyclohexanedimethanol and about 35 mol% of ethylene glycol. • Commercially available as “PCTG 5445” from Company.

  In the polyester resin of the composition range, the reason why there is little decrease in workability due to the progress of enthalpy relaxation is that the glass transition temperature is higher than that of a generally used amorphous polyester resin. There is also a theory that a bulky alicyclic structure is contained more than a general amorphous polyester resin. In any case, as a phenomenological theory, it has been confirmed that the problem of deterioration in workability over time does not occur in the configuration of the resin-coated metal plate of the present invention.

  As defined in the second aspect of the present invention, the second resin layer 20 is composed mainly of a blend composition of a polyester resin and an aromatic polycarbonate resin, or an aromatic polycarbonate resin alone. It may be. By mixing the aromatic polycarbonate-based resin, the glass transition temperature rises, and emboss return when laminating to a thick metal plate can be reduced. Further, as the glass transition temperature of the blend composition increases, the progress of enthalpy relaxation does not become a problem for realistic storage temperature and humidity conditions. For reference, FIG. 2 shows an example in which the relationship between the blend ratio and the glass transition temperature (Tg) when a polyester-based resin (PCTG-based) and an aromatic polycarbonate-based resin (PC) are blended is shown.

  When the above blend composition is used as the main component of the second resin layer 20, the polyester resin contained in the blend composition contains at least 50 mol% of the diol component of polyethylene terephthalate as 1.4-cyclohexanedimethanol. The one substituted with can be used. Such a polyester resin is preferable because it is excellent in compatibility with an aromatic polycarbonate resin and can take any blend ratio. Further, the amount of 1.4-cyclohexanedimethanol is preferably less than 75 mol% of the diol component so that the influence of crystallinity is not significant. Examples of the polyester resin having such a composition range include “PCTG 5445” manufactured by Eastman Chemical Company.

  In this blend composition, the aromatic polycarbonate resin is preferably 25 to 100% by mass, and more preferably 30 to 80% by mass, based on the mass of the entire blend composition (100% by mass). If the blend ratio of the aromatic polycarbonate resin is too small, the effect of improving the embossing heat resistance becomes poor. On the other hand, if the blend ratio of the aromatic polycarbonate resin is too large, the initial tensile breaking elongation of the sheet made of the blend composition becomes relatively small, and the workability may be insufficient depending on the thickness of the metal plate to be coated. is there.

  As a polyester-based resin contained in the blend composition, an amount of less than 55% by mass and an aromatic of 45% by mass or more obtained by replacing 20-50 mol% of the diol component of polyethylene terephthalate with 1.4-cyclohexanedimethanol. You may blend and use with polycarbonate-type resin. Polyester resins having a substitution amount of 1.4-cyclohexanedimethanol of less than 50 mol% are slightly inferior in compatibility with aromatic polycarbonate resins. On the other hand, this composition range includes general PETG containing about 30 mol% of 1.4-cyclohexanedimethanol, and has an advantage that low-cost raw materials can be used. When the blend ratio of the polyester-based resin having the above composition is 55% by mass or more, it is difficult to suppress a decrease in workability due to the progress of enthalpy relaxation. Further, the haze (cloudiness) of the second resin layer 20 may increase.

  By making the blend ratio of the polyester resin having the above composition less than 55% by mass, an effect of improving the workability with time can be seen. This is considered to be an effect of forming a matrix phase mainly composed of an aromatic polycarbonate resin. When the amount of 1.4-cyclohexanedimethanol substitution of the polyester resin is less than 20 mol%, the characteristics as a crystalline resin become remarkable, and crystallization proceeds when heated in an embossing machine even in the blend composition. There is a possibility that it may be difficult to apply, and there is a possibility that workability as a resin-coated metal plate may be lowered.

  When the ratio of the aromatic polycarbonate-based resin is 80% by mass or more, the initial tensile breaking elongation of the sheet made of the blend composition becomes relatively small, and depending on the thickness of the metal plate to be coated, there is a risk of insufficient workability.

  The aromatic polycarbonate-based resin that can be used in the blend composition is not particularly limited, but the most general-purpose bisphenol A type having the same molecular structure but using bisphenol A and phosgene as raw materials or not using phosgene. Polycarbonate resin can be used. The viscosity average molecular weight of the aromatic polycarbonate resin used in the present invention is preferably in the range of 20000 to 40000, more preferably in the range of 22000 to 30000. When the viscosity average molecular weight is too small, the mechanical strength, particularly the low temperature impact strength is lowered. On the other hand, when the viscosity average molecular weight is too large, the melt viscosity becomes very high and the molding processability decreases. Moreover, since polymerization requires a long time, it is not preferable from the viewpoint of production cycle and cost.

  The thickness of the second resin layer 20 is preferably in the range of 15 to 150 μm. The range of 20 to 100 μm is more preferable, and the range of 30 to 75 μm is particularly preferable. If the thickness of the second resin layer 20 is too thin, the first resin layer 10 is a layer mainly composed of a relatively flexible acrylic resin, so that the surface hardness of the laminated sheet is lowered and the scratch resistance is ensured. It becomes difficult to do. Further, if the thickness is too thick, the first resin layer 10 may be a laminated sheet with the second resin layer 20 in spite of using a layer mainly composed of an acrylic resin with good workability. Workability will be inferior. Further, since the second resin layer 20 is mainly composed of a polyester-based resin having light yellowing, the thickness of the second resin layer 20 is a predetermined value in order to prevent the light yellowing over time from becoming conspicuous. It is preferable not to make it thicker.

  In the second resin layer 20, various amounts of various additives for resin can be added to such an extent that the effects of the present invention are not impaired. Resin additive is the first resin layer, except that it may significantly reduce the transparency or cause voids when processing such as bending as a laminated sheet-coated metal plate, resulting in poor appearance. The same additives as those that can be used for 10 can be used. Moreover, you may add hydrolysis inhibitors, such as a carbodiimide type compound and an oxazoline type compound with which the effect is anticipated especially in a polyester-type resin. As such a hydrolysis inhibitor, those commercially available from various companies can be used. Depending on the application, an ultraviolet absorber or the like can be added for the purpose of suppressing the light yellowing of the second resin layer 20 over time.

  The second resin layer 20 is normally transparent. Regarding the coloring, even when the printing layer 30 described below does not exist, the second resin layer 20 is concealed with the first resin layer 10 having good calendering properties and excellent compatibility with small lots as the colored layer. It is preferable not to contain a high pigment. In the first invention and the second invention as well, the second resin layer is insufficient for both the temperature condition and the drive system load in the calender film forming equipment that has been used for conventional soft PVC sheet film formation, This is because it is necessary to obtain a sheet by an extrusion film forming method inferior in color changeability, and it is preferable to form a large amount of film in a single standard as a substantially transparent sheet.

  The second resin layer 20 may be colored while ensuring transparency by adding a dye-based transparent colorant, a fluorescent agent, a bluish imparting agent, or the like for the purpose of imparting design properties. Also, add various metallic powders such as aluminum powder, silver powder, gold powder, etc., glass flakes, surface-modified mica powder, ceramic powder, hologram foil, etc. with appropriate particle size, and disperse in a dot-like manner while ensuring transparency. Thus, a design that expresses radiance may be imparted. Thereby, in addition to the coloring design by coloring agents, such as a pigment in the 1st resin layer 10, in addition to the printing design of the printing layer 30 demonstrated below, the design provided to the 2nd resin layer 20 is combined, and the whole design is formed. be able to. However, it is preferable that the addition of these additives to the second resin layer 20 does not hinder the color changeability.

  In the present invention, the second resin layer 20 has a tensile elongation at break of 120% or more when subjected to a tensile test at 23 ° C. after being left in an environment of 40 ° C. × 90% RH for 30 days. It is essential. More preferably, the tensile elongation at break is 150% or more. If the tensile elongation at break after storage under the above conditions is less than 120%, a coated metal plate obtained by coating a laminated sheet using the second resin layer 20 on a relatively thick metal plate under realistic conditions. There are many problems in workability when bending is performed after storage in a warehouse. Basically, this condition can be achieved by using the second resin layer having the composition defined in the first invention and the second invention. Even when the above composition is used due to insufficient drying, the elongation at break after aging may be lower than the above value. Therefore, in the present invention, in each of the first invention and the second invention, the elongation at break as the film-forming sheet of the second resin layer 20 is defined as described above.

<Print layer 30>
The laminated sheet of the present invention may have a printed layer 30 between the first resin layer 10 and the second resin layer 20. The printing layer 30 can be applied by a known printing method such as gravure printing, offset printing, or screen printing. The pattern of the print layer 30 is arbitrary, such as a stone pattern, a wood grain, a geometric pattern, or an abstract pattern. Moreover, partial printing or full surface solid printing may be used, and both a partial printing layer and a solid printing layer may be provided. Moreover, you may provide a printing pattern so that a printing design and the embossing design provided by a post process may synchronize.

  The printed layer 30 may be formed on the surface of the first resin layer 10 on the side where the second resin layer 20 is laminated, and then laminated with the second resin layer 20 to form laminated sheets 120 and 130. Alternatively, a so-called back print type printing layer 30 is formed on the surface of the second resin layer 20 on the side laminated with the first resin layer 10, and then laminated with the first resin layer 10 as laminated sheets 120 and 130. Also good.

<Manufacturing method of laminated sheet for design coating (lamination integration of first resin layer 10 and second resin layer 20 and provision of embossed pattern)>
FIG. 3 shows an embossing machine 100 that has been conventionally used for giving an embossed pattern to a soft PVC sheet. The lamination integration of the first resin layer 10 and the second resin layer 20 of the present invention can be basically performed by heat fusion lamination using one part of the heating roll in the embossing machine 100 or the like. Is possible. Thus, it is preferable in terms of cost to stack the first resin layer 10 and the second resin layer 20 because it does not involve an increase in the number of steps and an increase in raw materials used. When the second resin layer 20 contains an aromatic polycarbonate-based resin, the adhesive strength at the heat fusion interface between the first resin layer 10 and the second resin layer 20 can be made stronger.

  The lamination and integration method of the first resin layer 10 and the second resin layer 20 is not limited to the above-mentioned heat fusion lamination, but is an isocyanate crosslinking agent mainly composed of a polyester resin or a polyether resin. So-called dry lamination method using a curing adhesive, a method using an ultraviolet curable adhesive or an electron beam / radiation curable adhesive, a method of interposing a hot melt adhesive, an extrusion film formation of the second resin layer 20 Generally used for adhesive lamination of two sheets, such as a method of co-extruding a first resin layer 10 made of acrylic resin or a resin layer having easy adhesion with a binder resin of printing ink Any method can be applied without limitation.

  Specifically, the thickness of the adhesive layer 40 in the dry lamination method is preferably about 1 to 20 μm in terms of dry film thickness. If the adhesive layer 40 is thinner than this, adhesion failure due to uneven application tends to occur, and if it is thicker than this, the workability of the laminated sheet may be lowered from the beginning. When the adhesive layer 40 is applied, coloring may be performed using a dye-based transparent colorant, a fluorescent agent, a bluish imparting agent, or the like for designability. Further, surface-modified mica powder, aluminum fine powder, hologram foil or the like may be added. Further, the adhesive layer 40 may contain appropriate amounts of various additives that are generally added to curable adhesives.

  The acrylic resin of the first resin layer 10 is an acrylic resin containing a core-shell type copolymer composition obtained by graft polymerization of an acrylic resin with an acrylic resin-based crosslinked elastic body component as a core. If it exists, it has non-adhesiveness with respect to the heating roll 1 heated to about 100-140 degreeC, and it is not necessary to take a special measure for the adhesion prevention to the heating roll 1. FIG.

  Even when the printing layer 30 is provided between the first resin layer 10 and the second resin layer 20, by appropriately selecting the binder resin of the printing ink or after applying the printing design layer on the printing line Each layer can also be heat-sealed and laminated by continuously applying the adhesion primer layer using a solid plate roll. As the printing ink used in the printing layer 30, an acrylic thermoplastic ink, a polyester-based cross-linkable ink whose cross-linking degree is appropriately adjusted, and the like can be preferably used.

  In the embossing machine 100 shown in FIG. 3, the sheet material 7 that is wound on the heating roll 1 in the order of the first resin layer 10 and the second resin layer 20 and laminated and heated passes through the take-off roll 2 and is then red. Predetermined processing is performed by the outer heater 3, and further, the nip roll 4, the embossing roll 5, and the cooling roll 6 are sent.

  The sheet material 7 laminated and integrated by the heating roll 1 as described above can subsequently be given an embossed pattern by the embossing roll 5 in the same manner as a conventional soft PVC sheet. That is, the sheet material 7 laminated and integrated by the heating roll 1 and preheated is stably peeled off from the heating roll by the take-off roll 2, and then heated to 160 to 190 ° C. by the infrared heater 3, An embossed pattern is imparted to the second resin layer 20 by the embossing roll 5. Thereafter, the laminated sheet is cooled by the cooling roll 6.

  Even at 160 to 190 ° C., which is the sheet heating temperature by the infrared heater 3, the first resin layer 10 is a layer having a relatively melt tension, so that the laminated sheet does not shrink, wrinkle or break. . Moreover, the 2nd resin layer 20 can obtain the embossed lamination sheet 130 of a favorable external appearance by having favorable embossing suitability.

<Laminated sheet>
The total thickness of the laminated sheet is preferably 300 μm or less. The reason for this is that if the total thickness of the laminated sheet is too thick, it becomes difficult to use a molding die that has been used for forming a flexible PVC resin-coated metal sheet. This is because the adaptability of the processing equipment is reduced.

<Metal plate 60>
As the metal plate 60 in the laminated sheet-coated metal plate 150 of the present invention, various steel plates such as hot-rolled steel plate, cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, tin-plated steel plate, stainless steel plate, aluminum plate, aluminum-based alloy A board etc. can be used. Moreover, these metal plates 60 can also be used after performing a normal chemical conversion treatment. The thickness of the metal plate 60 varies depending on the use of the laminated sheet-covered metal plate 150, but can be selected in the range of 0.1 to 10 mm.

  In general, the metal plate 60 has a thickness of about 0.40 to 0.60 mm for use in interior building materials. In the elevator use, the resin-coated metal plate 150 is not a simple decorative plate, but is used as a material for sharing strength. . Therefore, those having a thickness of 1.0 to 1.2 mm are used, and those having a thickness of 1.6 mm may be used. Since it is necessary to laminate and bend a resin sheet on a metal plate having this thickness, deterioration of workability with time is a problem particularly in elevator interior use.

<Method for producing laminated sheet-coated metal sheet>
The laminated sheet-coated metal plate 150 of the present invention can be manufactured by laminating the above laminated sheet on the metal plate 60. Examples of the adhesive that forms the adhesive layer 50 used when laminating include commonly used thermosetting adhesives such as acrylic adhesives, epoxy adhesives, urethane adhesives, and polyester adhesives. An agent can be mentioned. Since the 1st resin layer 10 is a layer which has acrylic resin as a main component, it is preferable to use an acrylic adhesive among said adhesives from the point of obtaining favorable adhesiveness.

  As a method of laminating the laminated sheet, using various commonly used coating equipment such as reverse coater, kiss coater, etc. on the above-described various metal plates 60, the metal surface to which the laminated sheet is laminated is dried. The adhesive is applied so that the thickness of the adhesive layer 50 is about 2 to 10 μm. Next, the coated surface is dried and heated by an infrared heater and / or a hot air heating furnace, and the surface temperature of the metal plate 60 is maintained at a temperature of about 180 to 250 ° C. Then, immediately using the roll laminator so that the first resin layer 10 side of the laminated sheet becomes an adhesive surface, the laminated sheet is adhered and cooled to obtain the laminated sheet-coated metal plate 150 of the present invention. Can do.

  In order to describe the present invention more specifically and in detail, the following examples are given, but the present invention is not limited to these examples.

<Film formation of the first resin layer 10>
As the 1st resin layer 10 (A1-A9), the various commercially available acrylic raw material which described the kind and compounding quantity in Table 1 was mix | blended. A total of 100 parts by mass of the resin composition, 0.5 parts by mass of “Metbrene L-1000” (Mitsubishi Rayon Co., Ltd.) as a lubricant, and 18 of a light brown pigment in which titanium oxide and an organic brown pigment are mixed Part by mass was added. These resin mixtures are subjected to sheet rolling under a roll temperature of 180 to 195 ° C. using a calender film forming apparatus comprising four metal rolls having a preliminary kneading roll in the previous step, and have a thickness of 150 μm and a width. A 1200 mm light brown sheet was formed. There was no particular problem with the calendering property for any of the formulations.

  Regarding the first resin layer 10 (A6), the surface of the first resin layer 10 on the side laminated with the second resin layer 20 is mainly composed of dark brown using an acrylic / urethane ink by a gravure coater. Abstract pattern printing was performed to form a printing layer 30.

In Table 1, “Metabrene W-377” is an acrylic resin containing a large amount of an acrylic resin-based crosslinked elastic body component manufactured by Mitsubishi Rayon Co., Ltd., and is commercially available as an acrylic resin for calendar film formation. is there.
“Metabrene H-660” is a polymethylmethacrylate resin containing no acrylic resin-based crosslinked elastic body component manufactured by Mitsubishi Rayon Co., Ltd.
“Parapet SA” is a soft acrylic raw material containing an acrylic resin-based crosslinked elastic body component manufactured by Kuraray Co., Ltd., and substitutes for soft PVC for injection molding applications.
“Parapet GR-F” is an acrylic resin containing an acrylic resin-based crosslinked elastic body component having flexibility suitable for overlay use, manufactured by Kuraray Co., Ltd.

  The first resin layer 10 (A10) is a low-density polyethylene (LDPE) -based pale brown colored calender sheet for a commercially available resin-coated metal plate, and has a thickness of 150 μm and an easily adhesive primer on the back surface. A layer is applied. The calendar sheet was given a satin embossed pattern at the time of acquisition, and the embossed pattern was not applied by the embossing machine 100.

  The first resin layer 10 (A11) is a calendar sheet colored in light brown mainly composed of a commercially available amorphous polyester resin. As the compounding of the resin, the non-crystalline polyester resin “Easter PETG6763” manufactured by Eastman Chemical Co., Ltd. or an amorphous polyester having a resin composition equivalent thereto is the main component, and the resin composition is 100 parts by mass to improve the calendar suitability. Therefore, it is considered that 10 to 20 parts by mass of MBS impact modifier and about 1.0 to 3.0 parts by mass of fatty acid ester lubricant are included. The thickness of the sheet is 150 μm and the width is 1200 mm.

<Film formation of the second resin layer 20>
As the second resin layer 20 (B1 to B14), various commercially available polyester resin materials and polycarbonate resin materials described in Table 2 were used. Using these resins as raw materials, a T-die was connected to a single-screw extruder with a vent of 65 mm in diameter, and a sheet having a thickness of 50 μm and a width of 1100 mm was obtained by taking up with a mirror casting roll held at 125 ° C. by an oil circulator. .

The composition of the raw material resin used for the second resin layer 20 is as follows.
Easter PETG6763 (manufactured by Eastman Chemical Co.): about 31 mol. Of ethylene glycol which is a diol component of polyethylene terephthalate. % Is an amorphous polyester resin having a structure in which 1.4% is substituted with 1.4-cyclohexanedimethanol. The glass transition temperature is 78.9 ° C, and the melting point is not observed.

  PCTG5445 (manufactured by Eastman Chemical Co.): About 65 mol. Of ethylene glycol which is a diol component of polyethylene terephthalate. % Is a low crystalline resin having a structure in which 1.4-cyclohexanedimethanol is substituted, and can be treated as substantially amorphous in the extrusion film forming step and embossing step. Glass transition temperature is 86.5 ° C, melting point is not observed.

  Novalex 7025A (manufactured by Mitsubishi Engineering Plastics): bisphenol A type polycarbonate resin. The glass transition temperature is 149.5 ° C., and the melting point is not observed.

<Laminated integration of first resin layer 10 and second resin layer 20 and embossing>
(Examples 1-15, Comparative Examples 1-7)
The first resin layer 10 and the second resin layer 20 were combined as shown in Table 3. These combined resins are used in the embossing machine 100 shown in FIG. 3 for the first resin layer 10 and the second resin layer 20 (or the first resin layer 10 and the second resin layer 20 provided with the printing layer 30). ) And heat embossing lamination and embossing pattern transfer. The heating roll 1 is set to 140 ° C., and the first resin layer 10 and the second resin layer 20 are supplied from two unwinding shafts as shown in FIG. It integrated by lamination. Subsequently, the laminated and integrated sheet is heated with a non-contact type infrared heater 3 until the sheet surface temperature reaches 180 ° C., and a textured embossed pattern is applied with the embossing roll 5, and at the same time the first resin layer 10 and the second resin layer 10. The adhesive lamination of the resin layer 20 was made more reliable. The embossing roll is maintained at 60 ° C. to 100 ° C. in accordance with the glass transition temperature of the second resin layer 20 by a hot water circulator, and has a satin pattern with Rmax = 50 μm. The resulting laminated sheet was evaluated for embossing suitability (adhesion resistance, fusing resistance and transferability) by the method described below. The results are also shown in Table 3.

(Comparative Examples 8 and 10)
In Comparative Example 8 and Comparative Example 10, the second resin layer 20 of the present invention is not laminated, and only the first resin layer 10 shown in Table 1 is used, and embossing suitability is obtained by the method shown below. (Adhesion resistance, fusing resistance and transferability) were evaluated. Moreover, it attached | subjected to the coating to the metal plate of the following process. Under the present circumstances, since the sheet | seat of the comparative example 10 produced the melt fracture of the sheet | seat when heated to 180 degreeC with the embossing application machine, the heating temperature was lowered | hung to 140 degreeC and the embossing pattern provision is performed. The evaluation results of Comparative Example 10 in Table 3 are obtained when the embossed pattern is transferred at the temperature.

(Comparative Example 9)
Moreover, the comparative example 9 was purchased as a sheet | seat of the state to which the embossed pattern of the satin was previously provided, and did not perform a series of suitability evaluation with an embossing machine, but covered the purchased sheet directly on the metal plate.

<Creation of laminated sheet-coated metal sheet>
Next, an acrylic thermosetting adhesive (manufactured by Mitsubishi Rayon Co., Ltd.) that is generally used for a polyvinyl chloride coated metal plate is applied to a metal surface so that the adhesive film thickness after drying is about 2 to 4 μm. It was applied to. Next, the coated surface was dried and heated by a hot air heating furnace and an infrared heater, and the surface temperature of the galvanized steel sheets having thicknesses of 1.2 mm and 1.6 mm was set to 225 ° C. Then, using the roll laminator, the laminated sheet (partially, single-layer sheet) produced above was covered and cooled by water cooling to produce a laminated sheet-coated steel sheet. All examples and comparative examples were laminated under the same conditions. The obtained laminated sheet-coated metal plate was evaluated by the following method. The results are shown in Table 3.

<Measurement standard, test method>
The measurement standards and test methods for the physical properties of the laminated sheets and laminated sheet-coated metal plates shown in Examples and Comparative Examples are as follows.

(1) Tensile breaking elongation at 23 ° C. of the first resin layer 10 JIS K7127-1999 (plastic-tensile property test) using a universal material testing machine (manufactured by Intesco) installed in a constant temperature room at 23 ° C. Tensile test was performed using a test piece shape in accordance with Method-Part 3: Test conditions for film and sheet), and elongation at break was measured. The test is performed at a test speed (pulling speed) of 200 mm / min with respect to the first resin layer single layer before producing the laminated sheet. The measurement direction is a flow direction (MD) during film formation and a direction (TD) perpendicular thereto. In each direction, measurement was performed 5 times, and the average value was evaluated.

  Moreover, regarding the acrylic resin of the first resin layer 10, it has been confirmed that there is no significant change in the tensile elongation at break at long-term storage at room temperature.

(2) Tensile elongation at break of second resin layer 20 at 23 ° C. (initial value and after time)
Using a universal material testing machine (manufactured by Intesco Co., Ltd.) installed in a thermostatic chamber at 23 ° C., a tensile test was performed using a test piece shape according to JIS K7127-1999, and elongation at break was measured. The test is carried out on the single layer of the second resin layer 20 before producing a laminated sheet at a test speed (pulling speed) of 200 mm / min. The measurement direction is a flow direction (MD) during film formation and a direction (TD) perpendicular thereto. In each direction, measurement was performed 5 times, and the average value was evaluated.

  The initial value of tensile elongation at break was measured immediately after the second resin layer 20 made into a sheet by extrusion film formation was conditioned for 24 hours in a thermostatic chamber at 23 ° C.

  The tensile elongation at break after the lapse of time was determined by allowing the second resin layer 20 made into a sheet by an extrusion film forming method to stand in a thermostatic chamber controlled at 40 ° C. × 90% RH for 30 days, and then in a thermostatic chamber at 23 ° C. After the humidity was adjusted for 24 hours, the measurement was performed immediately.

(3) Embossing suitability: Adhesion resistance When embossing was applied with the embossing machine 100 shown in FIG. 3, the sheet adhered to the heating roll was indicated by “x”, and the one not adhered was indicated by “◯”. It was.

(4) Embossing suitability: Fusing resistance When the embossing is applied with the embossing machine 100 shown in FIG. 3, the sheet is blown out while the sheet is heated by the heater. Those marked with remarkable elongation or wrinkles were marked with “△”, and those without these problems were marked with “◯”.

(5) Suitability for embossing: transferability The sheet embossed with the embossing machine 100 shown in FIG. 3 is visually observed, and “○” indicates that the embossed pattern is clearly transferred. The case where the transfer was shallow was indicated by “Δ”, and the case where the transfer was poor and the embossed pattern was shallow, or the surface was simply rough regardless of the embossed pattern was indicated by “x”. The evaluation of the embossed heat resistance is not carried out for those evaluated as “x” in this evaluation.

(6) Embossing heat resistance: at the time of laminating The appearance change of the embossing after laminating the laminated sheet to which embossing was applied by the embossing machine 100 shown in FIG. 3 was laminated with a metal plate was visually observed and compared with the laminated sheet before lamination. If the shape of the emboss is almost unchanged, “○”, if the embossed return is slightly compared to this, “△”, if the embossed return is noticeable, or if the embossed pattern disappears completely, A rough surface is indicated by “x”. Evaluation is carried out when laminating to a 1.2 mm steel plate, and the steel plate temperature and the amount of cooling water before lamination are the same in all examples and comparative examples.

(7) The initial stage of the workability test and after the lapse of time, a bending test is performed on the laminated sheet-covered metal plate, and the surface state of the laminated sheet in the bent portion is visually determined. The case where whitening occurred was evaluated as “Δ”, and the case where cracks occurred was evaluated as “x”. The bending test was performed as follows. Samples of 50 mm x 150 mm were prepared from the length direction and width direction of the laminated sheet-coated metal plate, respectively, kept at 23 ° C for 1 hour or longer, and then 90 ° (inner) using a hydraulic bending tester (hydraulic bender) Bending radius was 2 mm). Table 3 shows only the results after time.

(8) Surface hardness test JIS K5600-5-4: 1999 (Paint general test method-Part 5: Mechanical properties of coating film-Section 4) for a laminated sheet-coated metal plate obtained by laminating a laminated sheet to a metal plate 60 : Scratch hardness (pencil method)). Drawing in a temperature-controlled room at 23 ° C. using a jig that can draw a load of 9.8 N while maintaining a 45 ° angle with respect to the resin sheet surface of the resin-coated metal plate cut out to 80 mm × 60 mm Was done. The surface state of the resin sheet of the part was visually determined, and “◯” indicates that the 2B pencil was not scratched at all; [Delta] ", 3B pencils with scratches were displayed as" x ".

<Evaluation results>
In Comparative Example 1, the most common amorphous polyester resin is used for the second resin layer, but the tensile elongation at break after storage for 30 days in an environment of 40 ° C. × 90% RH is remarkable. As a result, the metal plate coated with the laminated sheet also resulted in a crack in the resin layer in the bending test. Also, embossing was recognized during lamination. This is probably due to the low glass transition temperature of the amorphous polyester resin of the second resin layer.

  In Comparative Examples 2 to 4, the polyester resin of Comparative Example 1 was blended with an aromatic polycarbonate resin, but the effect of improving the elongation at break after aging was insufficient. A crack has occurred. Further, in Comparative Examples 2 and 3 where the blend ratio of the aromatic polycarbonate resin was low, embossing return at the same level as in Comparative Example 1 was recognized.

  Comparative Example 5 is an example in which an acrylic resin having a tensile elongation at break larger than the range specified by the present invention is used for the first resin layer. In these examples, since the flexibility of the first resin layer was too high, sufficient surface hardness could not be obtained even when the resin layer was coated. Furthermore, if the thickness of the second resin layer is increased, the surface hardness should be improved, but it is more efficient to use the acrylic resin having the elongation at break specified in the present invention for the first resin layer. Can do.

  Comparative Example 6 is an example in which an acrylic resin having a tensile elongation at break smaller than the range defined by the present invention was used, and the resin composition defined by the present invention was used as the second resin layer. In this case, there is a problem in workability due to insufficient tensile elongation at break of the first resin layer.

  In Comparative Example 7, when the acrylic resin of the first resin layer has a smaller tensile elongation at break, when Comparative Example 6 is laminated on a steel plate having a thickness of 1.2 mm, slight cracks are generated. What has been completed is cracking in Comparative Example 7.

  Comparative Example 8 is an example in which an acrylic resin in the range specified by the present invention is used, but the second resin layer is not provided. In this example, there was no sticking to the heating roll with the embossing machine, and no significant elongation during heating of the heater, but the transfer of the embossed pattern became very shallow. The sheet is provided with calendar suitability by containing a large amount of an acrylic cross-linked elastic body component, and the sheet exhibits remarkable elastic recovery after the embossed pattern is transferred by an embossing machine. It appears that the transfer became shallow due to the so-called embossing return.

  Moreover, it is judged that the metal plate which coat | covered this sheet | seat is unsuitable for uses, such as an elevator interior material with a low surface hardness, and many opportunities to touch.

  Comparative Example 9 is a case where a commercially available LDPE calendar sheet is laminated on a steel plate alone. In this example, the emboss return at the time of lamination was remarkable. This is considered due to the low melting point of the LDPE resin. The metal plate coated with the sheet also had a low surface hardness, and showed significant whitening in the bending workability test.

  In Comparative Example 10, by reducing the sheet heating temperature in the embossing machine, it was possible to obtain a good embossed pattern transfer without causing adhesion to the heated metal roll, melt fracture, etc. The embossing return was a remarkable result. The resin composition of Comparative Example 10 is considered to be basically the same as the second resin layer of Comparative Example 1, but the embossing heat resistance is lower than that of Comparative Example 1 because the sheet temperature in the embossing machine is lowered. Presumed to be due.

  Further, as a result of the bending workability test, cracks in the resin layer were observed in Comparative Example 1, whereas marked whitening was observed in Comparative Example 10. This is because, although the MBS-based crosslinked rubber is added to the sheet of Comparative Example 10, the deterioration of workability over time accompanying the progress of enthalpy relaxation is suppressed, but the resin layer is stretched by bending. This is probably because fine voids are generated between the rubber particles and the matrix of the amorphous polyester resin.

  On the other hand, in Examples 1-15 which are in the range which this invention prescribes | regulates, the obtained lamination sheet and the lamination sheet covering metal plate showed the generally favorable performance.

  If each Example is evaluated individually, Examples 1-3 will further raise the blend ratio of aromatic polycarbonate-type resin with respect to Comparative Examples 2-4. In Example 1 in which the polycarbonate-based resin is 45% by mass, the elongation at break of the first resin layer after aging is a relatively good value. As a result, good workability was obtained when laminated to a metal plate having a thickness of 1.2 mm. However, when laminated to a metal plate having a thickness of 1.6 mm, the workability was poor.

  In Example 2 in which the blend ratio of the polycarbonate-based resin was 50% by mass, the elongation at break after aging was further improved, and in Example 3 at 65% by mass, the rupture elongation after aging was also good. In the metal plate laminated with these, good workability was obtained even when a metal plate having a thickness of 1.6 mm was used.

  The dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, and the diol component is composed of 25 mol% or more and less than 50 mol% of 1.4-cyclohexanedimethanol and 50 mol% or more and less than 75 mol% of ethylene glycol. In the aromatic polyester resin (PETG6763), the compatibility with the aromatic polycarbonate resin (Novalex 7025A) is not so good, and in the composition range in which the polyester resin accounts for 60% by mass or more in the blend composition, Compared to the case where the polyester resin is used alone, it is considered that a great improvement in physical properties cannot be expected.

  Example 4 is a case where the second resin layer 20 corresponding to claim 1 of the present invention is used, but the second resin layer 20 has a good value of tensile elongation at break after aging, and is a laminated sheet. A good result is also obtained in the bending workability of the metal plate coated with aging.

  However, some embossing return occurred during the lamination, and this seems to be caused by the low glass transition temperature of the polyester resin of the second resin layer as in Comparative Example 1. Even in elevator applications, there is a possibility that a problem arises when a relatively thick 1.2 mm or 1.6 mm metal plate is used.

  Examples 5 to 9 are cases in which a blend composition of PCTG5445 and an aromatic polycarbonate resin (Novalex 7025A) was used as the second resin layer 20. In these second resin layers 20, the dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, the diol component is 50 mol% or more and less than 75 mol% 1.4-cyclohexanedimethanol, and 25 mol% or more. It consists of the blend composition of the aromatic polyester-type resin which consists of less than 50 mol% ethylene glycol, and an aromatic polycarbonate-type resin. Since the polyester resin is excellent in compatibility with the aromatic polycarbonate resin, it is known that a composition having a single glass transition temperature can be obtained at any blend ratio.

  However, in Example 5 in which the blend ratio of the aromatic polycarbonate-based resin is 25% by mass, there is no significant difference in emboss return at the time of lamination compared to Example 4. In Examples 6 to 9 in which the blend ratio is 35% by mass or more, a good appearance without emboss return is obtained. As the blend ratio of the aromatic polycarbonate resin increased, the initial value of tensile elongation at break decreased, but in Example 9, there was no problem in workability.

  In Example 10, only the aromatic polycarbonate resin (Novalex 7025A) was used for the second resin layer 20. Since the glass transition temperature is high (Tg = 149.5 ° C), there is no problem with the embossing heat resistance during lamination, but fine cracking occurs when the laminated sheet is laminated on a 1.6 mm thick steel sheet. Whitening that seems to be caused by the occurrence of.

  Example 11 is a case where an acrylic resin having a breaking elongation close to 350% is used as the first resin layer 10, and since the flexibility thereof is high, some sheet elongation occurs when the sheet is heated in an embossing machine. In addition, the surface hardness of the metal plate coated with the laminated sheet is somewhat low.

  Examples 12 to 14 use the first resin layer 10 having the tensile elongation at break specified by the present invention in the same manner as Example 8, and good performance is obtained.

  Example 15 is a case where an acrylic resin having a tensile elongation at break of about 120% is used as the first resin layer 10, and when the same second resin layer 20 as in Example 8 is used, the thickness is 1.6 mm. The bending workability when laminated on a metal plate is slightly reduced.

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the invention is limited to the embodiments disclosed herein. Rather, the laminated sheet for design coating and the laminated sheet-coated metal plate can be appropriately changed without departing from the spirit or idea of the invention that can be read from the claims and the entire specification. Should be understood as being included in the technical scope of

It is a schematic diagram which shows the cross section of the lamination sheet of the basic composition of this invention. It is a schematic diagram which shows the lamination sheet cross section of the structure by which the printed pattern is provided between the 1st resin layer and the 2nd resin layer in addition to the structure of Fig.1 (a). It is a schematic diagram which shows the cross section of the lamination sheet by which the embossing pattern was provided to the 2nd resin layer side surface of the lamination sheet of FIG.1 (b). In the structure of Fig.1 (a), it is a schematic diagram which shows the cross section of the lamination sheet which provided the adhesive bond layer or the adhesive resin layer between the 1st resin layer and the 2nd resin layer. It is a schematic diagram which shows the cross section of the lamination sheet coating | coated metal plate with which the lamination sheet of the structure shown in FIG.1 (c) is laminated | stacked on the metal plate via the adhesive agent. It is a figure which shows the relationship between a blend ratio and a glass transition temperature (Tg) at the time of blending a polyester-type resin (PCTG type | system | group) and an aromatic polycarbonate-type resin (PC). It is a schematic diagram of an embossing machine.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Heating roll 2 Take off roll 3 Infrared heater 4 Nip roll 5 Embossing roll 6 Cooling roll 7 Sheet material 10 First resin layer 20 Second resin layer 30 Printing layer 40 Adhesive layer 50 Adhesive layer 60 Metal plate 100 Embossing machine 110 , 120, 130, 140 Laminated sheet 150 Laminated sheet coated metal plate

Claims (13)

A first resin layer mainly composed of an acrylic resin containing a core-shell type acrylic cross-linked elastic component;
The main component is an aromatic polyester resin in which the dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, and the diol component is 50 to 75 mol% of 1.4-cyclohexanedimethanol and 25 to 50 mol% of ethylene glycol. A second resin layer, and
The tensile breaking elongation at 23 ° C. of the first resin layer is 120 to 350%, and the tensile breaking elongation at 23 ° C. after leaving the second resin layer in an environment of 40 ° C. × 90% RH for 30 days. A laminate sheet for designable coating, characterized by being 120% or more. A first resin layer mainly composed of an acrylic resin containing a core-shell type acrylic cross-linked elastic component;
A second resin layer comprising as a main component an aromatic polycarbonate resin or a blend composition of a polyester resin and an aromatic polycarbonate resin,
The tensile breaking elongation at 23 ° C. of the first resin layer is 120 to 350%, and the tensile breaking elongation at 23 ° C. after leaving the second resin layer in an environment of 40 ° C. × 90% RH for 30 days. A laminate sheet for designable coating, characterized by being 120% or more.   The polyester resin in the blend composition is such that the dicarboxylic acid component of the resin is terephthalic acid or dimethyl terephthalic acid, and the diol component is 50 to 75 mol% of 1.4-cyclohexanedimethanol and 25 to 50 mol. The laminated sheet for designable coating according to claim 2, wherein the laminate sheet is an aromatic polyester-based resin composed of% ethylene glycol.   The laminated sheet for designable coating according to claim 2 or 3, wherein the aromatic polycarbonate resin in the blend composition is 25% by mass or more based on the total amount of the blend composition.   The polyester resin in the blend composition is such that the dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, the diol component is 25-50 mol% of 1.4-cyclohexanedimethanol, and 50-75 mol% of ethylene glycol. The blend composition is a blend composition of less than 55% by mass of the aromatic polyester resin and 45% by mass or more of an aromatic polycarbonate resin. 2. The laminate sheet for designable coating according to 2.   The laminated sheet for designable coating according to any one of claims 1 to 5, wherein the first resin layer has a colorant and the second resin layer is transparent.   The laminated sheet for design-covering according to any one of claims 1 to 6, wherein a printed layer is provided between the first resin layer and the second resin layer.   It has the uneven | corrugated shape formed by the embossing plate in said 2nd resin layer side surface, The laminated sheet for designable coating | covering in any one of Claims 1-7 characterized by the above-mentioned.   A laminated sheet-coated metal plate laminated on a metal plate with an adhesive using the first resin layer side of the laminated sheet for designable coating according to any one of claims 1 to 8 as an adhesive surface.   An elevator interior material using the laminated sheet-coated metal plate according to claim 9.   A steel furniture member using the laminated sheet-coated metal plate according to claim 9.   A home appliance housing member using the laminated sheet-coated metal plate according to claim 9.   A building interior material using the laminated sheet-coated metal plate according to claim 9.

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