JP2007045067A - Laminated sheet for designed coating and metal sheet coated with laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide laminated sheets for designed coatings in which variously colored sheets can be efficiently obtained by a calendaring film forming method and good embossed patterns can be imparted by the conventionally used embossing machine, and to provide a laminated sheet-coated metal sheet which is fabricated by covering with this laminated sheet and excellent in the balance of surface hardness and processability. <P>SOLUTION: The laminated sheet 100 for the designed coating comprises at least two layers of a first resin layer 10 and a second resin layer 20. The first resin layer is one composed mainly of an acrylic resin and having a storage modulus, in terms of the frequency of 10 Hz by the dynamic viscoelasticity tension method, of ≥5.0×10<SP>7</SP>Pa and ≤5.0×10<SP>8</SP>Pa at 60°C and ≥1.0×10<SP>6</SP>Pa and ≤1.0×10<SP>7</SP>Pa at 130°C. The second resin layer is one composed mainly of a substantially amorphous polyester resin or one composed mainly of an aromatic polycarbonate resin or one composed mainly of a blend composition of these. <P>COPYRIGHT: (C)2007,JPO&INPIT

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, the present invention relates to a laminated sheet-covered metal plate that can be suitably used for curtain rails, entrance doors, elevator interior materials, building interior materials, and steel furniture, and a design-covered laminated sheet for forming the same.

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 the 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.
In addition to this, in addition to this, the soft PVC sheet has very good calendering properties, and various additive compositions and various color sheets can be efficiently produced in small lots. Is also a big attraction.

  As a method for continuously embossing the long sheet of soft PVC, the sheet after film formation is softened by reheating and pressed with a roll engraved with an embossed pattern (hereinafter referred to as “embossed plate roll”). Thus, a method of continuously transferring the pattern is generally performed. Here, as a method for heating the sheet, a contact type in which the sheet is brought into contact with a heated metal roll, a non-contact type in which the sheet is heated without being brought into contact with the roll by an infrared heater, a hot air heater, or the like. There is. In an actual production line, only one of them may be used, but generally 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 replace and remove the embossing plate roll. In addition, since the diameter of the embossing plate roll is smaller than the casting roll of the extrusion film forming equipment, it is possible to easily and economically change the embossed pattern by preparing various embossing plate rolls. it can. 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 When manufacturing this flexible PVC laminated sheet, the sheet preheating in the embossing machine can be used to laminate and integrate two layers of sheets by heat fusion, requiring a special process for lamination Therefore, the productivity was good and the cost was excellent.

  However, in recent years, the use of the above-mentioned flexible PVC sheet has been limited due to problems such as VOC (Volatile Organic Components), endocrine disrupting action, and generation of 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.

  As an alternative material, a sheet made of a polyolefin resin was first studied from the viewpoint of cost. However, a polyolefin resin has a problem that a bent portion is whitened when it is bent as a resin-coated metal plate. In addition, when using a formulation that lowers the crystallinity to solve this problem, the surface hardness is low, and scratch resistance is a problem in applications such as entrance doors and elevator inner layer materials that are often 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.

  As a substitute for the soft PVC sheet, a soft acrylic resin to which a rubber component is added has been studied. Patent Document 2 proposes to use, as a transparent surface layer and a colored substrate layer, an acrylic sheet softened by adding a cross-linked elastic body component so that bending can be performed.

Patent Document 3 proposes coating a base resin sheet made of an acrylic resin with a transparent resin layer made of a polyester resin. Patent Document 4 also discloses a base material sheet made of a colored acrylic resin. A decorative sheet having a structure in which a transparent protective layer made of an amorphous polyethylene terephthalate resin is coated has been proposed.
JP 2003-145702 A JP 2004-142164 A JP 2000-094596 A JP 2000-301681 A

  However, the object of the invention of Patent Document 1 is to ensure surface hardness and impact resistance, and to prevent bending whitening of the processed portion of the base material layer made of polyethylene resin when the resin-coated metal plate is bent. Until is not considered. 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.

  Furthermore, in the configuration disclosed in Patent Document 2, it is difficult to achieve both surface hardness and workability as a resin-coated metal plate, and there is a problem in workability when the surface hardness is high in order to ensure scratch resistance. The reverse problem occurs in order to ensure workability. 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.

  The object of the invention of Patent Document 3 is to obtain a laminated sheet with good vacuum formability, and since a relatively hard acrylic resin is used, the processability as a resin-coated metal plate is sufficient. In addition, there is no description about a technical idea that can deal with a small lot by imparting a calendering property to an acrylic resin.

  Regarding Patent Document 4 as well, although mention is made of vacuum formability and V-cut processability, which is a processing method of a wood board decorative board, there is no description regarding physical properties that an acrylic resin should have in order to secure it, There is no description of the technical idea of imparting calendar film-forming properties to the acrylic resin.

  Therefore, the present invention is capable of efficiently obtaining sheets of various colors by the calendar film forming method, and can be imparted with a good embossed pattern by using a conventionally used embossing machine. It is an object of the present invention to provide a laminated sheet for coating, and a laminated sheet-coated metal plate that is produced by coating the laminated sheet and has an excellent balance between surface hardness and workability.

  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 mainly composed of an acrylic resin, and the storage elastic modulus at a frequency of 10 Hz in the dynamic viscoelastic tension method is 5.0 × 10 ⁷ Pa or more and 5.0 × 10 ^{8 at} 60 ° C. A first resin layer (10) having a Pa or lower and a temperature of 130 ° C. of 1.0 × 10 ⁶ Pa or more and 1.0 × 10 ⁷ Pa or less, and a substantially amorphous polyester resin. This is a laminated sheet for design coating (100) having a second resin layer (20) as a main component and having a total thickness in the range of 60 to 300 μm.

  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).

  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.

  In the first aspect of the present invention, in the polyester resin which is substantially amorphous in the second resin layer (20), the dicarboxylic acid component is terephthalic acid or dimethylterephthalic acid, and 25 to 75 mol% of the diol component is present. It is preferable that it is an aromatic polyester-type resin whose 75-25 mol% is ethylene glycol with 1.4-cyclohexanedimethanol.

The second aspect of the present invention comprises an acrylic resin as a main component, and a storage elastic modulus at a frequency of 10 Hz in a dynamic viscoelastic tension method is 5.0 × 10 ⁷ Pa or more and 5.0 × 10 ^{8 at} 60 ° C. A first resin layer (10) that is not higher than Pa and is 1.0 × 10 ⁶ Pa or higher and 1.0 × 10 ⁷ Pa or lower at 130 ° C., and a substantially amorphous polyester-based resin; A laminate sheet for design coating (100) having a second resin layer (20) mainly composed of a blend composition with an aromatic polycarbonate resin and having a total thickness in the range of 60 to 300 μm.

  In the second aspect of the present invention, the polyester resin that is substantially amorphous in the second resin layer (20) has a dicarboxylic acid component of terephthalic acid or dimethylterephthalic acid, and 50 to 75 mol% of the diol component. It is preferable that it is an aromatic polyester-type resin which is 1.5-cyclohexanedimethanol and 50-25 mol% is ethylene glycol.

The third aspect of the present invention is mainly composed of an acrylic resin, and the storage elastic modulus at a frequency of 10 Hz in the dynamic viscoelastic tension method is 5.0 × 10 ⁷ Pa or more and 5.0 × 10 ^{8 at} 60 ° C. The second resin layer is composed mainly of a first resin layer (10) that is not higher than Pa and that is 1.0 × 10 ⁶ Pa or higher and 1.0 × 10 ⁷ Pa or lower at 130 ° C. and an aromatic polycarbonate resin. It is a laminated sheet for design coating (100) having a resin layer (20) and having a total thickness in the range of 60 to 300 μm.

  In the first to third inventions, the acrylic resin is preferably an acrylic resin containing a core-shell type acrylic cross-linked elastic component. Moreover, in 1st-3rd this invention, it is preferable that a 1st resin layer (10) contains a coloring agent and a 2nd resin layer (20) is transparent.

  In the first to third inventions, a printing layer (30) may be provided between the first resin layer (10) and the second resin layer (20). Moreover, in 1st-3rd this invention, you may have the uneven | corrugated shape formed in the 2nd resin layer (20) side surface by the embossing plate.

  4th this invention has the metal plate (60) by which the 1st resin layer (10) side of this designable coating laminated sheet (100) and this designable coating laminated sheet was affixed with the adhesive agent. A laminated sheet-coated metal plate (200).

  The fifth aspect of the present invention is a curtain rail using the laminated sheet-coated metal plate (200). 6th this invention is an entrance door using said laminated sheet coating metal plate (200). 7th this invention is an elevator interior material using said laminated sheet covering metal plate (200). The eighth aspect of the present invention is a building interior material using the laminated sheet-coated metal plate (200).

  In the laminated sheet for designable coating (100) of the present invention, the first resin layer (10) is mainly composed of an acrylic resin and has dynamic viscoelasticity characteristics in a specific range. Excellent film formability and flexibility at room temperature. Moreover, since the 1st resin layer (10) has acrylic resin as a main component, it is excellent in coloring property. Moreover, the 1st resin layer (10) is excellent in adhesiveness with the 2nd resin layer (20) and a metal plate (60). Due to these features, according to the laminated sheet for designable coating (100) of the present invention, laminated sheets of various colors can be easily obtained in a small lot.

  In the first aspect of the present invention, since the second resin layer (20) is a layer mainly composed of a polyester resin that is substantially amorphous, the laminated sheet (100) of the present invention has a surface Excellent in hardness and good transferability of embossed pattern by embossing machine. 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.

  In 2nd this invention, the 2nd resin layer (20) is made into the layer which has as a main component the blend composition of a polyester-type resin and an aromatic polycarbonate-type resin as a 2nd resin layer (20). The glass transition temperature of the constituent resin can be increased. As a result, the embossing heat resistance of the embossed pattern imparted to the second resin layer (20) can be increased. Therefore, when the metal plate (60) heated at the time of lamination to the metal plate (60) is in contact with the metal plate (60), it is possible to make the embossed pattern remaining better. Furthermore, even when a test that comes into contact with high-temperature water such as a boiling water immersion test is included as a standard test as in a unit bath application, the embossed pattern remaining after the test can be made favorable.

  In 3rd this invention, the heat resistance of the embossed pattern provided to the 2nd resin layer (20) is still higher by making the 2nd resin layer (20) into a layer which has an aromatic polycarbonate-type resin as a main component. Can be.

  Hereinafter, the present invention will be described based on embodiments shown in the drawings.

  The laminated sheet for designable coating and the laminated sheet-coated metal plate of the present invention will be described below with reference to the drawings as appropriate.

  The basic structure of the laminated sheet for designable coating 100 of the present invention is schematically shown in FIG. The laminate sheet for designable coating 100 of the present invention is composed of at least two layers of a first resin layer 10 and a second resin layer 20. Hereinafter, each layer will be described.

<First resin layer 10>
The first resin layer 10 is mainly composed of an acrylic resin, and the storage elastic modulus at a frequency of 10 Hz in the dynamic viscoelastic tension method is 5.0 × 10 ⁷ Pa or more at 60 ° C. 0 × 10 ⁸ Pa or less, and at 130 ° C., 1.0 × 10 ⁶ Pa or more and 1.0 × 10 ⁷ Pa or less.

  When the storage elastic modulus at 60 ° C. is too high, the workability at normal temperature of the laminated sheet-covered metal plate 200 coated with the laminated sheet 100 tends to be insufficient. Further, when the storage elastic modulus at 60 ° C. is too low, the flexibility of the sheet becomes excessive, causing a problem in the handleability of the first resin layer 10 alone. Moreover, also in the lamination sheet 100 which laminated | stacked the 2nd resin layer 20, it becomes difficult to obtain the surface damage property.

  In addition, the workability at room temperature is defined by the storage elastic modulus at a frequency of 10 Hz at 60 ° C., because secondary processing such as bending of the laminated sheet-coated metal plate 200 is relatively slow such as roll forming or hydraulic bender. This is because there is a correlation between the storage elastic modulus at around 60 ° C. of 10 Hz.

  On the other hand, when the storage elastic modulus at 130 ° C. is too high, the load at the time of calendering tends to be excessive. On the other hand, when the storage elastic modulus at 130 ° C. is too low, troubles such as sheet breakage are likely to occur during calender film formation due to insufficient melt tension of the sheet, and it becomes difficult to obtain a sheet having a uniform thickness. In addition, although the resin temperature at the time of film forming with an actual calender roll becomes higher than 130 degreeC, calender film formability can be judged from the storage elastic modulus in 130 degreeC.

The “acrylic resin” constituting the first resin layer 10 is mainly composed of a polymer obtained by polymerizing a single composition or a plurality of compositions of an acrylic monomer represented by the following general formula (1). This includes things.
_{^{CH 2 = CR 1 -COOR 2 (}} 1)

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, as the acrylic resin in the first resin layer 10, an acrylic resin 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. Moreover, it is preferable to use a block copolymer type flexible acrylic resin having butyl acrylate or the like as a soft segment and methyl methacrylate or the like as a hard segment, and having a glass transition temperature derived from the hard segment of 85 ° C. or higher. it can.

  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.

  The acrylic resin constituting the first resin layer 10 is preferably an acrylic resin containing a crosslinked elastic body component.

  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, in order to obtain the storage elastic modulus range that the first resin layer 10 should have, it is often necessary to add a relatively large amount of the cross-linked elastic body component. It is preferable to use an “acrylic cross-linked elastic body component” that is excellent in compatibility with a resin and hardly causes bending whitening.

  “Acrylic cross-linked elastic component” is a multi-stage polymerization on a cross-linked acrylic rubber phase, graft polymerization of an acrylic composition to obtain compatibility with the matrix and graft onto the acrylic rubber phase. A phase is formed.

  Examples of the acrylic resin used for the crosslinked acrylic rubber phase include a polymer having an alkyl ester having 1 to 8 carbon atoms as a monomer. Moreover, in order to make workability at low temperature favorable, it is preferable that the main component is an acrylic resin having a glass transition temperature lower than 0 ° C., and has 4 carbon atoms such as butyl acrylate and 2-ethylhexyl acrylate. Polymers having ˜8 monomers as monomers are preferred. Further, as other vinyl monomer components copolymerizable with the above monomers, methacrylic acid esters such as methyl methacrylate and butyl methacrylate, aromatic vinyl compounds such as styrene, vinylcyan compounds such as acrylonitrile, and the like Copolymerized copolymers can also be used.

  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, 1 .Use of unsaturated carboxylic acid diesters of glycols such as 3-butylene glycol dimethacrylate, 1.4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, polyvinylbenzene such as divinylbenzene and trivinylbenzene, etc. it can.

  The crosslinked acrylic rubber phase is graft-polymerized with an acrylic composition for the purpose of improving the compatibility with the matrix resin, thereby forming a graft phase. An acrylic composition is a composition comprising a monomer mainly composed of a methacrylic acid ester. Here, “mainly” means containing 50 mol% or more, preferably 60 mol% or more of a methacrylic acid ester based on the whole acrylic composition (100% by mass).

  Examples of the methacrylic acid ester that is the main monomer that forms a graft phase by graft polymerization include alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate. It is done. Examples of the copolymer component that is copolymerized with the alkyl ester of methacrylic acid contained in the acrylic composition include acrylic acid ester components such as methyl acrylate, ethyl acrylate, and butyl acrylate, and aromatics such as styrene. Group vinyl compounds or vinylcyan compounds such as acrylonitrile.

  The acrylic cross-linked elastic component having the above basic structure is referred to as a core / shell type acrylic cross-linked elastic component, 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 component is commercially available in various grades with names such as “soft acrylic”, “soft acrylic”, and “flexible acrylic”. In the present invention, these can be preferably used. 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-links, etc., as long as bending whitening, weather resistance, heat resistance, etc. are not a problem. You may use an elastic body component etc. together.

  When the acrylic resin containing a relatively large amount of such a crosslinked elastic body component is used for the first resin layer 10 of the present invention, it is easy to obtain the storage elastic modulus at the predetermined 130 ° C. according to the present invention. The release property of the resin layer 10 from the metal roll is good, and the risk of sticking to the calendar roll is reduced without special measures for the lubricant or the like. Thus, by making the acrylic resin which comprises the 1st resin layer 10 into the acrylic resin containing a crosslinked elastic body component, what is suitable for forming the 1st resin layer 10 into a film by the calendering method The first resin layer 10 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.

  The storage elastic modulus at a predetermined 60 ° C. in the present invention is such that, for example, a plasticizer is added to the acrylic resin forming the first resin layer 10, or an acrylic ester-based resin such as butyl acrylate is used as the acrylic resin. This can be ensured by using a monomer having a high copolymerization ratio or using a block type acrylic elastomer.

  When the acrylic resin containing the above-mentioned core / shell type acrylic cross-linked elastic body component is used, the storage modulus at 130 ° C. is set within a predetermined range, the calendar suitability is improved, and the boiling water is obtained. Good processing on the laminated sheet-coated metal plate while imparting immersion properties (preventing flow deformation of the first resin layer 10 itself) and preserving the storage elastic modulus of the first resin layer 10 at 60 ° C. Sex can be imparted. Therefore, these effects can be achieved.

  When the first resin layer 10 is provided with design properties by various colors, the visual concealment effect of the base material covered with the laminated sheet such as the metal plate 60, and the printing layer 30 described below, A colorant can be added for the purpose of improving color development. 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 hiding properties, the thinner the first resin layer 10 is, the greater the required amount of pigment added. 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. Moreover, 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 100 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. One guideline is JIS K5600-4-1: 1999 (paint coating general test method-Part 4: Visual characteristics of paint 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 100 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 lubricants may be added to the first resin layer 10 for the purpose of improving the calendering property. Since the first resin layer 10 has a storage elastic modulus in the range specified in the present invention, a good melt tension at the time of calendering can be obtained, but release from the roll by adding a lubricant By improving the property, the calendar suitability can be further improved.

  As a lubricant to be added, a conventionally used lubricant may be used. Fatty acid-based lubricants such as stearic acid and montanic acid, metal soap-based lubricants such as calcium stearate, fatty acid ester-based lubricants, polyolefin waxes and acid-modified polyolefin waxes -Various things, such as hydrocarbon-type lubricants, such as paraffin wax, an acrylic polymer lubricant, can be mentioned.

  Among them, an acrylic polymer lubricant having high thermal stability and a long-lasting sliding effect is preferable, and “Methbrene L-1000” manufactured by Mitsubishi Rayon Co., Ltd. can be used. Alternatively, an acrylic polymer lubricant and another lubricant may be used in combination.

  The addition amount of the lubricant may be a general amount of about 0.2 to 3% by mass based on all resin components forming the first resin layer 10 (100% by mass). Further, as conventionally performed, the addition amount can be appropriately adjusted depending on the resin temperature during film formation in the calendar device, the set thickness of the first resin layer 10, and the like.

  Further, the first resin layer 10 includes a linear ultra-high molecular weight acrylic resin (for example, “Metblene P-531” manufactured by Mitsubishi Rayon Co., Ltd.) for improving the melt tension at the time of calendering. , Processing aids such as polytetrafluoroethylene that has been subjected to an easy dispersion treatment that develops into fibrils (for example, “Metblene A-3000” manufactured by Mitsubishi Rayon Co., Ltd.), gelation accelerator, bank shape improvement, Additives added for the purpose of improving the flow mark may be added.

  In addition, various additives other than those described above may be added in appropriate amounts to the first resin layer 10 as long as the properties are not impaired. As additives other than the above, various antioxidants such as phosphorus and phenol, process stabilizers such as lactone and phenol acrylate, heat stabilizer, ultraviolet absorber, hindered amine radical scavenger, impact modifier, Examples of additives commonly added to resin materials, such as various processing aids, metal deactivators, antibacterial and antifungal agents, antistatic agents, flame retardants, pigment dispersibility improvers, fillers and extenders it can.

  There is no restriction | limiting in particular as the film forming method of the 1st resin layer 10, Extrusion film forming methods, such as a calender film forming method, a T-die film forming method, and an inflation method, a solvent cast method, etc. can be mentioned. Among these, since the first resin layer 10 of the present invention has a storage elastic modulus in a specific range, a good calender film forming property can be obtained. It is particularly preferable to form a film.

  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 100 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>
By laminating the second resin layer 20 on the relatively soft first resin layer 10, it is possible to impart surface scratch resistance to the laminated sheet of the present invention. Further, when the first resin layer 10 contains a large amount of an acrylic cross-linked elastic body component, it is inferior in embossing suitability (transferability), and therefore, by laminating the second resin layer 20, The laminated sheet 100 can have excellent emboss transferability. Further, there is an effect of protecting the printing layer 30 described below.

  The second resin layer 20 in the laminated sheet for designable coating 100 of the first aspect of the present invention is a layer mainly composed of a polyester resin that is substantially amorphous. Moreover, in the laminated sheet 100 for designable coatings according to the first aspect of the present invention, the second resin layer 20 has a dicarboxylic acid component of terephthalic acid or dimethyl terephthalic acid, and a diol component of 25 to 25 in order to achieve the above effects. A layer mainly composed of a substantially amorphous aromatic polyester resin in which 75 mol% is 1.4-cyclohexanedimethanol and 75 to 25 mol% is ethylene glycol is preferable. Such aromatic polyester-based resins are mass-produced on a commercial basis, can use raw materials that can obtain a stable supply, and can enjoy merit in price.

  If the ratio of 1.4-cyclohexanedimethanol in the diol component is too small, the properties as a crystalline resin become remarkable, and crystallization may progress during heating with an embossing machine, which may reduce embossing suitability, There is a possibility that workability as a laminated sheet-coated metal plate may be lowered. Conversely, when the proportion of 1.4-cyclohexanedimethanol in the diol component is too large, the characteristics as a crystalline resin become remarkable, and the same problem may occur.

  As the polyester resin in the above composition range, Eastman Chemical whose dicarboxylic acid component is terephthalic acid and whose diol component is about 30 mol% of 1.4-cyclohexanedimethanol and about 70 mol% of ethylene glycol. -It can be obtained commercially as "Easter PETG 6673" from Company.

  In addition to this, the substantially amorphous polyester is neopentyl glycol copolymerized PET, and its crystallinity does not affect the embossing suitability in the embossing machine, and the processability as the laminated sheet-coated metal plate 200 Those that do not cause a decrease in the viscosity, polyethylene terephthalate copolymerized with isophthalic acid, and polybutylene terephthalate having the same properties can also be used as the resin component of the second resin layer 20.

  The second resin layer 20 in the laminate sheet for designable coating 100 of the second aspect of the present invention is a layer mainly composed of a blend composition of a substantially amorphous polyester resin and an aromatic polycarbonate resin. It is. By mixing the aromatic polycarbonate resin, the glass transition temperature rises, and the emboss return when laminating to the metal plate 60 can be reduced. Also, as a standard test, it is immersed in boiling water as a unit bath. Even when a test such as a test that comes into contact with high-temperature water is included, the embossed pattern remaining after the test can be made favorable.

  Moreover, when using said blend composition as a main component in the 2nd resin layer 20 in the lamination sheet 100 for the designable coating | cover of 2nd this invention, as polyester-type resin contained in this blend composition, it is dicarboxylic. Amorphous aromatic polyester resin in which the acid component is terephthalic acid or dimethylterephthalic acid, 50 to 75 mol% or more of the diol component is 1.4-cyclohexanedimethanol, and 50 to 25 mol% is ethylene glycol. Is preferably used. Such a polyester resin is preferable because it is excellent in compatibility with an aromatic polycarbonate resin and can take any blend ratio. Moreover, the effect of improving the heat resistance of embossing in the blend composition is remarkable, and since it is mass-produced on a commercial basis, a stable supply can be obtained and there is a merit in terms of price. Examples of the polyester resin having such a composition range include “PCTG 5445” manufactured by Eastman Chemical Company. In addition, when there is too much quantity of 1.4-cyclohexane dimethanol in a diol component, the influence of crystallinity will become remarkable.

  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 break elongation of the sheet made of the blend composition becomes relatively small, and processing is performed when a relatively thick metal plate is used for elevator applications. There may be a lack of sex.

  As the polyester resin contained in the blend composition, the dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, 25 to 50 mol% of the diol component is 1.4-cyclohexanedimethanol, and 75 to 50 mol% is ethylene. You may use the aromatic polyester-type resin which is glycol. However, such an aromatic polyester resin is somewhat compatible with an aromatic polycarbonate resin compared to an aromatic polyester resin in which 50 mol% or more of the diol component is 1.4-cyclohexanedimethanol. Become inferior. As a result, depending on the state of kneading of the blend composition, only the sheet having a large haze (cloudiness value) may be obtained as the second resin layer 20, but this is particularly troublesome when the large haze is not a problem. Can be used. Examples of the resin having such a composition range include “Easter PETG 6763” manufactured by Eastman Chemical Company, Inc., and the use of this resin can provide a merit in cost.

  The aromatic polycarbonate-based resin that can be used in the blend composition is not particularly limited, but the most general-purpose bisphenol having the same molecular structure but using bisphenol A and phosgene as raw materials or not using phosgene. A-type 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 second resin layer 20 in the design-coated laminated sheet 100 of the third aspect of the present invention is a layer mainly composed of an aromatic polycarbonate resin. Since the aromatic polycarbonate resin has a high glass transition temperature, the heat resistance of the emboss can be improved as in the case of the second invention. Moreover, since the second resin layer 20 mainly composed of an aromatic polycarbonate resin is excellent in compatibility with various ultraviolet absorbers, when these are added, as a front door application, as a standard test Even when an accelerated weathering test of about 3000 hours using a sunshine weather meter is included, the light yellowing resistance of the second resin layer 20 after the test can be made good.

  The aromatic polycarbonate resin constituting the second resin layer 20 in the laminated laminate for designable coating 100 of the third invention is the same as the aromatic polycarbonate resin mentioned as the blend composition in the second invention. Can be used.

  Examples of ultraviolet absorbers that can be added to the second resin layer 20 include benzophenone-based, benzotriazole-based, triazine-based, and the like. A triazine-based material which has little volatilization and decomposition at the time and good weather stability per se can be preferably used. An example of such a triazine-based ultraviolet absorber is “Tinuvin 1577” manufactured by Ciba Specialty Chemicals. For example, when a triazine-based ultraviolet absorber is used, the addition amount of the ultraviolet absorber is in the range of 2 to 14% by mass based on the mass of the entire second resin layer 20 (100% by mass), and is necessary. It is adjusted according to the weather resistance level.

  The thickness of the second resin layer is preferably in the range of 15 to 150 μm, more preferably in the range of 20 to 100 μm, and particularly preferably in the range of 30 to 75 μm. 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. If the thickness of the second resin layer 20 is too thick, the first resin layer 10 is a layer mainly composed of an acrylic resin having good processability by defining the storage elastic modulus at 60 ° C. of the present invention. In spite of using, the workability at the time of setting it as a lamination sheet with the 2nd resin layer 20 will be inferior.

  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. As the additive for resin, the first resin other than the one that induces whitening at the bent portion when the laminated sheet-coated metal plate 200 is subjected to processing such as bending, or that may cause cracking. The same additives as those that can be used for the layer 10 can be used. In the polyester resin, a hydrolysis inhibitor such as a carbodiimide compound or an oxazoline compound, which is expected to be particularly effective, may be added. As such a hydrolysis inhibitor, those commercially available from various companies can be used.

  The second resin layer 20 is preferably transparent. Regarding coloring, even when the printing layer 30 described below does not exist, the first resin layer 10 of the present invention is excellent in calendar film-forming properties, so that the first resin excellent in small lot compatibility with various colors. It is preferable that the second resin layer 20 does not contain a pigment with high concealability, using the layer 10 as a colored layer.

  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 to add these additives to the second resin layer 20 so as not to hinder the color changeability in the extrusion film formation. Moreover, when adding an ultraviolet absorber to the 2nd resin layer 20, the 2nd resin layer 20 is made into 2 layer structure, an ultraviolet absorber is added to the resin layer of the surface layer side, and the lamination | stacking side with the 1st resin layer 10 An additive that expresses a glitter design or the like may be added to the resin layer.

<Print layer 30>
As shown schematically in FIG. 1B, the laminated sheet 100 of the present invention has a printing layer 30 between the first resin layer 10 and the second resin layer 20. Good. 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. Furthermore, a heat-fusible coat layer for making the first resin layer 10 and the second resin layer 20 have better heat-fusibility may be applied simultaneously in the printing process.

  The printing layer 30 may be formed on the surface of the first resin layer 10 on the side to be laminated with the second resin layer 20, and then laminated with the second resin layer 20 to form a laminated sheet 100b, or the second resin A so-called back print type printing layer 30 may be formed on the surface of the layer 20 on the side where the first resin layer 10 is laminated, and then laminated with the first resin layer 10 to form a laminated sheet 100b.

<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. 2 shows an embossing machine 300 that has been used to give an embossed pattern to a conventional 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 300 or the like. Is possible. Thus, laminating the first resin layer 10 and the second resin layer 20 is preferable in terms of cost because it does not increase the number of steps and the number of 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. In FIG.1 (c), the layer structure of the form which gave the embossed pattern to the 2nd resin layer 20 side in the laminated sheet 100 for the designable coating | cover with this invention which has the printing layer 30 was shown typically.

  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. FIG. 1D schematically shows the layer configuration in the case where the adhesive layer 40 is provided between the first resin layer 10 and the second resin layer 20.

  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. When the adhesive layer 40 is thinner than this, adhesion failure due to uneven application tends to occur, and when it is thicker than this, the workability of the laminated sheet 100 may be lowered. When the adhesive layer 40 is applied, the adhesive layer 40 may be colored with a transparent colorant such as a dye, a fluorescent agent, a bluish imparting agent, or the like in order to impart design properties. Further, surface-modified mica powder, aluminum fine powder, hologram foil or the like may be added. Furthermore, the adhesive layer 40 may contain appropriate amounts of various additives that are generally added to curable adhesives.

  Even when the printing layer 30 is provided between the first resin layer 10 and the second resin layer 20, the layers can be heat-sealed and laminated by appropriately selecting the binder resin of the printing ink. Alternatively, each layer can be heat-sealed and laminated by continuously applying an adhesive primer layer using a solid plate roll after applying a printing design layer on a printing line. 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 300 shown in FIG. 2, the sheet material wound and laminated on the heating roll 1 in the order of the first resin layer 10 and the second resin layer 20 passes through the take-off roll 2 and passes through the infrared ray. Predetermined processing is performed by the heater 3, and further, the nip roll 4, the emboss roll 5, and the cooling roll 6 are sent.

  The sheet material 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 laminated and preheated by the heating roll 1 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 to be embossed. An embossed pattern is imparted to the second resin layer 20 by the roll 5. Thereafter, the laminated sheet 100 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 100 shrinks in width, wrinkles, breaks, etc. Absent. Moreover, since the 2nd resin layer 20 has favorable emboss provision suitability, the lamination sheet 100 by which embossing of the favorable external appearance was given can be obtained.

<Laminated sheet 100>
The total thickness of the laminated sheet 100 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 conventionally used for forming a flexible PVC resin-coated metal plate such as a bending process. This is because the adaptability of the next processing equipment is reduced.

<Metal plate 60>
The laminated sheet-coated metal plate 200 of the present invention includes the above-described laminated sheet for design coating 100 of the present invention, and the metal plate 60 on which the first resin layer 10 side of the laminated sheet for design coating is bonded with an adhesive. Have. The laminated sheet-covered metal plate 200 of the present invention has good workability and scratch resistance, and can be produced in small lots for various colors and designs of embossed patterns and designs of printed patterns. Is. As the metal plate 60, hot-rolled steel plate, cold-rolled steel plate, hot-dip galvanized steel plate, electrogalvanized steel plate, tin-plated steel plate, various steel plates such as stainless steel plate, aluminum plate, aluminum alloy plate and the like 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-coated metal plate 200, but can be selected within a range of 0.1 to 10 mm. Usually, for interior building materials, a material having a thickness of about 0.40 to 0.60 mm is often used.

<Method for Producing Laminated Sheet-Coated Metal Plate 200>
The laminated sheet-coated metal plate 200 of the present invention can be manufactured by laminating the design-coated laminated sheet 100 of the present invention to the metal plate 60. FIG. 1 (e) schematically shows the layer structure of the laminated sheet-coated metal plate 200 of the present invention. Examples of the adhesive that forms the adhesive layer 50 used for laminating include heat generally used for the application such as acrylic adhesive, epoxy adhesive, urethane adhesive, and polyester adhesive. A curable adhesive can be mentioned. Moreover, since the 1st resin layer 10 is a layer which has acrylic resin as a main component, it is preferable from the point which obtains favorable adhesiveness among said adhesives using an acrylic adhesive.

  As a method of laminating the laminated sheet 100 to the metal plate 60, a metal surface on which the laminated sheet is laminated using the commonly used coating equipment such as reverse coater and kiss coater on the various metal plates 60 described above. Further, the adhesive is applied so that the thickness of the adhesive layer 50 after drying 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 100 becomes an adhesive surface, the laminated sheet 100 is bonded and cooled, whereby the laminated sheet-coated metal plate 200 of the present invention is cooled. Obtainable. When the laminated sheet 100 is coated on the metal plate 60, the embossing on the surface of the laminated sheet 100 becomes shallow due to heat transfer from the heated metal plate 60, so that cooling is performed by rapid cooling such as water cooling. It is preferable to do this.

<Use of laminated sheet-coated metal plate 200>
The laminated sheet-coated metal plate 200 of the present invention can be easily processed into various processed products such as curtain rails, entrance doors, elevator interior materials, building interior materials, steel furniture, and the like. Furthermore, the laminated sheet 100 for designable coating according to the present invention is coated with a wooden plate, an inorganic fiber plate, a thermoplastic resin plate, a thermosetting resin plate, etc. in addition to being used by coating the metal plate 60. It can use suitably for the purpose of raising.

  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 resin for forming the first resin layer 10 (a-1 to a-14), various commercially available acrylic raw materials whose types and amounts are listed in Table 1 were blended. A total of 100 parts by mass of the resin composition, 0.5 parts by mass of “Methbrene L-1000” (Mitsubishi Rayon Co., Ltd.) as a lubricant, and a light blue pigment in which titanium oxide and an organic dark blue pigment are mixed 16 parts by mass were 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 120 μm and a width. A 1200 mm light blue sheet was formed.

  Especially when a good calendered sheet with a thickness of 120 μm was obtained without any problem, “○”, although the film-forming conditions were finely adjusted due to some sheet elongation, adhesion to a heating roll, etc. When the calendered film sheet was obtained, “△”, when the sheet elongation was remarkable, or when a good sheet could not be obtained due to melt fracture, “x” was used to evaluate the calender film forming property. . The evaluation results are shown in Table 1. In addition, about what had a problem in film forming property, subsequent evaluation, such as lamination | stacking integration with a 2nd resin layer, is not implemented.

  For the first resin layer 10 that was able to be formed into a calender without any particular problem, a deep blue color was formed on the surface of the first resin layer 10 on the side laminated with the second resin layer 20 using an acrylic / urethane ink. The printed layer 30 was formed by printing an abstract pattern mainly composed of

In Table 1, “methabrene W-377” is an acrylic resin made by Mitsubishi Rayon Co., Ltd. containing a large amount of an acrylic crosslinked elastic body component.
“Metabrene H-660” is a polymethyl methacrylate (PMMA) resin that does not contain an acrylic cross-linked elastic body component manufactured by Mitsubishi Rayon Co., Ltd.
“Parapet SA” is a soft acrylic raw material containing an acrylic cross-linked elastic body component manufactured by Kuraray Co., Ltd., and substitutes soft PVC for injection molding applications.
“Parapet GR-F” is an acrylic resin containing an acrylic crosslinked elastic body component having flexibility suitable for overlay applications manufactured by Kuraray Co., Ltd.

<Film formation of the second resin layer 20>
As the second resin layer 20 (b-1 to b-9), various commercially available polyester resin materials and aromatic polycarbonate resin materials shown in Table 2 were used. Using these resins as raw materials, a T-die is connected to a single screw extruder with a vent of 65 mm in diameter, and the glass transition temperature (Tg) of each second resin layer 20 is 20 by an oil circulator or hot water circulator. A sheet having a thickness of 50 μm and a width of 1100 mm was obtained by taking-up with a mirror-casting roll maintained at a temperature as low as ˜30 ° C.

  In Table 2, “Easter PETG6763” is about 30 mol. Of ethylene glycol which is a diol component of polyethylene terephthalate manufactured by Eastman Chemical Company. % 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” is about 65 mol. Of ethylene glycol which is a diol component of polyethylene terephthalate manufactured by Eastman Chemical Company. % Is a low crystalline resin having a structure in which 1.4-cyclohexanedimethanol is substituted, and can be handled as substantially amorphous in the process of extrusion film formation and the process of embossing. Glass transition temperature is 86.5 ° C, melting point is not observed.

  “NOVALEX 7025A” is a bisphenol A type polycarbonate resin having a viscosity average molecular weight of 25,000 manufactured by Mitsubishi Engineering Plastics. 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 1-18, Comparative Examples 1-3)
The first resin layer 10 and the second resin layer 20 were combined as shown in Table 3. These combined resins are heat-bonded and integrated with the surface of the first resin layer 10 provided with the printed pattern 30 and the second resin layer 20 by the embossing machine 300 shown in FIG. The pattern was transferred. The heating roll 1 was set to 140 ° C., the first resin layer 10 and the second resin layer 20 were supplied from two unwinding shafts, and were integrated by heat fusion lamination at the contact portion with the heating roll 1. Subsequently, the laminated and integrated sheets are heated with a non-contact type infrared heater 3 until the sheet surface temperature reaches 180 ° C., and a textured embossed pattern is imparted 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 5 is maintained at 60 ° C. to 100 ° C. according to 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 100 was evaluated for embossing suitability (adhesion resistance, fusing resistance and transferability) by the method described below. The evaluation results are shown in Table 3.

(Comparative Examples 4 and 5)
In Comparative Example 4 and Comparative Example 5, the second resin layer 20 of the present invention was not laminated, and only the first resin layer 10 shown in Table 1 was used, and embossing suitability (adhesion resistance, Fusing resistance and transferability) were evaluated. Moreover, it attached | subjected to the coating to the metal plate 60 of the following process.

<Preparation of laminated sheet-coated metal plate 200>
Next, an acrylic thermosetting adhesive (manufactured by Mitsubishi Rayon Co., Ltd.) that is generally used for a polyvinyl chloride coated metal sheet is dried on the surface of a galvanized steel sheet having a thickness of 0.45 mm. Was applied with a roll coater so as to be about 2 to 4 μm. Next, the coated surface was dried and heated with a hot air heating furnace and an infrared heater, and the surface temperature of the galvanized steel sheet was set to 225 ° C. Then, immediately using the roll laminator, the laminated sheet 100 (partially, a single-layer sheet consisting only of the first resin layer 10) prepared above is coated, and cooled by water cooling to form the laminated sheet-coated metal plate 200. Produced. All examples and comparative examples were laminated under the same conditions. The obtained laminated sheet-coated metal plate 200 was evaluated by the following method. The results are shown in Table 3.

<Measurement standard, test method>
The following measurements and evaluations were performed on the single-layer sheet made of the first resin layer 10 produced above, the laminated sheet for design coating, and the laminated sheet-coated metal plate.

(1) Measurement of storage elastic modulus of first resin layer 10 The MD direction of the first resin layer 10 was measured with a viscoelastic spectrometer manufactured by Iwamoto Seisakusho. The measurement method was in accordance with the usual tensile method and temperature dispersion measurement, and the temperature was increased from −100 ° C. to 3 ° C./min. After measuring to 250 ° C., the storage elastic modulus at 60 ° C. and 130 ° C. was read. It was. In addition, about the composition of the 1st resin layer 10 for which the calendar film formation was difficult, the sample for storage elastic modulus measurement was obtained by kneading the same compound with an 8-inch test roll. These measurement results are shown in Table 1.

(2) Suitability for embossing: Adhesion resistance When embossing was applied with the embossing machine 300 shown in FIG. 2, the sheet adhered to the heating roll was indicated with “x”, and the one not adhered was indicated with “◯”. It was.

(3) Embossing suitability: Fusing resistance When the embossing is applied by the embossing machine 300 shown in FIG. 2, the sheet is blown out while the sheet is heated by a heater. Those marked with remarkable elongation or wrinkles were marked with “△”, and those without these problems were marked with “◯”.

(4) Embossing suitability: transferability The sheet embossed by the embossing machine 300 shown in FIG. 2 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.

(5) Embossing heat resistance: high temperature air heat resistance Embossing after leaving a metal plate laminated with a laminated sheet embossed by the embossing machine 300 shown in FIG. 2 in a hot air circulation oven at 105 ° C. for 3 hours Visually observe the change in the appearance of `` ○ '' if the shape of the emboss is almost unchanged compared to before putting it in the oven, `` △ '' if the embossed return is slightly compared to this The case where the embossed return is remarkable or the embossed pattern completely disappeared and the surface is simply rough is indicated by “x”.

  (6) Embossing heat resistance: Boiling water immersion

  The appearance change of the embossing after visually immersing the metal plate laminated with the embossed laminated sheet by the embossing machine 300 shown in FIG. 2 in boiling water for 3 hours is compared with that before immersing in boiling water. “○” indicates that the shape of the emboss is almost unchanged, “△” indicates that the embossed return has occurred slightly compared to this, and if the embossed return is noticeable or the embossed pattern disappears completely, it is simply the surface Are marked with "x".

(7) Workability test: Bending workability test 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”, the case where cracks occurred, and the case where significant bending whitening occurred was evaluated as “x”. FIG. 3 shows an outline of the screw bending tester used in this evaluation (FIG. 3 (a)) and an enlarged view of the test piece portion (FIG. 3 (b)).

  The bending test was performed as follows. First, samples of 50 mm × 150 mm are prepared from the length direction and the width direction of the laminated sheet-covered metal plate 200, respectively, and using a manual folding machine, the laminated sheet-covered surface is 180 degrees with an inner radius of 2 mm and the outer side. (Preliminary bending test piece 210 as shown in FIG. 3B) was produced.

  Using a screw bending test apparatus 400 as shown in FIG. 3A, contact bending (inner radius 0 mm) was performed on the test piece 210 that had been subjected to the preliminary bending. The screw bending test apparatus 400 includes a lower mold 440 and an upper mold 430. The upper mold 430 is provided at the lower end of the screw 420 that can move in the vertical direction, and the operation provided at the upper portion of the screw 420. The handle 410 is moved up and down manually. The test apparatus was placed in a room maintained at 23 ° C., and the measurement test piece 210 was subjected to preliminary bending and screw contact bending after being maintained at 23 ° C. for 1 hour or longer.

(8) Surface Hardness Test JIS K5600-5-4: 1999 (Paint General Test Method-Part 5: Mechanical Properties of Coating Film-Section 4) : Scratch hardness (pencil method)). In a constant temperature room of 23 ° C., use a jig that can draw a wire with a load of 9.8 N while maintaining an angle of 45 ° with respect to the resin sheet surface of the laminated sheet-coated metal plate 200 cut out to 80 mm × 60 mm. I did a line drawing. The surface state of the resin sheet of the part was visually determined, and “○” indicates that the 2B pencil was not scratched at all, and “2B” indicates that the scratch was entered, but 3B pencil did not scratch at all. “Δ” indicates that the 3B pencil was also scratched as “x”.

<Evaluation results>
Comparative Example 1 is a case where an acrylic resin having a storage modulus of 60 lower than the range of the present invention was used for the first resin layer, and there was no problem in workability of the laminated sheet-coated metal plate. The flexibility was excessive, and there was a problem in the handleability of the first resin layer alone, and at the same time, the surface hardness of the laminated sheet-coated metal plate was insufficient. In addition, the storage elastic modulus at 130 ° C. is close to the lower limit of the range of the present invention, and calendar film formation is possible, but the sheet melt tension at the time of film formation is slightly insufficient, and the laminated sheet is formed with an embossing machine. When heated, the sheet stretched somewhat.

  Comparative Example 2 and Comparative Example 3 are cases where the first resin layer made of an acrylic resin having a storage elastic modulus at 60 ° C. higher than the range of the present invention was used, and the workability of the laminated sheet-coated metal plate was poor. The result is satisfactory. Since the storage elastic modulus at 130 ° C. is within the range of the present invention, there was no problem in the calendering property.

  In Comparative Example 4, the first resin layer having a storage elastic modulus of 60 ° C. within the range of the present invention was embossed with an embossing machine without laminating the second resin layer, and then laminated to a metal plate. Although there was no sticking to the superheated roll with an embossing machine or significant elongation during heating at 180 ° C. by a heater, the transfer of the embossed pattern became very shallow. The sheet contains a large amount of an acrylic cross-linked elastic body component, so that the calendar film-forming property is good, but it appears as a feature that shows remarkable elastic recovery after embossing, It is thought that the transfer became shallow due to the so-called embossing return. Moreover, it is thought that the metal plate which coat | covered this 1st resin layer is low in surface hardness, and is not suitable for an interior building material or a semi-exterior building material use with many opportunities to touch.

  Comparative Example 5 is a case where the first resin layer made of an acrylic resin having a storage elastic modulus at 60 ° C. higher than the range of the present invention is used as a single layer for embossing and laminating. The transferability was bad. Further, in the case of the first resin layer single layer, the processability was insufficient, and furthermore, the surface hardness was only lower than that of the metal plate coated with the laminated sheet of the present invention.

  On the other hand, in Examples 1-18 in the range which this invention prescribes | regulates, the obtained lamination sheet and the lamination sheet covering metal plate showed the generally favorable performance. When each example is evaluated individually, Example 1 and Example 5 are cases where only a substantially amorphous polyester resin is used as the second resin layer, but when immersed in boiling water. The embossing heat resistance of is slightly worse.

  In Example 2, substantially 30 mol. Of ethylene glycol, which is a diol component of polyethylene terephthalate, was used as a substantially amorphous polyester resin. % Is a case where a blend composition of 65% by mass of an amorphous polyester resin having a structure substituted with 1.4-cyclohexanedimethanol and 35% by mass of an aromatic polycarbonate resin is used as the second resin layer. The embossing heat resistance after immersion in boiling water was the same as in Example 1. On the other hand, Example 3 and Example 4 are cases where the amorphous polyester resin having the composition is 50% by mass or less, but the immersion in boiling water is improved.

  In Example 6, as a substantially amorphous polyester-based resin, about 65 mol. Of ethylene glycol which is a diol component of polyethylene terephthalate was used. In the case where 65% by mass of an amorphous polyester resin having a structure in which% is replaced with 1.4-cyclohexanedimethanol is used and the second resin layer is used as a blend composition with an aromatic polycarbonate resin, The embossing heat resistance after water immersion is improved. This is because the amorphous polyester resin having the above composition is excellent in compatibility with the aromatic polycarbonate resin, so that a remarkable improvement effect can be obtained by adding a small amount of the aromatic polycarbonate resin. . Similarly, in Example 7 and Example 8, the emboss heat resistance after immersion in boiling water is improved.

  Although Example 9 is a case where only an aromatic polycarbonate resin is used as the resin component of the second resin layer, good results have been obtained regarding the embossing heat resistance after immersion in boiling water. Example 10 is a case where the storage elastic modulus at 130 ° C. of the first resin layer is close to the lower limit of the range of the present invention, and some sheet elongation or the like was caused during calendering, but embossing was applied. Similar results were obtained when heating in the machine.

  Example 12 and Example 18 are cases where the storage elastic modulus at 60 ° C. of the first resin layer is close to the upper limit of the range of the present invention, and fine whitening was observed in the bending workability test. May be restricted in use. In Example 13, the storage elastic modulus at 60 ° C. is close to the lower limit of the range of the present invention, and the surface hardness is somewhat low.

  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-covered metal plate, which can be appropriately changed within the scope not departing from the gist or concept of the invention that can be read from the claims and the entire specification, are also included in the present invention. Should be understood as being included in the technical scope of

FIG. 1A is a schematic diagram of a laminated sheet for design covering 100a having a basic configuration of the present invention, which is composed of a first resin layer 10 and a second resin layer 20. FIG. 1B is a schematic diagram of a laminated sheet 100 b in which a printing layer 30 is provided between the first resin layer 10 and the second resin layer 20. FIG.1 (c) is a schematic diagram of the laminated sheet 100c of the form which provided the embossed pattern on the surface at the side of the 2nd resin layer 20 of the laminated sheet of FIG.1 (b). FIG. 1D is a schematic view of a laminated sheet 100 d in which an adhesive layer 40 or an adhesive resin layer 40 is provided between the first resin layer 10 and the second resin layer 20. FIG. 1 (e) is a schematic view of a laminated sheet-covered metal plate 200 of the present invention in which the laminated sheet of FIG. 1 (c) is laminated on a metal plate 60 via an adhesive layer 50. 3 is a schematic diagram of an embossing machine 300. FIG. FIG. 3A is a schematic diagram showing an outline of the screw bending tester 400 used for the bending workability test. FIG. 3B is an enlarged view of the test piece portion 210 in the screw bending tester.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Laminated sheet for designable coatings 200 Laminated sheet covering metal plate 10 First resin layer 20 Second resin layer 30 Print layer 40 Adhesive layer, adhesive resin layer 50 Adhesive layer 60 Metal plate 300 Embossing machine 1 Heating roll 2 Take-off roll 3 Infrared heater 4 Nip roll 5 Emboss roll 6 Cooling roll 400 Screw bending tester 410 Upper mold lifting handle 420 Upper mold lifting screw 430 Upper mold 440 Lower mold 210 Test piece

Claims (14)

The main component is an acrylic resin, and the storage elastic modulus at a frequency of 10 Hz in the dynamic viscoelastic tension method is 5.0 × 10 ⁷ Pa or more and 5.0 × 10 ⁸ Pa or less at 60 ° C. and 130 A first resin layer that is 1.0 × 10 ⁶ Pa or more and 1.0 × 10 ⁷ Pa or less and a second resin layer mainly composed of a substantially amorphous polyester-based resin at And a laminated sheet for designable coating having a total thickness in the range of 60 to 300 μm.   The substantially amorphous polyester resin of the second resin layer is such that the dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, and 25 to 75 mol% of the diol component is 1.4-cyclohexanedimethanol, The laminated sheet for designable coating according to claim 1, which is an aromatic polyester resin in which 75 to 25 mol% is ethylene glycol. The main component is an acrylic resin, and the storage elastic modulus at a frequency of 10 Hz in the dynamic viscoelastic tension method is 5.0 × 10 ⁷ Pa or more and 5.0 × 10 ⁸ Pa or less at 60 ° C. and 130 A blend composition of a first resin layer that is 1.0 × 10 ⁶ Pa or more and 1.0 × 10 ⁷ Pa or less, and a substantially amorphous polyester-based resin and aromatic polycarbonate-based resin at ° C. A laminate sheet for covering with a design, which has a second resin layer containing as a main component and has a total thickness in the range of 60 to 300 μm.   The substantially amorphous polyester resin of the second resin layer is such that the dicarboxylic acid component is terephthalic acid or dimethyl terephthalic acid, and 50 to 75 mol% of the diol component is 1.4-cyclohexanedimethanol, The laminated sheet for designable coating according to claim 3, which is an aromatic polyester resin in which 50 to 25 mol% is ethylene glycol. The main component is an acrylic resin, and the storage elastic modulus at a frequency of 10 Hz in the dynamic viscoelastic tension method is 5.0 × 10 ⁷ Pa or more and 5.0 × 10 ⁸ Pa or less at 60 ° C. and 130 At 1 ° C., it has a first resin layer that is 1.0 × 10 ⁶ Pa or more and 1.0 × 10 ⁷ Pa or less, and a second resin layer mainly composed of an aromatic polycarbonate resin, and has a total thickness. A laminated sheet for designable coating that is in the range of 60 to 300 μm.   The laminated sheet for design coating according to any one of claims 1 to 5, wherein the acrylic resin is an acrylic resin containing a core-shell type acrylic cross-linked elastic body component.   The laminated sheet for designable coating according to any one of claims 1 to 6, wherein the first resin layer contains a colorant and the second resin layer is transparent.   The laminated sheet for designable coating according to any one of claims 1 to 7, comprising a printing layer between the first resin layer and the second resin layer.   The laminated sheet for designable coating according to any one of claims 1 to 8, which has an uneven shape formed by an embossed plate on the surface of the second resin layer.   A laminated sheet-covered metal plate comprising: the laminated sheet for designable coating according to any one of claims 1 to 9; and a metal plate having a first resin layer side of the laminated sheet for designable coating attached thereto with an adhesive.   A curtain rail using the laminated sheet-coated metal plate according to claim 10.   An entrance door using the laminated sheet-coated metal plate according to claim 10.   An elevator interior material using the laminated sheet-coated metal plate according to claim 10.   A building interior material using the laminated sheet-coated metal plate according to claim 10.

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