JP5290495B2 - Laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a calendered sheet, especially having excellent calenderability and excellent adhesion to a two-pack type urethane resin, allowing excellent adhesion of ink, and providing excellent transparency and whitening resistance; and to provide a sheet and a laminated sheet using the composition. <P>SOLUTION: The resin composition for the calendered sheet is obtained by compounding (A) 100 pts.wt. of a composition comprising (a) 50-99 mass% of a polyester-based resin having at least 5 min half crystallization time from a molten state, and (b) 1-50 mass% crosslinked product of a graft copolymer comprising a conjugated diene compound and an aromatic vinyl compound, with (c) 0.2-10 pts.mass of a 28-32C linear fatty acid and/or its derivative-based wax. The sheet and the laminated sheet are obtained by subjecting the composition to calendering. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a resin composition for a calendered sheet, a sheet using the same, and a laminated sheet. Specifically, the calendered sheet is excellent in calender moldability, in particular, adhesion to a two-component curable urethane resin, and ink adhesion. Further, the present invention relates to a resin composition for a calendered sheet having excellent transparency and whitening resistance, and a sheet and a laminate sheet using the same.

Conventionally, vinyl chloride resin films have been used in large amounts in decorative sheets used for furniture, doors, door frames, waistboards, baseboards, window frames, and other surface materials. The vinyl chloride resin decorative sheet is laminated on a heating drum of a doubling machine, with a transparent vinyl chloride resin film and a printed colored vinyl chloride resin film superimposed on each other and thermocompression bonded. It was manufactured by embossing. However, since vinyl chloride resin has problems when incineration conditions are bad, a decorative sheet to replace vinyl chloride resin has been demanded due to recent social demands for environmental problems.
Therefore, it has been studied to use an amorphous polyester resin film instead of the vinyl chloride resin film.

  For example, in Patent Document 1 (Japanese Patent Laid-Open No. 2001-40188), butadiene 70 to 100% by mass, aromatic vinyl monomer or aromatic (meth) acrylate monomer 30 to 0% by mass, and copolymerizable therewith 25 to 55 parts by mass of a butadiene copolymer consisting of 10 to 0% by mass of a vinyl monomer and 5 to 0% by mass of a crosslinkable monomer, 30 to 100% by mass of an aromatic vinyl monomer, (meth) Graft copolymer (A) 1 obtained by polymerizing 75 to 45 parts by mass of a monomer mixture composed of 70 to 0% by mass of an acrylic acid alkyl ester and 0 to 20% by mass of a vinyl monomer copolymerizable therewith A resin composition comprising -30% by mass and 99-70% by mass of an amorphous polyethylene terephthalate resin (B) is proposed, and this resin composition is said to satisfy both transparency and impact resistance at the same time.

  However, when the resin composition described in Patent Document 1 is calendered to produce a sheet, the mesh installed in the strainer is clogged or the calender roll peelability is poor. There is a big problem in sex.

JP 2001-40188 A

  Accordingly, an object of the present invention is to provide a resin composition for a calendered sheet that is particularly excellent in calendar moldability and excellent in adhesion to a two-component curable urethane resin and ink, and further excellent in transparency and whitening resistance. It is to provide a sheet and a laminated sheet using the same.

The invention according to claim 1 is a laminated sheet characterized in that a coating layer of a two-component curable urethane resin is further provided on a sheet formed by calendering the following resin composition for a calendered sheet. .
The resin composition for calendar molding sheet:
50 to 99% by mass of a polyester-based resin (a) in which the dicarboxylic acid component is terephthalic acid and the diol component is composed of 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol , and
A composition comprising a cross-linked product of a conjugated diene compound, ethylene glycol dimethacrylate and, if necessary, styrene, and a graft copolymer cross-linked product (b) of 1 to 50% by mass of a shell made of an aromatic vinyl compound. A resin composition for a calendered sheet, wherein 0.2 to 10 parts by mass of a linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax (c) thereof is blended with 100 parts by mass of the product (A). object.
In the invention according to claim 2, in the component (b), the ratio of the conjugated diene compound and the aromatic vinyl compound is 20 to 60% by mass of the conjugated diene compound and 40 to 80% by mass of the aromatic vinyl compound. It is a laminated sheet of Claim 1 characterized by the above-mentioned.
The invention according to claim 3 is characterized in that the two-component cured urethane resin coating layer contains 0.5 to 20 parts by mass of wax per 100 parts by mass of urethane resin. It is a laminated sheet of description.

  According to the present invention, a linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax thereof is blended in a specific range with respect to a composition comprising a cross-linked product (rubber component) of a polyester resin and a graft copolymer. Therefore, there is little clogging of the mesh installed in the strainer at the time of calendar molding, there are no defects such as bank marks on the molded calendar sheet, no irregularity due to poor dispersion of the rubber component, rubber component Excellent roll moldability (prevents stickiness to the metal roll during take-off), excellent calendar moldability, excellent adhesion to two-part curable urethane resin, excellent ink adhesion, and more transparent The resin composition for calendar molding sheets excellent in the property and whitening resistance, a sheet | seat using this, and a lamination sheet can be provided.

Hereinafter, the present invention will be described in more detail.
Polyester resin (a)
The polyester resin (a) used in the present invention is a material known in the art, and is disclosed in, for example, Japanese Patent No. 3280374 . The term "polyester" as used in your herein, such is intended to include also the copolyester. Amorphous polyesters are preferred because they have an infinite crystallization half time .

As component (a), for example, terephthalic acid or dimethyl terephthalic acid and ethylene glycol as main components are preferably produced by an esterification reaction and a polycondensation reaction.
The component (a) also includes a copolymer type obtained by copolymerizing a third component in addition to the above dicarboxylic acid and glycol components, and this type is preferred in the present invention.
In a preferred embodiment of the present invention, 1,4-cyclohexanedimethanol, terephthalic acid, isophthalic acid and the like are suitable as the third component.
Particularly preferred components (a) are exemplified below.
The dicarboxylic acid component is terephthalic acid, and the diol component is ethylene glycol 50 to 99 mol% (preferably 60 to 80 mol%) and 1,4-cyclohexanedimethanol 1 to 50 mol% (preferably 20 to 40 mol%). ).
The viscosity of component (a) is preferably 0.65 to 0.85 as an IV value.
The method for producing the polyester resin (a) used in the present invention is already widely known in the art, and is disclosed in, for example, US Pat. No. 5,340,907.

Graft copolymer cross-linked product (b)
The graft copolymer cross-linked product (b) used in the present invention is a cross-linked product having a core made of a conjugated diene compound, ethylene glycol dimethacrylate and, if necessary, styrene, and a shell made of an aromatic vinyl compound. It is a polymer .
Examples of the conjugated diene compound include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Can be mentioned. As an optional component in the polymerization of conjugated diene compound constituting the core, it is possible to present the styrene emissions.

  Examples of the aromatic vinyl compound used in the graft portion constituting the shell include styrene, 4-methoxystyrene, 4-ethoxystyrene, 4-propoxystyrene, 4-butoxystyrene, 2-methylstyrene, 3-methylstyrene, 4 -Methylstyrene, 4-ethylstyrene, 2,5-dimethylstyrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 4-bromostyrene, 2,5-dichlorostyrene, Examples include α-methylstyrene. However, the shell does not contain (meth) acrylic acid alkyl ester. In the present invention, since the shell does not contain (meth) acrylic acid alkyl ester, it has better calendar moldability than conventional techniques, adhesion to other thermoplastic resins, adhesion to two-component curable urethane resin, ink In addition to excellent adhesion, it also has excellent transparency and whitening resistance.

  In the component (b), the ratio of the conjugated diene compound and the aromatic vinyl compound is preferably 20 to 60% by mass of the conjugated diene compound and 40 to 80% by mass of the aromatic vinyl compound. More preferably, it is 35-50 mass% of conjugated diene compounds and 50-65 mass% of aromatic vinyl compounds.

Grayed raft copolymer emulsion polymerization, suspension polymerization, can be obtained by solution polymerization emulsion polymerization is preferred. The emulsion polymerization is produced by a known emulsification method and polymerization sequence.

In the component of the present invention (b), cross-linking is intends line when the polymerization of conjugated diene compound constituting the core.
Examples of the crosslinkable monomer, ethylene glycol dimethacrylate is preferred because of excellent impact resistance improving effect.
Examples of the organic peroxide used for crosslinking include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, , 5-Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)- 3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl Peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl Oxides, lauroyl peroxide, may be mentioned tert- butyl cumyl peroxide and the like. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di, from the viewpoint of odor, colorability, and scorch safety. -(Tert-Butylperoxy) hexyne-3 is particularly preferred.
The addition amount of the crosslinkable monomer is 0.1 to 5% by mass, preferably 2 to 4% by mass in the component (b).
Moreover, the addition amount of an organic peroxide is 0.05-3 mass parts with respect to 100 mass parts of components (b), for example, Preferably it is 0.05-1 mass part.

  The composition (A) in the present invention comprises 50 to 99% by mass of the polyester resin (a) and 1 to 50% by mass of the graft copolymer cross-linked product (b). Preferably, the polyester resin (a) 55 It consists of -92 mass% and graft copolymer crosslinked material (b) 8-45 mass%.

C28-C32 linear fatty acid and / or derivative wax (c)
The component (c) used in the present invention has the effect of improving the dispersibility of the component (b) in the present composition and improving the roll peelability of the composition. Component (b) is superior in dispersibility and roll peelability of the composition than conventional rubber, but in the present invention, the synergistic effect with component (c) is extremely remarkable.
As a component (c) used by this invention, it can be the simple substance of C28-C32 linear fatty acid or its derivative (s), or a mixture, for example. Examples of the derivatives include saponified and esterified linear fatty acids having 28 to 32 carbon atoms. The esterified product is preferably a product obtained by esterifying a linear fatty acid having 28 to 32 carbon atoms with glycols. The esterified product using such glycols has a structure represented by the following formula (1).

  In the formula, R represents a linear portion of a fatty acid, and Q represents an alkylene group having 2 or 3 carbon atoms. The esterified product of the formula (1) has two molecules of fatty acid bonded via the Q group, and this form is also included in the component (c) in the present invention.

  Particularly preferred component (c) in the present invention is a mixture of montanic acid esterified with ethylene glycol or butylene glycol, optimally a mixture of montanic acid partially esterified with butylene glycol and the remainder saponified with calcium hydroxide. It is. As such an optimal component (c), a commercially available product can be used, for example, Montanic acid partially saponified ester HW-OP (melting point: 75 ° C.) manufactured by Clariant Japan.

  The compounding ratio of the component (c) is 0.2 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the composition (A). When the blending ratio of the component (c) is less than 0.2 parts by mass, the component (b) is agglomerated and fluffs due to poor dispersion occur. Also, many meshes installed on the strainer are clogged. Furthermore, roll peelability also deteriorates. When the amount is more than 10 parts by mass, there is stickiness due to blowing to the sheet surface, which is not preferable.

  On the other hand, when the number of carbon atoms in the component (c) is less than 28, the component (b) is aggregated, and irregularities due to poor dispersion occur. Also, many meshes installed on the strainer are clogged. Furthermore, roll peelability also deteriorates. When the ratio exceeds 32, the component (b) is aggregated, and irregularities due to poor dispersion occur. Also, many meshes installed on the strainer are clogged. Furthermore, roll peelability also deteriorates.

As a method for producing the composition of the present invention, each of the above components is prepared individually, kneaded using a normal kneading apparatus such as a Henschel mixer, a tumbler, etc., and a single screw extruder, a twin screw extruder Banbury mixer, etc. A method of forming a composition by an apparatus used for forming the composition can be employed. In addition, the composition of the present invention includes, as necessary, an antioxidant, a heat stabilizer, a light resistance improver, an ultraviolet absorber, a lubricant, a plasticizer, a release agent, a charging agent, which are used as usual additives. Inhibitors, slidability improvers, colorants, and the like can also be added. Further, for the purpose of improving chemical resistance, the composition of the present invention may be mixed with at least one crystalline polyester resin selected from crystalline polyethylene terephthalate resin and polybutylene terephthalate resin having crystallinity. Good.
However, it is preferable that the composition of the present invention does not contain an acrylonitrile-styrene copolymer having a mass average molecular weight of 1,000,000 or more.

The compositions of the present invention are particularly useful for calendering to form sheets. That is, in the calendar molding using the composition of the present invention, the above-mentioned calendar moldability is very good. The type of calendar molding machine is not particularly limited. For example, there is no restriction | limiting in particular in the calendar apparatus to be used, For example, an upright type 3 roll, an upright type 4 roll, an L type 4 roll, a reverse L type 4 roll, a Z type roll etc. can be mentioned. Further, the calendar processing conditions are not particularly limited. For example, the temperature of the calender roll can appropriately adopt a range of 160 to 220 ° C.
The thickness of the sheet obtained after calendering the resin composition of the present invention (hereinafter referred to as a calendered sheet) is, for example, 30 to 1000 μm, preferably 50 to 500 μm.

In the present invention, a coating layer of a two-component curable urethane resin can be provided with good adhesion on the calendered sheet obtained as described above. By providing a coating layer of a two-component curable urethane resin on the surface of the calendered sheet, the scratch resistance and stain resistance of the calendered sheet can be improved.
The coating layer of the two-component curable urethane resin preferably contains 0.5 to 20 parts by mass, more preferably 1 to 10 parts by mass of wax per 100 parts by mass of the urethane resin. By blending the wax, the scratch resistance of the calendered sheet obtained as described above can be further improved. If the wax content is less than 0.5 parts by mass, the scratch resistance of the calendered sheet may be insufficient. On the other hand, if it exceeds 20 parts by mass, the wax may bleed on the surface of the calendered sheet and the appearance of the calendered sheet may be impaired.
The coating film layer of a two-component curable urethane resin is a coating film layer formed by mixing and applying a polyol component and a polyisocyanate component and then curing. The thickness of the coating layer of the two-component curable urethane resin is preferably 1 to 10 μm, and more preferably 3 to 7 μm. The polyol component used in the present invention is not particularly limited. For example, an oil-modified alkyd resin having a polyester bond in the main chain, an oil-free polyester, a polycaprolactone polyol, a polycarbonate polyol, an acrylic polyol, a hydroxyl group-containing vinyl polymer, and a hydroxyl group. Examples thereof include fluororesins, polyether polyols, and epoxy polyols. Among these, acrylic polyols can be suitably used. The polyol component is preferably used as a solution dissolved in an organic solvent. Examples of the solvent to be used include solvents having no active hydrogen such as toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. There are no particular restrictions on the polyisocyanate used in the present invention, for example, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and these burettes. And isocyanurate bodies. Among these, non-yellowing hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate can be suitably used. The wax used for the coating layer of the two-component curable urethane resin is not particularly limited. For example, hydrocarbon wax such as paraffin, polyethylene wax, polypropylene wax, stearic acid, hydroxystearic acid, composite stearic acid, oleic acid, etc. Fatty acid wax, stearic acid amide, oxystearic acid amide, oleic acid amide, erucyl amide, ricinoleic acid amide, behenic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide wax, stearic acid- Examples thereof include aliphatic ester waxes such as n-butyl, aliphatic metal soap waxes, and urea-formaldehyde waxes. The wax is preferably dispersed in advance in the solution of the polyol component.

The coating layer of the two-component curable urethane resin may be transparent or colored. Such a laminated sheet of the present invention is particularly suitable for membrane press molding, vacuum press molding, compressed air press molding and the like.
The coating layer of the two-component curable urethane resin is colored by adding an appropriate amount of a known pigment or dye to the urethane resin solution. When the coating layer is colored, for example, the surface can be embossed to impart design properties, and can be suitably used as a mouthpiece material (edge material) or the like.

  The present invention also provides a laminated sheet obtained by printing a printed pattern layer containing a colored ink on the calendered sheet obtained as described above. Such a laminated sheet is very excellent in adhesion between each layer. The binder contained in the colored ink is at least one selected from the group consisting of vinyl chloride-vinyl acetate copolymer, polyurethane resin, polyester resin, acrylic resin, epoxy resin, silicone-modified resin, polyisocyanate compound, polycarbonate resin, and amino resin. It is preferred that the seed is the main component. Among these, a vinyl chloride-vinyl acetate copolymer is more preferable because it has good adhesion to a calendar molded sheet.

It is also possible to laminate the calendered sheet or laminated sheet and another thermoplastic resin sheet. As another thermoplastic resin, an amorphous polyester resin is preferable, but a crystalline polyester resin may be added to the amorphous polyester resin.
Apart from the above, a calendered sheet and a sheet made of the component (a) in the present invention may be laminated.
FIG. 1 is a cross-sectional view for explaining a form in which another thermoplastic resin sheet is laminated on such a laminated sheet of the present invention. In FIG. 1, a laminated sheet 1 is configured by sequentially forming a printed pattern layer 12 and a sheet 13 made of another thermoplastic resin on a calendar molded sheet 11. The printed pattern layer 12 can be formed by employing, for example, a gravure printing method. Lamination of the sheet 13 can be performed by a film laminating method using a known adhesive or an extrusion laminating method. The calendar molded sheet 11 and / or the sheet 13 may be colored.

  In addition, the laminated sheet of the present invention can be used for wallpaper to constitute its surface. In this case, it is desirable that the laminated sheet has a thickness of 10 to 100 μm. When used as wallpaper, for example, a foamable vinyl chloride paste may be applied to a paper base, and the laminated sheet of the present invention may be heat-laminated on the surface.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not restrict | limited to the following example.

In the following example, any of the following various materials was used.
(1) Polyester resin (a)
(I) Eastman Chemical Co., PETG6763
Glycol component: 70 mol% ethylene glycol and 30 mol% 1,4-cyclohexanedimethanol
Dicarboxylic acid component: Polyester consisting of terephthalic acid Crystallization half time: Infinite

(2) Crosslinked product of graft copolymer comprising conjugated diene compound and aromatic vinyl compound having the following composition (b)
As a conjugated diene compound, 43% by mass of butadiene is contained. As an aromatic vinyl compound, 54% by mass of styrene is contained. Contains 3% by weight of ethylene glycol dimethacrylate.
This component (b) is composed of a crosslinked SBR latex consisting of butadiene, styrene and ethylene glycol dimethacrylate, then mixed with water, sodium sulfoxylate formaldehyde, styrene, cumene hydroperoxide, and grafted styrene onto the rubber latex. The sample was obtained by coagulation, filtration, washing and drying.

(3) C28-C32 linear fatty acid and / or derivative wax (c)
Manufacturer: Clariant Japan Product Name: HW-OP (Montanic acid partially saponified ester. Saponified portion is calcium salt, melting point 75 ° C)

(4) Comparative component of component (c) (i) Calcium stearate (ii)
Manufacturing company: Nippon Seika Co., Ltd.
Product name: Neutron (Oleamide)

(5) Comparative component of component (b) Graft copolymer (i)
Manufacturing company: Kaneka Chemical Co., Ltd. Trade name: Kane Ace B-56
Composition: Methacrylate / Styrene / Butadiene rubber graft copolymer Rubber particle size: 0.1-0.5 μm

(Examples 1-3 and Comparative Examples 1-6)
(Calendar moldability)
Various compositions having the formulation shown in Table 1 were melt-kneaded using a Banbury mixer and calendered to obtain a sheet having a thickness of 100 μm. As the calendar molding machine, an inverted L shape was used. The calendar condition was a calendar roll temperature of 180 ° C.
The frequency of replacing the screen (100 mesh wire mesh) in the strainer part in this molding process was examined.
Further, the roll peelability was checked as follows: ○: uniformly peeled from the roll, Δ: inferior smoothness of the sheet obtained without being peeled uniformly from the roll, and ×: the sheet was not adhered and peeled without being peeled.
The surface property of the calendered sheet was evaluated by the following evaluation method by visually observing the surface of the calendered sheet. ◯ indicates that there are no surface defects such as bank marks, scrapes, and air marks (holes remaining on the surface due to air leakage), Δ indicates that the bank marks can be confirmed faintly, and X indicates that surface defects are recognized.
Further, the transparency of the calendered sheet (thickness: 100 μm) was measured as a haze value according to JIS K7105.
Measuring device: Evaluation was performed by measuring with a direct reading haze meter manufactured by Toyo Seiki Seisakusho.
In the evaluation of transparency, a haze value of 10% or less was evaluated as ◎, a haze value of 20% or less as ◯, a haze value of less than 60% as Δ, and a haze value of 60% or more as x.
Further, the whitening property of the calendered sheet was evaluated by the following test methods and evaluation criteria.
A calendered sheet with a thickness of 0.1 mm (thickness: 100 μm) is attached to two stainless steel plates (6 cm x 5 cm, 1 mm thickness) that are in contact with each other with the long sides parallel, and folded at 90 ° and folded. The degree of whitening of the surface was visually observed and evaluated according to the following criteria.
A: Whitening is not recognized. ○: Slight whitening is observed. X: Big whitening is recognized.
The results are shown in Table 1.

(Laminated sheet (1))
To a solution consisting of 100 parts by mass of acrylic polyol, 100 parts by mass of toluene, and 100 parts by mass of ethyl acetate, 5 parts by mass of polypropylene wax [Croda Japan Co., Ltd., WNl135] is added and dispersed uniformly, and further 5 masses of hexamethylene diisocyanate. Part was added to prepare a two-component curable urethane resin paint. This was apply | coated on the said calendar molding sheet | seat, the coating film of thickness 5 micrometers was formed, and the lamination sheet (1) was obtained.
The adhesion of the obtained laminated sheet (1) was tested. This adhesion test was performed in accordance with JIS K 5400. A 100 mm square grid with a 1 mm square was attached with a rotary cutter, and cello tape [manufactured by Nichiban, registered trademark] was pressure-bonded, followed by a 90-degree peel test. Adhesion was evaluated by counting the number of remaining films in 100 squares.
The results are shown in Table 1.

(Laminated sheet (2))
On one surface of the calendered sheet obtained above, a wood grain pattern was formed by gravure printing using a colored ink having a vinyl chloride-vinyl acetate copolymer as a binder, thereby forming a printed pattern layer.
The adhesion of the obtained laminated sheet (2) was tested in the same manner as the laminated sheet (1).
The results are shown in Table 1. In addition, the example regarding the laminated sheet (2) is a reference example.

From the results of Table 1, it can be seen that in each example using the composition of the present invention, the screen replacement frequency of the strainer part is less than that of the comparative example, the roll peelability is good, and the calenderability is excellent. .
Moreover, it turns out that the laminated sheet of this invention is excellent in the adhesiveness between each layer.

  According to the present invention, particularly excellent in calendar moldability, excellent adhesion to a two-component curable urethane resin, excellent adhesion of ink, and further excellent in transparency and whitening resistance, a resin composition for a calendar molded sheet, Sheets and laminate sheets using the same can be provided.

It is sectional drawing for demonstrating an example of a lamination sheet.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Laminated sheet 11 Calendar forming sheet 12 Print pattern layer 13 Sheet | seat which consists of thermoplastic resins

Claims (3)

A laminated sheet comprising a sheet obtained by calendering the following resin composition for a calendered sheet, further provided with a two-component curable urethane resin coating layer.
The resin composition for calendar molding sheet:
50 to 99% by mass of a polyester-based resin (a) in which the dicarboxylic acid component is terephthalic acid and the diol component is composed of 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol , and
A composition comprising a cross-linked product of a conjugated diene compound, ethylene glycol dimethacrylate and, if necessary, styrene, and a graft copolymer cross-linked product (b) of 1 to 50% by mass of a shell made of an aromatic vinyl compound. A resin composition for a calendered sheet, wherein 0.2 to 10 parts by mass of a linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax (c) thereof is blended with 100 parts by mass of the product (A). object. Wherein the component (b), the proportion of the conjugated diene compound and an aromatic vinyl compound, to claim 1, characterized in that the conjugated diene compound 20-60 wt% and an aromatic vinyl compound from 40 to 80 wt% The laminated sheet as described. The laminated sheet according to claim 1 or 2 , wherein the coating layer of the two-component cured urethane resin contains 0.5 to 20 parts by mass of wax per 100 parts by mass of the urethane resin.

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