JP4634275B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet, and more particularly to a decorative sheet having excellent adhesion between a polyester-based resin and a two-component curable urethane resin, and excellent solvent resistance and emboss transferability.

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. 11-34269), a surface protective layer made of a two-component curable urethane resin coating is provided on the surface side of an amorphous polyethylene terephthalate resin-based colored film, and the surface protection is performed. An amorphous polyethylene terephthalate resin-based decorative sheet having an embossed pattern formed on the layer is disclosed. In Patent Document 2 (Japanese Patent Laid-Open No. 11-34270), a pattern printing layer is provided on the back side of a transparent amorphous polyethylene terephthalate resin film, and a coating film of a two-component curable urethane resin is provided on the front side. An amorphous polyethylene terephthalate resin-based decorative sheet having a surface protective layer and an embossed pattern formed on the surface protective layer is disclosed.

  However, the decorative sheets described in Patent Documents 1 and 2 have a problem that the adhesiveness between the amorphous polyethylene terephthalate resin and the two-component curable urethane resin is poor, and therefore the solvent resistance is poor. There is also room for improvement in emboss transferability.

JP-A-11-34269 JP-A-11-34270

  Accordingly, an object of the present invention is to provide a decorative sheet having excellent adhesion between a polyester-based resin and a two-component curable urethane resin and excellent solvent resistance and emboss transferability.

The present invention is as follows.
(1) An embossed pattern is formed on a film having the following polyester resin (a) as a main component, and a surface protective layer comprising a coating film of a two-component curable urethane resin is provided on the embossed pattern. A decorative sheet.
Polyester resin (a):
A dicarboxylic acid component comprising terephthalic acid and a diol component comprising 60.5-72.5 mol% ethylene glycol, 25-37 mol% 1,4-cyclohexanedimethanol and 2.5-6 mol% diethylene glycol ( Provided that the total of ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%).
(2) The decorative sheet according to (1), wherein the polyester resin (a) has a number average molecular weight of 16000 to 24000 as measured by GPC measurement (RI detector).
(3) The decorative sheet according to (1) or (2), wherein the film is obtained by calendar molding.
(4) The said film mix | blends 0.2-10 mass parts of C28-32 linear fatty acid and / or its derivative-type wax (b) with respect to 100 mass parts of said polyester-type resin (a), The decorative sheet according to any one of (1) to (3), wherein the obtained resin composition is calendered.
(5) The decorative sheet according to (1) or (2), wherein the film is obtained by extrusion molding.
(6) Graft copolymer in which the film is graft-polymerized with 50% to 99% by weight of the polyester resin (a) and an aromatic vinyl compound and / or a (meth) acrylic acid ester compound on the conjugated diene rubber particles ( c) a cross-linked product (d) of a block copolymer comprising a polymer block A mainly composed of an aromatic vinyl compound and a polymer block B mainly composed of a conjugated diene compound, an aromatic vinyl compound and acrylic rubber particles And / or a graft copolymer (e) obtained by graft polymerization of a (meth) acrylic acid ester compound, and at least one selected from the group consisting of a thermoplastic polyester elastomer (f). The decorative sheet according to any one of (1) to (5).
(7) The decorative sheet according to (6), wherein the component (c) is a crosslinked body crosslinked with a crosslinking monomer.
(8) The decorative sheet according to (6), wherein the polymer block A in the component (d) is mainly composed of styrene and the polymer block B is mainly composed of butadiene.
(9) The coating film of the two-part curable urethane resin contains 0.5 to 20 parts by mass of wax per 100 parts by mass of the urethane resin. The decorative sheet as described.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet excellent in the adhesiveness of a polyester-type resin and a two-component curable urethane resin, and excellent in solvent resistance and emboss transfer property 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 comprises a dicarboxylic acid component comprising terephthalic acid, 60.5-72.5 mol% ethylene glycol, 25-37 mol% 1,4-cyclohexanedimethanol and 2 A diol component composed of 5 to 6 mol% of diethylene glycol (provided that the total of ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%).

In order to prepare a polyester containing the diethylene glycol moiety in a predetermined ratio, for example, a predetermined amount of diethylene glycol is used as a diol component. However, when ethylene glycol is used instead of diethylene glycol, a diethylene glycol moiety is formed by the condensation reaction. Usually, in a polyester containing an ethylene terephthalate part, a diethylene glycol part is formed by the condensation reaction of the ethylene glycol in the production process. The content of the diethylene glycol moiety varies depending on the polyester production method, the reaction conditions, the catalyst used, and the like. Example 1 of JP-A-63-150331 discloses a heat-shrinkable polyester film made of polyethylene terephthalate, which contains 2 mol% of diethylene glycol.
When the diol component contains about 31.5 mol% of 1,4-cyclohexanedimethanol, the amount of ethylene glycol at the time of charging is less than 70% compared to the synthesis of the above polyethylene terephthalate, so that 1,4- The amount of diethylene glycol by-product in the cyclohexanedimethanol-modified polyester resin was small, and was about 1.8 mol% at the maximum.
The polyester-based resin (a) in the present invention generally contains a larger amount of diethylene glycol portion than the amount of diethylene glycol portion by-produced when producing a polyester-based resin as a whole. Therefore, in the present invention, in order to contain the predetermined amount of diethylene glycol, a necessary amount of diethylene glycol is usually used as the diol component in addition to ethylene glycol, depending on the content. Alternatively, the amount of diethylene glycol by-produced from ethylene glycol can also be controlled by optimizing the polyester production conditions and catalyst.
Any of the polyester resins (a) in the present invention can be produced by a conventional method. For example, (copolymerization) polyester is prepared using a direct esterification method in which a dicarboxylic acid and a diol are directly reacted; a transesterification method in which a dimethyl ester of a dicarboxylic acid and a diol are reacted. The preparation may be carried out by either a batch method or a continuous method.

The content of diethylene glycol is 2.5 to 6 mol%, preferably 2.8 to 5 mol%, more preferably 2.8 to 4 mol%.
Although Provista manufactured by Eastman Chemical Co. contains trimellitic anhydride instead of diethylene glycol as the third component, it is not preferable for the purpose of the present invention.

The polyester resin (a) is a polyester having a crystallization half time from a molten state of at least 5 minutes, preferably at least 12 minutes. Crystallization half time is measured using a Perkin-Elmer model DSC-2 differential scanning calorimeter. A 15.0 mg sample is sealed in an aluminum pan and heated at 290 ° C. for 2 minutes at a rate of about 320 ° C./min. The sample is then immediately cooled in the presence of helium to a predetermined isothermal crystallization temperature at a rate of about 320 ° C./min (20 ° C./min if the apparatus is not possible). The crystallization half time is determined as the time interval from reaching the isothermal crystallization temperature to the point of the crystallization peak on the DSC curve.
In addition, when diethylene glycol is less than 2.5 mol% or more than 6 mol%, the wettability with the two-component curable polyurethane resin is deteriorated, so that the adhesion is also deteriorated, and the polyester resin (a) is a main component. As a result, a part where the two-component curable urethane resin does not enter the embossed concave portion of the film to be formed is inferior in solvent resistance, and the transferability of the emboss to the film containing the polyester resin (a) as a main component also deteriorates. .
In addition, even when ethylene glycol and 1,4-cyclohexanedimethanol are outside the above ranges, the wettability and adhesion to the two-component curable polyurethane resin deteriorate, resulting in poor solvent resistance and polyester. Transferability of the emboss to the film containing the resin (a) as a main component also deteriorates.
Further, when the ethylene glycol is outside the above range, the crystallization of the polyester resin occurs, the film shrinkage becomes extremely large, the flexibility is impaired, and 1,4-cyclohexanedimethanol is outside the above range. Polyester resin is crystallized, resulting in extremely large film shrinkage and loss of flexibility.
In the amount relationship between ethylene glycol and 1,4-cyclohexanedimethanol, the crystallinity is lowest (the crystallization time is extremely long) within the preferred range. Thereby, shrinkage | contraction of a film is suppressed and a softness | flexibility increases. Moreover, the thickness controllability at both ends during calendar sheet molding is enhanced, the strainer mesh replacement frequency is reduced, and the roll peelability is further improved.

The polyester resin (a) used in the present invention preferably has a number average molecular weight of 16000 to 24000 as measured by GPC (RI detector) (performed under the following measurement conditions). If it is in this range, the calendering temperature becomes high, and the thickness controllability at both ends of the sheet is very good.
Measuring device name: HPLC VP manufactured by Shimadzu Corporation
Column used: Shodex K806L (8 mmφ × 300 mm) × 2 Solvents: Special grade sample concentration for chloroform liquid chromatography: 0.2% (w / v)
Flow rate: 1 ml / min
Detector: RI
Injection volume: 100 μL
Measurement temperature: 35 ° C

The polyester-based resin (a) can be subjected to extrusion molding based on a known means. For example, an extruded film having a thickness of 10 to 300 μm, preferably 30 to 150 μm can be obtained.
In addition, for the film in the present invention, an antioxidant, a heat stabilizer, a light resistance improver, an ultraviolet absorber, a lubricant, a plasticizer, a release agent, an antistatic agent, which are used as usual additives, if necessary. Agents, slidability improvers, colorants and the like can also be added. Furthermore, for the purpose of improving chemical resistance, at least one crystalline polyester resin selected from polyethylene terephthalate resin and polybutylene terephthalate resin having crystallinity may be mixed. These various additives are preferably 50% by mass or less in the film of the present invention.

  It is also a preferred embodiment of the present invention that the polyester resin (a) is blended with the following wax and various resins and the resulting composition is subjected to calender molding.

C28-32 linear fatty acid and / or derivative wax (b)
The component (b) used in the present invention has, for example, the following effects of improving the dispersibility of the rubber component and improving the roll peelability of the composition.
As a component (b) 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 through the Q group, and this form is also included in the component (b) in the present invention.

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

  The compounding ratio of the component (b) 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 polyester resin (a). When the blending ratio of the component (b) is less than 0.2 parts by mass, the rubber component is aggregated, and irregularities due to poor dispersion occur. In addition, when the calendar is formed, the mesh installed on the strainer is often 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.

  Further, when the component (b) has less than 28 carbon atoms, the rubber component 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 rubber component is aggregated, and irregularities due to poor dispersion occur. Also, many meshes installed on the strainer are clogged. Furthermore, roll peelability also deteriorates.

Graft copolymer (c)
The graft copolymer (c) is a graft copolymer obtained by graft polymerizing an aromatic vinyl compound and / or a (meth) acrylic acid ester compound to a conjugated diene rubber particle.
Examples of the conjugated diene compound used for preparing the conjugated diene rubber particles include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 1,3- Examples thereof include pentadiene and 1,3-hexadiene. When polymerizing the conjugated diene compound constituting the core, a copolymerizable monomer such as styrene or methyl methacrylate may be present as an optional component. The particle diameter of the conjugated diene rubber particles is preferably 0.05 to 1.0 μm. More preferably, it is 0.05-0.5 micrometer.

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.
As the (meth) acrylic acid ester compound, those having 1 to 8 carbon atoms are suitable. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. are mentioned. These can also be used in combination. Of these, methyl (meth) acrylate is desirable.

  In the component (c), the ratio of the conjugated diene compound (c1) to the aromatic vinyl compound and / or the (meth) acrylic ester compound (c2) is (c1) 20 to 60% by mass and (c2) the aromatic vinyl It is preferable that it is 40-80 mass% of compounds. More preferably, they are (c1) 35-50 mass% and (b2) 50-65 mass%. In (c2), the aromatic vinyl compound and the (meth) acrylic acid ester compound may or may not be used in combination. In this invention, the form which uses together an aromatic vinyl compound and a (meth) acrylic acid ester compound is preferable.

  The graft copolymer (c) can be obtained by emulsion polymerization, suspension polymerization, solution polymerization or the like, but emulsion polymerization is preferred. For emulsion polymerization, known emulsification methods and polymerization sequences are employed.

The graft copolymer (c) used in the present invention is preferably a crosslinked product crosslinked with a crosslinking monomer. By crosslinking the graft copolymer, it is preferable because the impact resistance is improved and the melt viscosity is improved, so that there is no blurring or air mark on the surface of the sheet at the time of calendering, and peeling stability from the metal roll can be obtained. Crosslinking is preferably performed when the conjugated diene compound constituting the core is polymerized, but it is also possible to crosslink the graft body grafted with the shell.
Examples of the crosslinkable monomer include monomers having two or more reactive double bonds, for example, aromatic divinyl monomers such as divinylbenzene; ethylene glycol di (meth) acrylate, butylene glycol di (meth) ) Acrylates, hexanediol di (meth) acrylates, oligoethylene glycol di (meth) acrylates, trimethylolpropane di (meth) acrylates, alkane polyol polyacrylates such as trimethylolpropane tri (meth) acrylate, etc. Ethylene glycol dimethacrylate is preferred because of its excellent impact resistance improvement 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 preferably 0.1 to 5% by mass, more preferably 2 to 4% by mass with respect to 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 (c), for example, Preferably it is 0.05-1 mass part.

Cross-linked block copolymer (d)
The cross-linked product (d) of the block copolymer is a cross-linked product of a block copolymer comprising a polymer block A mainly composed of an aromatic vinyl compound and a polymer block B mainly composed of a conjugated diene compound.
The block copolymer is preferably composed of at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. For example, an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as ABA, BABA, ABBABA, or the like can be given.

  The block copolymer as a whole preferably contains an aromatic vinyl compound in an amount of preferably 5 to 60% by mass, more preferably 20 to 50% by mass.

The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of only an aromatic vinyl compound, or 50% by mass or more of the aromatic vinyl compound, preferably 70% by mass or more of the conjugated diene compound. It is a polymer block.
The polymer block B mainly composed of a conjugated diene compound is preferably composed of only a conjugated diene compound, or is a copolymer of 50% by mass or more, preferably 70% by mass or more of an aromatic vinyl compound with a conjugated diene compound. It is a coalesced block.

  The number average molecular weight of the block copolymer is preferably in the range of 5,000 to 1,500,000, more preferably 10,000 to 550,000, still more preferably 100,000 to 400,000. Distribution is 10 or less. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

  Further, in the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of conjugated diene compounds, the distribution of units derived from the conjugated diene compound or aromatic vinyl compound in the molecular chain is random, It may be tapered (in which the monomer component increases or decreases along the molecular chain), partially in a block form, or any combination thereof. When there are two or more polymer blocks A mainly composed of aromatic vinyl compounds or polymer blocks B mainly composed of conjugated diene compounds, each polymer block has a different structure even if each has the same structure. There may be.

  As the aromatic vinyl compound constituting the block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. preferable. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and These combinations are preferred. Most suitable is butadiene.

  Specific examples of the block copolymer include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and the like.

  Many methods for producing these block copolymers have been proposed. As typical methods, for example, a lithium catalyst or a Ziegler-type catalyst is prepared by the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert medium.

In the present invention, a polyfunctional compound is used to crosslink the block copolymer. By cross-linking the copolymer, the impact resistance is improved and the melt viscosity is improved, so there is no blurring or air marks on the sheet surface during molding, especially during calendar molding, and it is possible to obtain peeling stability from the metal roll. preferable.
Examples of the polyfunctional compound include monomers having two or more reactive double bonds, for example, aromatic divinyl monomers such as divinylbenzene; ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate Alkane polyol polyacrylates such as hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc. Ethylene glycol dimethacrylate is preferred because of its excellent property 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 amount of the polyfunctional compound added is 0.1 to 5% by mass, preferably 2 to 4% by mass in the component (d).
Moreover, the addition amount of an organic peroxide is 0.05-3 mass parts with respect to 100 mass parts of components (d), for example, Preferably it is 0.05-1 mass part.

Graft copolymer (e)
The graft copolymer (e) is a graft copolymer obtained by graft-polymerizing an aromatic vinyl compound and / or a (meth) acrylic acid ester compound to acrylic rubber particles.
Acrylic rubber particles can be obtained by polymerizing an acrylate ester. As the acrylic ester, those having 2 to 8 carbon atoms of the alcohol component are suitable, and examples thereof include ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate and the like. When the acrylic acid ester constituting the core is polymerized, a vinyl aromatic such as styrene or another copolymerizable monomer may be copolymerized as an optional component. The particle diameter of the acrylic rubber particles is preferably 0.05 to 1.0 μm. More preferably, it is 0.05-0.5 micrometer.

  The aromatic vinyl compound and (meth) acrylic acid ester compound used in the graft part constituting the shell, and the use ratio and preparation method thereof are the same as those described in the component (c) above (however, “Conjugated diene compound (b1)” is replaced with “acrylic ester (b1)” in the usage ratio). Moreover, the compound used for a graft part can also be used together, and the ratio is as having demonstrated with the said component (c). Furthermore, it is also preferable that the component (e) is a cross-linked product cross-linked with a cross-linkable monomer as described in the component (c).

Thermoplastic polyester elastomer (f)
The thermoplastic polyester elastomer (f) is preferably, for example, the following general formula (2) or (3)

A terephthalic acid crystalline polyester hard segment (polybutylene terephthalate (PBT) or polybutylene naphthalate (PBN)) represented by formula (4):

(Wherein x represents an integer of 2 to 4 and p represents an integer of 8 to 140), an aliphatic polyether soft segment (polytetramethylene diglycol (PTMG), polypropylene represented by a molecular weight of 600 to 6000) And a segment copolyester having a molecular weight of 5,000 to 100,000 composed of glycol (PPG) and polyethylene glycol (PEG).
By setting the molecular weight of the thermoplastic polyester elastomer within the above range, the resulting decorative sheet has better physical properties such as impact resistance, tensile strength, cold resistance, and molding processability.
Moreover, the physical property, for example, impact resistance, of the decorative sheet of the present invention can be imparted by appropriately selecting the molar ratio between the hard segment and the soft segment.
For example, the hard segment / soft segment molar ratio is preferably such that the soft segment is 50 mol% or more.

In the present invention, the film is at least one selected from the group consisting of 50 to 99% by mass of a polyester resin (a) and the components (c), (d), (e), and (f). It is good to consist of mass%. The components (c), (d), (e) and (f) may be used in combination.
More specifically, when the graft copolymer (c) is used, (a) component 50 to 99% by mass and (c) component 1 to 50% by mass, preferably (a) polyester resin 55 to 92 mass% and (c) graft copolymer 8-45 mass% are good.
Moreover, when using the crosslinked body (d) of a block copolymer, (a) component 50-99 mass% and (d) component 1-50 mass%, Preferably (a) component 55-92 mass% And (d) 8-45 mass% of component is good.
When the graft copolymer (e) is used, the component (a) is 50 to 99% by mass and the component (e) is 1 to 50% by mass, preferably the component (a) 55 to 92% by mass and the component (e). 8-45 mass% is good.
Furthermore, when using either (c) and (d) component and (e) component together, (a) 50-98 mass% of component, (c) and (d) any one of 1 49 mass% and (e) component 1 to 49 weight% are good. However, the total of the components (a), (c), (d) and (e) is 100% by weight.
Moreover, when using a thermoplastic polyester-type elastomer (f), (a) component 50-99 mass% and (f) component 1-50 mass%, Preferably (a) component 70-99.9 mass% and ( f) Component 0.1 to 30% by mass, more preferably (a) component 70 to 99% by mass and (f) component 1.0 to 30% by mass.

  The mixing method of the polyester resin (a), the component (b), and at least one selected from the group consisting of the components (c), (d), (e) and (f) Prepared separately, kneaded using a normal kneading apparatus, such as a Henschel mixer, tumbler, etc., and shaped by an apparatus used for normal shaping such as a single screw extruder, twin screw extruder Banbury mixer and the composition The method made can be adopted.

In the calendar molding, there is no particular limitation on the calendar device to be used, and examples thereof include an upright type 3 roll, an upright type 4 roll, an L type 4 roll, an inverted L type 4 roll, and a Z type roll. . 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 film obtained by calendar molding is, for example, 30 to 1000 μm, preferably 50 to 500 μm.

  In this invention, the embossing pattern is formed in the film which has the said polyester-type resin (a) as a main component. As is well known, the embossed pattern can be applied using a heated embossing roll, and as the embossed pattern, for example, desired unevenness such as wood grain, sand grain, cloth grain can be formed, There is no particular restriction.

Next, a surface protective layer made of a coating film of a two-component curable urethane resin is provided on the formed embossed pattern. This will be described below.
Since the decorative sheet of the present invention has good wettability with the two-component curable urethane resin, the two-component curable urethane resin can easily enter the embossed recesses on the surface of the polyester resin (a), and has solvent resistance and adhesion. Improves. Moreover, it is excellent in the emboss transfer property of the polyester-type resin (a) surface. Moreover, the coating film of a two-component curable urethane resin can improve the scratch resistance and stain resistance of the decorative sheet.
The two-component curable urethane resin coating film 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 decorative sheet can be further improved. If the wax content is less than 0.5 parts by mass, the decorative sheet may have insufficient scratch resistance. Conversely, if it exceeds 20 parts by mass, the wax may bleed on the surface of the decorative sheet and the appearance of the decorative sheet may be impaired.
The coating film of a two-component curable urethane resin is a coating film that is formed by mixing a polyol component and a polyisocyanate component and then applying the mixture to form a curing reaction. The thickness of the coating film 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. There is no particular limitation on the wax used for the coating film of the two-component curable urethane resin, 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 and other aliphatic amide waxes, stearic acid-n Examples thereof include aliphatic ester waxes such as 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 film of the two-component curable urethane resin may be transparent or colored. Such a decorative sheet of the present invention may be further subjected to membrane press molding, vacuum press molding, pressure press molding and the like.
The coating 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 film is colored, for example, the surface can be embossed to impart design properties, and can be suitably used as a end piece (edge material) or the like.

  In the present invention, by using a specific polyester-based resin (a), particularly a specific amount of diethylene glycol, the reason is not clear. However, as described above, the wettability with the two-component curable urethane resin is improved, and the polyester The two-component curable urethane resin can easily enter the embossed recesses on the surface of the resin (a), and the solvent resistance and adhesion are improved. Moreover, it contributes also to the improvement of the emboss transfer property to the polyester-type resin (a) 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-1)
Mn = 21000
Glycol component: 65.7 mol% ethylene glycol, 31.5 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.
In addition, the composition ratio of each of the above components is ¹³ C-NMR (nuclear magnetic resonance apparatus (NMR) GX-400 manufactured by JEOL), and about 40 mg of a sample is dissolved in deuterated chloroform in a 5 mm diameter sample tube. It was measured and confirmed as a measurement sample (the same applies to the following).

(2) Polyester resin (a-2)
Mn = 21000
Glycol component: 64.5 mol% ethylene glycol, 31.5 mol% 1,4-cyclohexanedimethanol and 4.0 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(3) Polyester resin (a-3)
Mn = 20500
Glycol component: 66.0 mol% ethylene glycol, 31.5 mol% 1,4-cyclohexanedimethanol and 2.5 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(4) Polyester resin (a-4)
Mn = 21,500
Glycol component: 62.5 mol% ethylene glycol, 31.5 mol% 1,4-cyclohexanedimethanol and 6.0 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(5) Polyester resin (a-5)
Mn = 20500
Glycol component: 71.0 mol% ethylene glycol, 26.2 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(6) Polyester resin (a-6)
Mn = 21000
Glycol component: 61.5 mol% ethylene glycol, 35.7 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(7) Comparative polyester resin (a′-1)
Mn = 20500
Glycol component: 66.7 mol% ethylene glycol, 31.5 mol% 1,4-cyclohexanedimethanol and 1.8 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(8) Comparative polyester resin (a′-2)
Mn = 21,500
Glycol component: 66.3 mol% ethylene glycol, 31.5 mol% 1,4-cyclohexanedimethanol and 2.2 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(9) Comparative polyester resin (a'-3)
Mn = 20500
Glycol component: 62.3 mol% ethylene glycol, 31.5 mol% 1,4-cyclohexanedimethanol and 6.2 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(10) Comparative polyester resin (a′-4)
Mn = 21000
Glycol component: ethylene glycol 40.0 mol%, 1,4-cyclohexanedimethanol 57.2 mol% and diethylene glycol 2.8 mol%
Dicarboxylic acid component: Polyester composed of terephthalic acid.

(11) Comparative polyester resin (a′-5)
Glycol component: 85.0 mol% ethylene glycol, 12.2 mol% 1,4-cyclohexanedimethanol and 2.8 mol% diethylene glycol
Dicarboxylic acid component: Polyester composed of terephthalic acid.

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

(13) Graft copolymer (c-1)
Manufacturing company: Kaneka Chemical Co., Ltd. Trade name: Kane Ace B-22
Composition: Methyl methacrylate / styrene / butadiene rubber graft copolymer Rubber particle size: 0.1 to 0.5 μm

(14) Graft copolymer (c-2) (crosslinked product of graft copolymer comprising conjugated diene compound and aromatic vinyl compound having the following composition)
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 composed 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.

(15) Graft copolymer (e)
Manufacturer: Kaneka Chemical Industry Name: Kane Ace FM
Composition: Methacrylate / acrylonitrile / butyl acrylate (acrylic rubber) graft copolymer Rubber particle size: 0.05 to 0.1 μm

(16) Thermoplastic polyester elastomer (f)
Manufacturing company: Made by Toray DuPont Company name: Hytrel 4057
Composition: Chemical structure is a copolymer of hard segment (PBT) and soft segment (polyether)

(Examples 1-18 and Comparative Examples 1-15)
(Calendar moldability)
Various compositions having the formulation shown in Table 1 were melt-kneaded using a Banbury mixer, extruded or calendered to obtain a film having a thickness of 80 μm. As the extruder, a single shaft, a diameter of 90 mm, and L / D = 28 were used. The extrusion temperature condition was 230 ° C. As the calendar molding machine, an inverted L shape was used. The calendar condition was a calendar roll temperature of 185 ° C.
Next, using a heated embossing device, embossing at a roll temperature of 150 ° C. was performed to form a pimple-like embossed pattern on the film. In addition, the average roughness Ra of the embossing roll of the eye shape in a heating embossing apparatus is 10 micrometers.
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 applied onto the film to form a coating film having a thickness of 5 μm.
The resulting decorative sheet was examined for solvent resistance. Specifically, special grade toluene (manufactured by Kanto Chemical Co., Inc.) was included in absorbent cotton and rubbed 20 times, so that ◎: no change at all, ○: slight change in gloss, Δ: slightly cloudy, ×: Evaluated as having no gloss at all.
Further, the transparency of the decorative sheet 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 less than 60% was evaluated as Δ, and a haze value of 60% or more was evaluated as ×.
Furthermore, the emboss transfer rate to the film was examined. Specifically, the average roughness Ra of the film was measured according to JIS B0601-1994, and evaluated as ◎: 8 μm or more, ○: Ra 7 μm or more and less than 8 μm, Δ: Ra 5 μm or more and less than 7 μm, ×: Ra 5 μm or less. .
Moreover, the adhesiveness of the decorative sheet 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.
(Circle): 100/100, (triangle | delta): It evaluated as 99-95 / 100, x: less than 95/100.
The results are shown in Table 1.

  From the results of Table 1, in each example using the composition of the present invention, compared with the comparative example, the adhesion with the coating film of the two-component curable urethane resin, the solvent resistance, and the transparency are excellent, and the film It can be seen that the embossing transferability to is excellent.

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet excellent in the adhesiveness of a polyester-type resin and a two-component curable urethane resin, and excellent in solvent resistance and emboss transfer property can be provided.

Claims (9)

A cosmetic comprising an embossed pattern formed on a film comprising the following polyester resin (a) as a main component, and a surface protective layer comprising a coating film of a two-component curable urethane resin on the embossed pattern. Sheet.
Polyester resin (a):
A dicarboxylic acid component comprising terephthalic acid and a diol component comprising 60.5-72.5 mol% ethylene glycol, 25-37 mol% 1,4-cyclohexanedimethanol and 2.5-6 mol% diethylene glycol ( Provided that the total of ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol is 100 mol%).   The decorative sheet according to claim 1, wherein the polyester resin (a) has a number average molecular weight of 16000 to 24000 as measured by GPC measurement (RI detector).   The decorative sheet according to claim 1 or 2, wherein the film is obtained by calendering.   The film was obtained by blending 0.2 to 10 parts by mass of a linear fatty acid having 28 to 32 carbon atoms and / or a derivative wax (b) thereof with respect to 100 parts by mass of the polyester resin (a). The decorative sheet according to any one of claims 1 to 3, wherein the resin composition is calendered.   The decorative sheet according to claim 1 or 2, wherein the film is obtained by extrusion molding. The film is a polyester copolymer (a) 50 to 99% by weight, and a graft copolymer (c) obtained by graft polymerizing an aromatic vinyl compound and / or a (meth) acrylic acid ester compound to a conjugated diene rubber particle, A cross-linked product (d) of a block copolymer composed of a polymer block A mainly composed of an aromatic vinyl compound and a polymer block B mainly composed of a conjugated diene compound, an aromatic vinyl compound and / or ( The graft copolymer (e) obtained by graft polymerization of a (meth) acrylate compound and at least one selected from the group consisting of a thermoplastic polyester elastomer (f) is 1 to 50% by weight. Item 6. The decorative sheet according to any one of Items 1 to 5.   The decorative sheet according to claim 6, wherein the component (c) is a crosslinked product crosslinked with a crosslinking monomer.   The decorative sheet according to claim 6, wherein the polymer block A in the component (d) is mainly composed of styrene and the polymer block B is mainly composed of butadiene.   The decorative sheet according to any one of claims 1 to 8, wherein the coating film of the two-component curable urethane resin contains 0.5 to 20 parts by mass of wax per 100 parts by mass of the urethane resin.