JP6639878B2 - Polyester resin laminate and decorative film - Google Patents

Description

  The present invention relates to a polyester resin laminate and a decorative film using the same.

  Conventionally, furniture such as cabinets, storage cabinets, cupboards, desks, etc .; household appliances such as refrigerators, washing machines, air conditioners, mobile phones, personal computers; and building materials such as floors, walls, bathrooms, wood, plywood, laminated wood , A board made of a wood-based material such as a particle board or a hard board; or a board made of a metal-based material such as iron or aluminum and a decorative film attached to the surface thereof. ing. A decorative film is required to have not only decorative properties but also high impact resistance, bending resistance, moldability and the like in a well-balanced manner. In recent years, polyester-based resin films, particularly non-crystalline polyester-based resin films have high transparency and gloss, and are excellent in impact resistance, bending resistance, and moldability. It is frequently used for decorative films. However, the polyester resin film has a problem that the adhesiveness with the printing layer is insufficient for applying to three-dimensional molding such as membrane press molding, vacuum molding, and vacuum pressure molding.

  Therefore, "Amorphous polyethylene terephthalate comprising a resin obtained by copolymerizing a dicarboxylic acid component composed of terephthalic acid and a diol component composed of 25 to 35 mol% of 1,4-cyclohexanedimethanol and 65 to 75 mol% of ethylene glycol. A base layer made of a colored resin material containing a base resin as a main component, and a printing formed of a colored ink formed on one surface of the base layer and containing a binder containing a vinyl chloride-vinyl acetate copolymer as a main component. A pattern layer, a dicarboxylic acid component composed of terephthalic acid and a diol component composed of 25-35 mol% of 1,4-cyclohexanedimethanol and 65-75 mol% of ethylene glycol, which are formed on the printed pattern layer by lamination. Transparent amorphous polyethylene terephthalate resin composed of copolymerized resin It provided that a transparent layer, the three-dimensional processing decorative sheet, characterized in that the lamination strength between the transparent layer and the base layer is obtained. "Is proposed (Patent Document 1). However, according to the study of the present inventors, the technique of Patent Document 1 has insufficient adhesion between the polyester resin film and the printing layer in order to decorate an article having a complicated shape.

Japanese Patent No. 3678063

  An object of the present invention is to apply a polyester resin laminate excellent in adhesion to a print layer and to a membrane press molding, a vacuum molding, and a vacuum pressure molding using the same to apply an article having a complicated shape. An object of the present invention is to provide a decorative film that can be decorated.

  As a result of intensive studies, the present inventor has found that the above object can be achieved by using a specific polyester resin.

That is, the present invention provides (A) a (B) vinyl chloride-vinyl acetate copolymer on at least one surface of a resin film containing a (a) polyester copolymer having the following properties (1) to (5). Is a laminate in which a printing layer made of a coloring ink containing is formed.
(1) Assuming that the total of the structural units derived from the dicarboxylic acid component is 100 mol%, 98 to 100 mol% of the structural units derived from terephthalic acid is included.
(2) Assuming that the total of the structural units derived from the diol component is 100 mol%, 60.5 to 72.5 mol% of the structural units derived from ethylene glycol, 1.5 to 6 mol% of the structural units derived from diethylene glycol, and Contains 26 to 38 mol% of structural units derived from 1,4-cyclohexanedimethanol.
(3) The structural unit derived from the 1,4-cyclohexanedimethanol is composed of 65 to 75 mol% of the trans isomer and 35 to 25 mol% of the cis isomer, wherein the trans isomer and the cis isomer are used. Is 100 mol%.
(4) The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene obtained from the differential molecular weight distribution curve measured by gel permeation chromatography is 2.9 to 3.8. is there.
(5) The number average molecular weight (Mn) is 16,000 to 24,000.

  According to a second aspect of the present invention, in the polyester-based copolymer (a), 60.5 to 71.5 mol% of a structural unit derived from ethylene glycol is defined as 100 mol% of a total of structural units derived from a diol component, The laminate according to the first invention, comprising 2 to 5 mol% of a structural unit derived from 1, and 26 to 37 mol% of a structural unit derived from 1,4-cyclohexanedimethanol.

In a third aspect, the colored ink comprises a vehicle comprising (P) 60 to 95% by mass of a vinyl chloride-vinyl acetate copolymer; and (Q) 40 to 5% by mass of a polymethyl methacrylate-based resin. Here, the laminate according to the first or second invention, wherein the sum of the component (P) and the component (Q) is 100% by mass.

  According to a fourth aspect of the present invention, there is provided (A1) a layer of a transparent resin film containing the (a) polyester-based copolymer, (B) a printing layer made of a colored ink containing a vinyl chloride-vinyl acetate copolymer, and (A2) (A) The laminate according to any one of the first to third inventions, having a layer of a colored resin film containing a polyester-based copolymer in this order.

  The polyester resin laminate of the present invention is excellent in adhesion to a print layer. Therefore, the decorative film using the polyester-based resin laminate of the present invention can be applied to three-dimensional forming such as membrane press forming, vacuum forming, and vacuum press forming, and can decorate an article having a complicated shape.

This is a substrate used in evaluation of vacuum formability. It is a figure explaining a vacuum forming method. It is an example of a ¹ H-NMR spectrum measurement.

  In this specification, the term “resin” is used as a term including “a resin mixture containing two or more resins” and “a resin composition containing components other than the resin”. The term “film” is used as a term including “sheet”.

  The laminate of the present invention comprises (B) a vinyl chloride-vinyl acetate copolymer on at least one surface of a resin film containing (A) a polyester-based copolymer having the following properties (1) to (5). A printing layer made of a colored ink containing the coalesced is formed.

(A) Resin film:
The (A) resin film is (a) a film made of a polyester-based copolymer, or (a) a film made of a resin mixture or a resin composition of a polyester-based copolymer and an optional component used as desired. .

(A) Polyester copolymer:
The component (a) is preferably 98 to 100 mol%, more preferably 99 to 100 mol%, more preferably 99 to 100 mol%, of the structural units derived from terephthalic acid, with the total of the structural units derived from the dicarboxylic acid component (1) being 100 mol%. Is contained in an amount of 100 mol%. When the component (a) contains a structural unit derived from terephthalic acid in the above amount as a structural unit derived from a dicarboxylic acid component, a polyester resin laminate excellent in adhesion to a print layer can be obtained.

  Examples of the dicarboxylic acid component other than terephthalic acid that can be used for the component (a) include aromatic polycarboxylic acids such as isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid and derivatives thereof; oxalic acid, malonic acid, and succinic acid , Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylate Aliphatic polycarboxylic acids such as acrylates and derivatives thereof; and the like. As the dicarboxylic acid component other than terephthalic acid, one or more of these can be used.

  The component (a) is composed of 60.5 to 72.5 mol% of a structural unit derived from ethylene glycol and a structural unit derived from diethylene glycol, with the total sum of the structural units derived from the (2) diol component being 100 mol%. 5 to 6 mol%, and 26 to 38 mol% of structural units derived from 1,4-cyclohexanedimethanol. Preferably, assuming that the total of the structural units derived from the diol component is 100 mol%, 60.5 to 71.5 mol% of the structural units derived from ethylene glycol, 2 to 5 mol% of the structural units derived from diethylene glycol, and 1, Contains 26 to 37 mol% of structural units derived from 4-cyclohexanedimethanol. Here, the sum of the constituent units derived from ethylene glycol, the constituent units derived from diethylene glycol, and the constituent units derived from 1,4-cyclohexanedimethanol is usually 98 to 100 mol%, preferably 99 to 100 mol%, Preferably it is 100 mol%. When the component (a) is contained in the above amount as a structural unit derived from the diol component, a polyester resin laminate excellent in adhesion to the print layer can be obtained.

  The diol components other than ethylene glycol, diethylene glycol and 1,4-cyclohexanedimethanol that can be used for the component (a) include neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol and 1,4-butanediol. Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, and 2,2,4,4-tetramethyl-1,3-cyclobutane Examples include polyhydric alcohol components such as diols. As the diol component other than the above-mentioned ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol, one or more of these can be used.

  The constituent unit of the component (a) derived from (3) the 1,4-cyclohexanedimethanol is composed of 65 to 75 mol% of the trans isomer and 35 to 25 mol% of the cis isomer. Here, the sum of the trans isomer and the cis isomer is 100 mol%. When the ratio between the trans isomer and the cis isomer is within the above range, a polyester resin laminate having excellent adhesion to the print layer can be obtained.

  The 1,4-cyclohexanedimethanol can be obtained by a known method, for example, a method of hydrogenating 1,4-cyclohexanedicarboxylic acid dimethyl ester in the presence of a copper chromium catalyst and then distilling the same. The ratio between the trans isomer and the cis isomer can be adjusted by a known method, for example, the method described in Japanese Patent No. 2537401.

The ratio of the structural unit derived from each component in the component (a) and the ratio between the trans isomer and the cis isomer of the structural unit derived from 1,4-cyclohexanedimethanol are determined by ¹³ C-NMR or ¹ H. -It can be determined using NMR.

¹³ C-NMR spectrum, for example, a sample 20mg was dissolved in chloroform -d ₁ solvent 0.6 mL, using a 125MHz nuclear magnetic resonance device can be measured under the following conditions.
Chemical shift standard Chloroform-d ₁ : 77 ppm
Measurement mode Single pulse proton broadband decoupling Pulse width 45 ° (5.00 μs)
Number of points 64K
Observation range 250 ppm (-25 to 225 ppm)
Repetition time 5.5 seconds Total number of times 256 Measurement temperature 23 ° C
Window function exponential (BF: 1.0 Hz)

¹ H-NMR spectrum, for example, a sample 20mg was dissolved in chloroform -d ₁ solvent 0.6 mL, using a nuclear magnetic resonance apparatus 400MHz, it can be measured under the following conditions. FIG. 3 shows a measurement example.
Chemical shift standard Chloroform: 7.24 ppm
Measurement mode Single pulse Pulse width 45 ° (5.14 μs)
Points 16k
Measurement range 15 ppm (-2.5 to 12.5 ppm)
Repetition time 7.8 seconds Total number of times 64 Measurement temperature 23 ° C
Window function exponential (BF: 0.18 Hz)

The peak assignments are described in “Polymer Analysis Handbook (First Edition, September 20, 2008, First Edition, edited by the Society for Analytical Chemistry of Japan, edited by the Society for Polymer Analysis, Asakura Shoten Co., Ltd., pages 496-503)” and “ Based on the NMR database (http://polymer.nims.go.jp/NMR/) of the National Institute for Materials Science, Material Information Station, and refer to the peak area ratio for each component in the component (a). The ratio can be calculated. The measurement of ¹³ C-NMR and ¹ H-NMR can also be performed by an analytical institution such as Mitsui Chemical Analysis Center.

  The component (a) is (4) the ratio (Mw / Mn) between the mass average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene determined from a differential molecular weight distribution curve measured by gel permeation chromatography (GPC). Is 2.9 to 3.8, preferably 3.3 to 3.6. When the Mw / Mn of the component (a) is within the above range, a polyester resin laminate excellent in adhesion to a print layer is obtained.

  The component (a) has (5) the number average molecular weight (Mn) of 16,000 to 24,000. When the Mn of the component (a) is within the above range, a polyester resin laminate excellent in adhesion to a print layer is obtained.

  Gel permeation chromatography (GPC) is measured by a high-performance liquid chromatography system “LC-2000Plus (trade name)” of JASCO Corporation (Degasser, liquid pump “PU-2080 (trade name)”, an autosampler “ AS-2055 (trade name) ", a system including a column oven and an RI (differential refractive index) detector); and a column packed with Showa Denko's styrene divinylbenzene copolymer," Shodex GPC K- ". 806L (trade name) "connected and used; chloroform for high performance liquid chromatography (including ethanol as a stabilizer) of Wako Pure Chemical Industries, Ltd. as a mobile phase; flow rate of 1.0 ml / min, column Temperature 40 ° C, sample concentration 1 mg / ml, sample injection amount 100 my It can be carried out under the conditions of Rorittoru. The elution amount in each holding volume is determined from the amount detected by the RI detector, assuming that the refractive index of the polyester does not depend on the molecular weight. The calibration curve from the holding capacity to the molecular weight in terms of polystyrene is obtained by standard polystyrene “EasiCal PS-1 (trade name)” (Agilent Technology) (Molecular weight of Plain A: 6870000, 841700, 152800, 28770, 2930; Plain). B (molecular weight 2348000, 327300, 74800, 10110, 580). The analysis program uses "ChromNAV GPC (trade name)" of JASCO Corporation. Regarding the theory of GPC and the actual measurement, please refer to Kyoritsu Shuppan Co., Ltd.'s reference book such as "Size Exclusion Chromatography High-Performance Liquid Chromatography of Polymers, Author: Sadao Mori, First Edition, First Printing, December 10, 1991". Can be referenced.

  The component (a) uses terephthalic acid as a dicarboxylic acid component and other dicarboxylic acids used as required in a predetermined amount, and as a diol component, ethylene glycol, diethylene glycol, 1,4-cyclohexanedimethanol, and optionally It can be obtained by using a predetermined amount of other diol components to be used and copolymerizing by a known method. The method of the above copolymerization may be a direct esterification reaction or a transesterification reaction, and is not limited. Further, it may be a batch type or a continuous type, and is not limited.

  It is known that when ethylene glycol is used as a diol component in the production of polyester, structural units derived from diethylene glycol generated by a condensation reaction of ethylene glycol are produced in the production process. However, the amount of the structural unit derived from diethylene glycol in the component (a) greatly exceeds the amount of the structural unit derived from diethylene glycol generated by a condensation reaction of ethylene glycol in a usual production method. Therefore, in order to obtain the component (a), usually, a predetermined amount of diethylene glycol is used as the diol component. However, in order to obtain the component (a), a method for increasing the amount of diethylene glycol produced as a by-product by increasing the condensation reaction of ethylene glycol so that the amount of structural units derived from diethylene glycol is within a predetermined range is eliminated. Not something.

  The resin mixture or resin composition of the above-mentioned (a) polyester-based copolymer and optional components used as desired contains the above-mentioned component (a) in an amount of usually 75% by mass or more, preferably 85% by mass or more.

  As the above optional components, thermoplastic resins other than the above component (a); pigments, inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, weather resistance stabilizers, heat stabilizers, release agents, antistatic agents And additives such as surfactants. The mixing amount of these optional components is usually about 0.1 to 30 parts by mass when the component (a) is 100 parts by mass.

  Among the above optional components, preferred are core-shell rubbers. Examples of the core shell rubber include methacrylic acid ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, acrylonitrile / styrene / acryl An acid ester graft copolymer, a methacrylic ester / acrylic ester rubber graft copolymer, a methacrylic ester / acrylonitrile / acrylic ester rubber graft copolymer, and the like can be given. One or a mixture of two or more of these can be used as the core-shell rubber.

  The polyester resin film used in the laminate of the present invention is made of a resin mixture or a resin composition of the above component (a) or the component (a) and an optional component used as desired, and is provided with an arbitrary device, for example, a calender roll. It can be obtained using a processing machine, an apparatus equipped with an extruder and a T-die, and the like. Examples of the calender roll processing machine include an upright type three roll, an upright type four roll, an L type four roll, an inverted L type four roll and a Z type roll. Examples of the extruder include a single-screw extruder, a co-rotating twin-screw extruder, and a different-rotating twin-screw extruder. Examples of the T die include a manifold die, a fish tail die, and a coat hanger die.

  The thickness of the resin film (A) may be usually 30 to 1000 μm, preferably 50 to 600 μm, more preferably 80 to 300 μm.

(B) Printing layer:
The printing layer (B) is made of a coloring ink containing a vinyl chloride-vinyl acetate copolymer. The coloring ink is obtained by appropriately mixing a pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like with a vehicle. The vehicle contains a vinyl chloride-vinyl acetate copolymer in an amount of usually at least 25% by mass, preferably at least 50% by mass, more preferably at least 60% by mass. Therefore, the laminate of the present invention is a polyester resin laminate having excellent adhesion to the print layer.

  Preferable examples of the vinyl chloride-vinyl acetate copolymer include a structural unit derived from vinyl acetate in an amount of 5 to 25% by mass, preferably 10 to 20% by mass, with the total of the structural units being 100% by mass. Can be included.

  Examples of other vehicles other than the vinyl chloride-vinyl acetate copolymer that can be contained in the coloring ink include, for example, acrylic resins, urethane resins, polyester resins, and cellulose resins. One or more of these can be used as the other vehicle. Among these, an acrylic resin is preferable, a polyalkyl methacrylate resin is more preferable, and a polymethyl methacrylate resin (the total of the structural units is 100% by mass, and the structural unit derived from methyl methacrylate is 95% by mass. Or more, preferably 97% by mass or more, more preferably 99% by mass or more).

  Preferred examples of the vehicle include 60 to 95% by mass, preferably 70 to 90% by mass of the vinyl chloride-vinyl acetate copolymer; and 40 to 5% by mass, preferably 30 to 10% by mass of an alkyl polymethacrylate resin. %;

  The pigment used in the coloring ink is not particularly limited, and known pigments can be used as desired. Examples of the pigment include inorganic pigments such as titanium oxide (white), carbon black, red iron oxide, and ultramarine (ultramarine); organic pigments such as aniline black, quinacridone red, isoindolinone yellow, and phthalocyanine blue; Extenders such as calcium carbonate, barium sulfate, silicon oxide, and aluminum oxide; As the pigment, one or a mixture of two or more of these pigments can be used.

  The content of the pigment in the colored ink depends on the compatibility between the vehicle and the pigment from the viewpoint of adhesion between the (A) resin film and the (B) printing layer, with the vehicle being 100 parts by mass. , Usually 100 parts by mass or less, preferably 50 parts by mass or less. There is no particular lower limit for the content, and the content can be arbitrarily set according to the desired design.

  Examples of the solvent used for the coloring ink include methanol, ethanol, 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, acetone, and mixtures thereof. . Among these, a solvent containing 1-methoxy-2-propanol in an amount of 40% by mass or more is preferable from the viewpoint that the surface gloss of the resin film (A) is not impaired in forming the print layer (B). A solvent containing 80% by mass or more of 1-methoxy-2-propanol is more preferable.

  The pattern provided by the printing layer (B) is not particularly limited, and an arbitrary pattern can be provided. Examples of the pattern include a metal pattern such as a hairline, a grain pattern, a stone pattern imitating the surface of a rock such as marble, a fabric pattern imitating a grain or cloth pattern, a tiled pattern, a brickwork pattern, and a parquet. Patterns, patchwork, and the like.

  The method for forming the printing layer (B) on the resin film (A) is not particularly limited, and a known printing method can be used. Specifically, there may be mentioned methods such as letterpress printing, gravure printing, lithographic offset printing, and screen printing.

  The thickness of the printing layer (B) is not particularly limited, but may be usually 0.5 to 10 μm, preferably 1 to 5 μm.

  In addition, the (A) resin film may be subjected to an easy adhesion treatment such as a corona discharge treatment or an anchor coat in advance on the (B) printing layer forming surface. After performing corona discharge treatment, an anchor coat may be further formed.

  The decorative film of the present invention is preferably, in order from the surface layer side, (A1) a layer of the (a) transparent resin film containing a polyester-based copolymer, and (B) a coloring containing a vinyl chloride-vinyl acetate copolymer. It has a printing layer made of ink, and (A2) a layer of a colored resin film containing the (a) polyester-based copolymer. By providing the resin film layer containing the polyester copolymer (a) on both sides of the printing layer (B), the effect of suppressing cracks and cracks in printing is further enhanced. By providing the above (A1) transparent resin film layer on the above (B) printing layer, a design with a sense of depth can be provided.

  A method of decorating an article having a complicated shape by applying the decorative film of the present invention to three-dimensional molding such as membrane press molding, vacuum molding, and vacuum pressure molding will be described with reference to an example of vacuum molding.

FIG. 2 shows an example of vacuum forming. When performing vacuum forming, first, as shown in FIG. 2A, the decorative film (1) is heated and softened by an infrared heater (2) or the like. Subsequently, the softened decorative film (1) is removed from the infrared heater (2), and is quickly coated on the substrate (3) (FIG. 2 (b)). Thereafter, the space (4) between the decorative film (1) and the substrate (3) is depressurized, and the decorative film (1) is brought into close contact with the substrate (3), and is covered with a decorative film (decoration). A molded product (5) is obtained (FIG. 2 (c)). The pressure in the space (4) is preferably 10 KPa or less, more preferably 1 KPa or less, from the viewpoint of sufficiently adhering without leaving air between the decorative film (1) and the base (3). Note that the adhesion force increases as the pressure in the space (4) decreases, but it is practically necessary to reduce the pressure in consideration of the fact that the cost is accelerated and the mechanical strength of the substrate or the film is taken into consideration. The lower limit of the pressure in (4) is about 10 ⁻⁵ KPa.

  Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Measurement method (a) Cross-cut test:
According to JIS K 5600-5-6: 1999, 100 squares (1 square = 1 mm × 1 mm) are cut from the printed layer side of the laminate, and then a tape for adhesion test is stuck on the grid and the finger is cut. After being squeezed, it was peeled off. The evaluation criteria were in accordance with Table 1 of the above JIS standard.
Category 0: The edges of the cut are completely smooth, and there is no peeling of any grid.
Category 1: Small peeling of the coating film at the intersection of cuts. Affected in the crosscut portion does not clearly exceed 5%.
Category 2: The coating peels off along the edges of the cut and / or at intersections. Affected in the crosscut section is clearly more than 5% but not more than 15%.
Classification 3: The coating film is partially or completely peeled off along the edge of the cut, and / or various parts of the eyes are partially or completely peeled off. Affected in the crosscut portion is clearly more than 15% but not more than 35%.
Class 4: The coating film is partially or completely peeled off along the edge of the cut, and / or several eyes are partially or completely peeled off. Affected in the crosscut portion is clearly over 35% but not over 65%.
Category 5: When the degree of peeling exceeds category 4.

(B) Vacuum formability:
(1) Production of resin substrate:
Using ABS / PC alloy resin "Exceloy CK50 (trade name)" manufactured by Techno Polymer Co., Ltd., using a 100-ton injection molding machine, cylinder temperature 260 ° C, mold temperature 70 ° C, injection speed 250mm / sec, and holding Under a condition of a pressure of 50 MPa, a substrate made of a thermoplastic resin was injection molded. FIG. 1 is a photograph of the obtained substrate.
(2) Production of molded articles:
Using the substrate obtained in the above (1) and the decorative film, a molded product in which the surface of the substrate was decorated with the decorative film as described above was obtained by using a vacuum forming method. At this time, the pressure in the space (4) was 1.0 × 10 ⁻³ KPa. The printed layer was located outside the molded product. The obtained molded article was conditioned for 24 hours or more in an environment at a temperature of 23 ° C. and a relative humidity of 50%.
(3) Evaluation of vacuum formability:
The appearance of the molded article obtained in the above (2) was visually observed and evaluated according to the following criteria.
：: No defective appearance such as cracks, cracks, swelling, and irregularities is observed.
Δ: At a portion having a small radius of curvature, poor appearance such as slight cracking or cracking is observed.
×: Appearance defects such as cracks, cracks, blisters, and irregularities are observed.

Raw materials used (a) polyester-based copolymer:
(A-1) to (a-8) Polyester copolymers having the characteristics shown in Table 1 or 2.

(A ′) Comparative polyester copolymer:
(A'-1) to (a'-6) Polyester copolymers having the properties shown in Table 2 or 3.

  In the above table, TPA is the amount of structural units derived from terephthalic acid, CHA is the amount of structural units derived from 1,4-cyclohexanedicarboxylic acid, DEG is the amount of structural units derived from diethylene glycol, EG Is the amount of the structural unit derived from ethylene glycol, CHDM is the amount of the structural unit derived from 1,4-cyclohexanedimethanol, and trans is the trans isomer in the structural unit derived from 1,4-cyclohexanedimethanol. And the cis mean the ratio of the cis isomer in the structural unit derived from 1,4-cyclohexanedimethanol.

(B) Colored ink:
(B-1)
80% by mass of vinyl chloride-vinyl acetate copolymer (content of structural units derived from vinyl acetate: 15% by mass) and 20% by mass of polymethyl methacrylate resin (content of structural units derived from methyl methacrylate: 100% by mass) % Ink as a vehicle with a mixture of%. The red pigment is contained in an amount of 52 parts by mass based on 100 parts by mass of the vehicle. The solvent is a mixed solvent of methyl ethyl ketone: 1-methoxy-2-propanol = 20: 80 (mass ratio).
(B-2)
80% by mass of vinyl chloride-vinyl acetate copolymer (content of structural units derived from vinyl acetate: 15% by mass) and 20% by mass of polymethyl methacrylate resin (content of structural units derived from methyl methacrylate: 100% by mass) A blue ink with a mixture of% and vehicle. The blue pigment is contained in an amount of 47 parts by mass based on 100 parts by mass of the vehicle. The solvent is a mixed solvent of methyl ethyl ketone: 1-methoxy-2-propanol = 20: 80 (mass ratio).
(B-3)
55% by mass of vinyl chloride-vinyl acetate copolymer (content of structural units derived from vinyl acetate: 15% by mass) and 45% by mass of polymethyl methacrylate resin (content of structural units derived from methyl methacrylate: 100% by mass) % Ink as a vehicle with a mixture of%. The red pigment is contained in an amount of 52 parts by mass based on 100 parts by mass of the vehicle. The solvent is a mixed solvent of methyl ethyl ketone: 1-methoxy-2-propanol = 20: 80 (mass ratio).
(B-4)
55% by mass of vinyl chloride-vinyl acetate copolymer (content of structural units derived from vinyl acetate: 15% by mass) and 45% by mass of polymethyl methacrylate resin (content of structural units derived from methyl methacrylate: 100% by mass) A blue ink with a mixture of% and vehicle. The blue pigment is contained in an amount of 47 parts by mass based on 100 parts by mass of the vehicle. The solvent is a mixed solvent of methyl ethyl ketone: 1-methoxy-2-propanol = 20: 80 (mass ratio).

(B ') Comparative coloring ink:
(B'-1)
Red ink using acrylic resin as vehicle. The red pigment is contained in an amount of 52 parts by mass based on 100 parts by mass of the vehicle. The solvent is a mixed solvent of methyl ethyl ketone: 1-methoxy-2-propanol = 20: 80 (mass ratio).
(B'-2)
Blue ink using acrylic resin as vehicle. The blue pigment is contained in an amount of 47 parts by mass based on 100 parts by mass of the vehicle. The solvent is a mixed solvent of methyl ethyl ketone: 1-methoxy-2-propanol = 20: 80 (mass ratio).

Example 1
Using a resin composition of 100 parts by mass of the above (a-1) and 12 parts by mass of titanium oxide (white pigment) “Taipeku CR-60-2 (trade name)” by Ishihara Sangyo Co., Ltd., an extruder and a T-die were used. Using a film forming apparatus provided, a resin film having a thickness of 200 μm was formed at a die exit resin temperature of 230 ° C. Subsequently, a printed layer having a thickness of 3 μm was formed on one surface of the resin film obtained above using the above (b-1) and the above (b-2) by a direct gravure printing method. The above tests (a) to (d) were performed. Table 1 shows the results.

Examples 2 to 8, Comparative Examples 1 to 6
All of the procedures were performed in the same manner as in Example 1 except that the polyester-based copolymer shown in any one of Tables 1 to 3 was used instead of the above (a-1). The results are shown in any one of Tables 1 to 3.

Comparative Example 7
The same procedures were performed as in Example 1 except that (b′-1) and (b′-2) were used instead of (b-1) and (b-2). Table 3 shows the results.

  The laminate of the present invention has good adhesion (cross-cut test) between the (A) resin film and the (B) printing layer, and also has a good appearance of a vacuum-formed product. On the other hand, in the comparative example, the adhesion between the resin film and the printing layer was insufficient, and the appearance of the vacuum molded product was also unsatisfactory.

1: decorative film 2: heater 3: substrate 4: space between decorative film and substrate 5: molded product

Claims (8)

(A) A colored ink containing a vinyl chloride-vinyl acetate copolymer (B) on at least one surface of a resin film containing a (a) polyester copolymer having the following properties (1) to (5): A laminate on which a printing layer is formed.
(1) Assuming that the total of the structural units derived from the dicarboxylic acid component is 100 mol%, 98 to 100 mol% of the structural units derived from terephthalic acid is included.
(2) Assuming that the total of the structural units derived from the diol component is 100 mol%, 60.5 to 72.5 mol% of the structural units derived from ethylene glycol, 1.5 to 6 mol% of the structural units derived from diethylene glycol, and Contains 26 to 38 mol% of structural units derived from 1,4-cyclohexanedimethanol.
(3) The structural unit derived from the 1,4-cyclohexanedimethanol is composed of 65 to 75 mol% of the trans isomer and 35 to 25 mol% of the cis isomer, wherein the trans isomer and the cis isomer are used. Is 100 mol%.
(4) The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene obtained from the differential molecular weight distribution curve measured by gel permeation chromatography is 2.9 to 3.8. is there.
(5) The number average molecular weight (Mn) is 16,000 to 24,000.   (A) 60.5 to 71.5 mol% of a structural unit derived from ethylene glycol, and a structural unit 2 derived from diethylene glycol, wherein the total amount of the structural units derived from the diol component is 100 mol%. 2. The laminate according to claim 1, comprising from 5 to 5 mol% and from 26 to 37 mol% of structural units derived from 1,4-cyclohexanedimethanol. The coloring ink,
A vehicle comprising (P) a vinyl chloride-vinyl acetate copolymer 60 to 95% by mass; and (Q) a polymethyl methacrylate resin 40 to 5% by mass;
The laminate according to claim 1 or 2, wherein the sum of the component (P) and the component (Q) is 100% by mass.   The laminate according to any one of claims 1 to 3, wherein the (A) resin film includes the (a) polyester-based copolymer and a core-shell rubber. (A1) a layer of the transparent resin film containing the (a) polyester-based copolymer,
A printing layer comprising a colored ink containing a (B) vinyl chloride-vinyl acetate copolymer, and (A2) a layer of a colored resin film containing the (a) polyester-based copolymer, in this order. 5. The laminate according to any one of 4 . A decorative film comprising the laminate according to any one of claims 1 to 5 . An article comprising the decorative film according to claim 6 .   A method of using the laminate according to any one of claims 1 to 5 for three-dimensional molding.