JP5286043B2 - Vacuum forming sheet - Google Patents

Description

  The present invention relates to a vacuum forming sheet, and more specifically, without generating a drag line (streak-like trace) on the surface of a three-dimensional coated molded product, heat resistant appearance (50 ° C. × 400 hours, 80 ° C. × 400 hours), excellent in productivity (simplification of the process), with no release material deterioration when stored for a long time with a release material, and in addition, heat-resistant adhesiveness in a three-dimensional coated molded product (50 ° C. × 400 The present invention relates to a vacuum forming sheet excellent in time, 80 ° C. × 400 hours.

  Conventionally, automotive interior / exterior parts, home appliance parts, building material parts, etc. for decorative purposes have been subjected to molding such as injection molding, vacuum molding and in-mold molding, and then the surface of the molded product is applied by spray coating or the like. , Dried and heat-cured to impart design properties such as surface protection, coloring and decoration of the molded product. However, such a coating has a problem of low productivity because it requires a work environment problem with respect to the discharge of the volatile organic solvent and a work process and production equipment such as coating, drying, and heat curing for each molded product.

  On the other hand, in recent years, a decorative laminated sheet made of a soft thermoplastic resin having a design property at the time of molding processing is provided, and the decorative laminated sheet is bonded to the surface of the molded product, thereby providing a coated molded product having a design property. Many methods have been proposed to obtain The decorative laminated sheet is made of a thermoplastic resin that can follow the three-dimensional deformation during thermoforming, so there are no problems such as cracking, tearing or peeling of the coating film during molding, and there is no painting process So work environment and productivity are excellent.

  For example, the following Patent Documents 1 to 3 disclose a method for obtaining the above-described coated molded product by employing a vacuum molding method.

In Patent Document 4, a decorative layer is provided on one surface of a thermoformable transparent plastic film. On the decorative layer, a softening point is 80 ° C., a loss elastic modulus at 130 ° C. is 10,000 Pa, and a film thickness. Discloses a molded sheet for decorating a molded product, wherein an adhesive layer having a thickness of 20 to 150 μm is provided.
However, the three-dimensional coated molded product molded using the molded decorative sheet of the patent document has a problem that a drag line (streak-like trace) appears on the surface, and heat resistant appearance (50 ° C. × 400 hours, 80 ° C. × 400 hours) and productivity (simplification of processes) is inferior. Furthermore, a three-dimensional coated molded article prepared using an adhesive as described in the patent document has a problem that it is inferior in heat-resistant adhesion (50 ° C. × 400 hours, 80 ° C. × 400 hours).

Patent Document 5 discloses the manufacture of a vehicle window frame panel in which the surface of an aluminum window frame panel is coated with a synthetic resin sheet having a pressure-sensitive adhesive layer having a mesh-shaped communication groove formed on the surface thereof by vacuum lamination molding. A first step of placing both molding chambers of a vacuum molding machine having a first molding chamber and a second molding chamber into a substantially vacuum state, and secondly softening the synthetic resin decorative sheet by heating. Process, third step of covering the softened synthetic resin decorative sheet on the aluminum window frame panel disposed in the second molding chamber, increasing the pressure in the first molding chamber to the shape of the aluminum window frame panel The manufacturing method of the window frame panel for vehicles characterized by consisting of the 4th process which pressurizes this synthetic resin decorative sheet so that it follows is disclosed.
However, when the synthetic resin sheet of the patent document is stored for a long time with a release material, there is a problem that the appearance is deteriorated due to the difference in shrinkage rate between the synthetic resin sheet and the release material. Furthermore, the three-dimensional coated molded article prepared using the adhesive or pressure-sensitive adhesive described in the patent document has a problem that it is inferior in heat resistant adhesiveness (50 ° C. × 400 hours, 80 ° C. × 400 hours). . There was also room for improvement in the drag lines (streak-like traces) appearing on the surface of the three-dimensional coated molded product.
Japanese Examined Patent Publication No. 56-45768 Japanese Patent No. 3016518 Japanese Patent No. 3733564 JP 2007-70518 A JP 2004-237510 A

  Therefore, the object of the present invention is not to generate drag lines (streak-like traces) on the surface of the three-dimensional coated molded product, but to have heat resistant appearance (50 ° C. × 400 hours, 80 ° C. × 400 hours), productivity (process (Simplification) is excellent, and when it is stored for a long time with a release material, the appearance of the sheet does not deteriorate, and furthermore, the heat-resistant adhesiveness (50 ° C. × 400 hours, 80 ° C. × 400 hours) in a three-dimensional coated molded product The object is to provide an excellent vacuum forming sheet.

The present invention is as follows.
1. It is a sheet for vacuum forming having an adhesive layer (I) on the lower surface of the surface layer film (A),
The surface layer film (a) is an acrylic resin film (A), a biaxially stretched copolymer polyethylene terephthalate film (B), an unstretched amorphous polyethylene terephthalate resin film (C), a polyvinyl chloride resin film ( D) or a polycarbonate-based resin film (E), and the adhesive layer (A) is obtained by blending 1.5 to 2.5 equivalents of polyisocyanate in the following thermoplastic saturated copolymer polyester resin and curing. And has one or more grooves on the surface opposite to the surface bonded to the surface film (a), and the grooves are present only on the inner side of the opposite surface of the adhesive layer (a). And a groove that does not communicate with the side surface of the adhesive layer (a) and a groove that communicates with the side surface on the opposite surface.
Thermoplastic saturated copolyester resin: an acid component composed of 20 to 40 mol% terephthalic acid, 20 to 40 mol% isophthalic acid and 25 to 50 mol% adipic acid (however, the total of the acid components is 100 mol%); The glycol component is composed of 10 to 50 mol% of 1,4-butanediol and 50 to 90 mol% of 1,6-hexanediol (however, the total of the glycol components is 100 mol%).
2. 2. The vacuum forming sheet according to 1 above, wherein the thermoplastic saturated copolymer polyester resin has a softening temperature of 55 to 85 ° C.
3. 3. The vacuum forming sheet as described in 1 or 2 above, wherein a backer layer (c) is provided between the surface layer film (a) and the adhesive layer (a).
4). 4. The vacuum forming sheet as described in 3 above, wherein the backer layer (c) is an unstretched amorphous polyethylene terephthalate resin film (F) or a polyvinyl chloride resin film (G).
5. 5. The vacuum forming sheet as described in any one of 1 to 4 above, wherein the polyisocyanate is a polyisocyanate composed of hexamethylene diisocyanate.
6). The unstretched amorphous polyethylene terephthalate resin film (C) comprises an acid component composed of terephthalic acid, and a glycol component composed of 60 to 90 mol% ethylene glycol and 10 to 40 mol% cyclohexanedimethanol (however, the glycol component) The total is 100 mol%). The vacuum forming sheet as described in any one of 1 to 5 above.
7). The unstretched amorphous polyethylene terephthalate resin film (F) comprises an acid component composed of terephthalic acid, and a glycol component composed of 60 to 90 mol% ethylene glycol and 10 to 40 mol% cyclohexanedimethanol (however, the glycol component) (5) is a sheet for vacuum forming as described in (4) above.
8). 2. The vacuum forming sheet according to 1 above, wherein the groove has a width of 5 to 100 μm and a depth of 5 to 50 μm.
9. In the front view of the opposite surface of the adhesive layer (a), the grooves not leading to the side surface are linear, linearly branched, cruciform, circular, elliptical or polygonal, and each shape is intermittent. 9. The vacuum forming sheet according to 1 or 8, which may be formed of a plurality of grooves.
10. In the front view of the opposite surface of the adhesive layer (a), the grooves that do not lead to the side surface are present at a density of 1 × 10 to 3.7 × 10 ⁶ per cm ² , 1 or 8 The sheet | seat for vacuum forming in any one of -9.
11. In the front view of the opposite surface of the adhesive layer (a), the plurality of grooves leading to the side surface are arranged in a striped pattern, or each of the adhesive layers separated by the grooves is circular, 11. The vacuum forming sheet according to any one of 1 or 8 to 10 above, which is arranged so as to be elliptical or polygonal.
12 12. The vacuum forming sheet according to 9 or 11, wherein the polygon is a triangle, a quadrangle, or a hexagon.
13. The vacuum forming sheet according to any one of 1 to 12, which is used for vacuum forming by the following vacuum forming method.
Vacuum forming method: The vacuum forming sheet according to any one of 1 to 12 described above and a laminated base material on which the vacuum forming sheet is laminated are arranged opposite to each other, and the first side is placed on the laminated base material side by the vacuum forming sheet. The second chamber is hermetically partitioned from each other on the opposite side, the first chamber and the second chamber are decompressed, and the vacuum forming sheet is heated and softened, and then the vacuum forming sheet And the laminated base material are brought into contact with each other, and thereafter, the decompression of the second chamber is released, and the vacuum forming sheet is placed on the outer surface of the laminated base material by the differential pressure between the first chamber and the second chamber. Vacuum forming method that adheres and laminates.
14 14. A molded product comprising the vacuum molding sheet according to any one of 1 to 13 and a base material made of an ABS resin or an alloy of an ABS resin and a polycarbonate resin, which are laminated by vacuum molding.

  In the present invention, the type of the surface layer film (a) is specified, the composition of the thermoplastic saturated copolymer polyester resin and the amount of polyisocyanate used in the adhesive layer (a) are set within a specific range, and the adhesive is used. Since a predetermined groove is formed on a specific surface of the layer (A), no drag line (streak-like trace) is generated on the surface of the three-dimensional coated molded product, and heat resistant appearance (50 ° C. × 400 hours, 80 ° C. × 400 hours), excellent in productivity (simplification of the process), with no release material deterioration when stored for a long time with a release material, and in addition, heat-resistant adhesiveness in a three-dimensional coated molded product (50 ° C. × 400 The sheet for vacuum forming excellent in time, 80 ° C. × 400 hours) can be provided. Moreover, the vacuum molded product of the vacuum molding sheet of the present invention and a base material made of an ABS resin or an alloy of ABS resin and polycarbonate resin is particularly excellent in adhesion.

  Hereinafter, the present invention will be described in more detail. FIG. 1 is a cross-sectional view for explaining the configuration of the vacuum forming sheet of the present invention. The sheet for vacuum forming 1 of the present invention has an adhesive layer (A) on the lower surface of the surface layer film (A), and a backer between the surface layer film (A) and the adhesive layer (A) as necessary. It has a layer (c). One or more grooves (not shown) are present on the surface 100 of the adhesive layer (A) opposite to the surface bonded to the surface layer film (A). This groove further has a groove that exists only inside the reverse surface 100 and does not communicate with the side surface of the adhesive layer (a), and a groove that communicates with the reverse surface 100 up to the side surface.

Surface film (A)
The surface layer film (a) in the present invention includes an acrylic resin film (A), a biaxially stretched copolymer polyethylene terephthalate film (B), an unstretched amorphous polyethylene terephthalate resin film (C), and a polyvinyl chloride resin. It must be a film (D) or a polycarbonate resin film (E). If it is a film other than these, the effects of the present invention cannot be achieved.

  Examples of the acrylic resin film (A) include polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polyacrylonitrile, or a film made of a copolymer having a (meth) acrylate unit and a styrene unit or a urethane structure. Can do. Furthermore, a mixed resin of the acrylic resin and the thermoplastic polyurethane resin, a mixed resin of the acrylic resin and acrylic rubber, or the like can be used. In the present invention, the acrylic resin, a mixed resin of an acrylic resin and a thermoplastic polyurethane resin, a mixed resin of an acrylic resin and an acrylic rubber, or the like is formed by, for example, a casting method or a calendar method. An unstretched acrylic resin film can be obtained. In the present invention, the above-mentioned unstretched film may be used as the acrylic resin film, and in the case of a stretchable acrylic resin, stretching obtained by uniaxial or biaxial stretching treatment by a conventionally known method. A film may be used.

The biaxially stretched copolymer polyethylene terephthalate film (B) is a resin film obtained by using two or more acid components and / or glycol components. For example, the dicarboxylic acid component is terephthalic acid. A neopentyl glycol copolymerized amorphous polyethylene terephthalate resin in which the glycol components are ethylene glycol 60 to 90 mol% and neopentyl glycol 10 to 40 mol%, and the dicarboxylic acid component is 60 to 98 mol% terephthalic acid and isophthalic acid An isophthalic acid copolymerized amorphous polyethylene terephthalate resin having a glycol component of 2 to 40 mol% and ethylene glycol can be used.
Among these, isophthalic acid copolymerized amorphous polyethylene terephthalate resin is particularly preferable from the viewpoints of biaxial stretchability, three-dimensional moldability, hairline processability, embossability, and the like.
In order to obtain the biaxially stretched copolymer polyethylene terephthalate film (B), a film forming method such as a known tenter method or a tube method can be applied.

As the unstretched amorphous polyethylene terephthalate resin film (C), at least terephthalic acid is used as an acid component, ethylene glycol is used as a glycol component, and an amorphous polyethylene terephthalate resin obtained by reacting them is obtained by known means. The film-formed one can be mentioned.
Among these, from the viewpoint of the effect of the present invention, the unstretched amorphous polyethylene terephthalate resin film (C) is composed of an acid component composed of terephthalic acid, 60 to 90 mol% of ethylene glycol and 10 to 40 mol% of cyclohexanedimethanol. A film of an amorphous polyethylene terephthalate resin composed of a glycol component (however, the total of the glycol components is 100 mol%) is preferable.

  As the polyvinyl chloride resin film (D), any film produced from a hard, semi-rigid or soft composition containing a known vinyl chloride resin as a main component can be used.

As the polycarbonate resin film (E), a dihydric phenol and phosgene are used as raw materials, a polycarbonate resin obtained by an interfacial polycondensation method, or a dihydric phenol and a carbonate precursor such as diphenyl carbonate as raw materials, and a transesterification method. The film of the polycarbonate-type resin obtained by is mentioned.
As the polycarbonate-based resin, a resin obtained by using 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is usually used as a dihydric phenol. In addition, flame retardant polycarbonate resin obtained by using a mixture of bisphenol A and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane (tetrabromobisphenol A) is used as the dihydric phenol. You can also Furthermore, a bisphenol A polycarbonate-polyorganosiloxane copolymer can also be used as a polycarbonate resin with improved impact resistance and flame retardancy.

  The thickness of the surface layer film (a) is preferably 25 μm to 250 μm, and more preferably 50 μm to 150 μm.

Adhesive layer (I)
The adhesive layer (A) in the present invention is obtained by blending 1.5 to 2.5 equivalents of polyisocyanate into the following thermoplastic saturated copolymer polyester resin and curing.
Thermoplastic saturated copolyester resin: an acid component composed of 20 to 40 mol% terephthalic acid, 20 to 40 mol% isophthalic acid and 25 to 50 mol% adipic acid (however, the total of the acid components is 100 mol%); The glycol component is composed of 10 to 50 mol% of 1,4-butanediol and 50 to 90 mol% of 1,6-hexanediol (however, the total of the glycol components is 100 mol%).
In addition, in the acid component, when the minimum amount or the maximum amount of one component is set, the usage amounts of the other two components are adjusted so that the total amount becomes 100 mol%. For example, when the minimum amount of 20 mol% of terephthalic acid is employed, the amount of isophthalic acid and adipic acid used may be adjusted so that the total amount is 100 mol%.

  If any one of the above acid components falls outside the above range, the effects of the present invention cannot be achieved.

  A more preferable thermoplastic saturated copolymer polyester resin is an acid component composed of 25 to 35 mol% terephthalic acid, 25 to 35 mol% isophthalic acid and 30 to 45 mol% adipic acid (however, the total of the acid components is 100 mol%). ) And a glycol component composed of 20 to 40 mol% 1,4-butanediol and 60 to 80 mol% 1,6-hexanediol (however, the total of the glycol components is 100 mol%).

The adhesive layer (A) in the present invention is obtained by blending 1.5 to 2.5 equivalents of polyisocyanate into the above-mentioned thermoplastic saturated copolymer polyester resin and curing it.
Polyisocyanate monomers include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate ( XDI), hydrogenated XDI, triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanate methyloctane, lysine ester triisocyanate, 1,3,6-hexamethylenetri Examples thereof include isocyanate and bicycloheptane triisocyanate. Among these, hexamethylene diisocyanate is preferably used in terms of excellent initial tack, initial adhesion, and heat-resistant adhesion.
In addition, the equivalent of polyisocyanate as used in the field of this invention can be calculated | required by calculation from NCO% in polyisocyanate and the hydroxyl value (KOHmg / g) of a thermoplastic saturated copolyester resin.
In the present invention, the amount of polyisocyanate used is more preferably 1.8 to 2.2 equivalents.

  Moreover, it is preferable that the softening temperature of a thermoplastic saturated copolyester resin is 55-85 degreeC. When the thermoplastic saturated copolyester resin satisfies this softening temperature range, the vacuum moldability is enhanced and the initial tackiness, initial adhesion, and heat-resistant adhesiveness are all significantly improved. The reason is not clear, but according to the study by the present inventors, when the softening temperature of the thermoplastic saturated copolyester resin is 55 to 85 ° C., the thermoplastic saturated copolyester resin has microcrystalline properties. This is presumably because the adhesive force is improved over time from the beginning, and heat resistant adhesiveness can be secured. The softening temperature is a value measured by JIS K-2531 (ring and ball method). The softening temperature can be adjusted by changing the amounts of the acid component and glycol component used.

  The thickness of the adhesive layer (a) after curing is preferably 5 μm to 50 μm, and more preferably 10 μm to 40 μm.

  In the present invention, a backer layer (c) can be provided between the surface layer film (a) and the adhesive layer (a). Due to the presence of the backer layer (c), the vacuum formability is increased and this is preferable.

  The backer layer (c) is not particularly limited, but is preferably an unstretched amorphous polyethylene terephthalate resin film (F) or a polyvinyl chloride resin film (G) from the viewpoint of vacuum moldability.

The unstretched amorphous polyethylene terephthalate resin film (F) includes an acid component composed of terephthalic acid and a glycol component composed of 60 to 90 mol% ethylene glycol and 10 to 40 mol% cyclohexanedimethanol (however, the glycol component) Is preferably 100% by mole).
In addition, as the polyvinyl chloride resin film (G), any film produced from a hard, semi-rigid or soft composition containing a known vinyl chloride resin as a main component can be used.

  The thickness of the backer layer (c) is preferably 50 μm to 300 μm, more preferably 100 μm to 200 μm.

Next, the groove | channel provided in the reverse surface 100 of an adhesive bond layer (I) is demonstrated.
FIG. 2 is a perspective view of one embodiment of the vacuum forming sheet of the present invention as seen from the reverse surface 100 side.
As shown in FIG. 2, the reverse surface 100 has one or more grooves 4. Here, the groove | channel 4 exists only in the inner side of the reverse surface 100 of an adhesive bond layer (a), and does not lead to the side surface of an adhesive bond layer (a).

  Since the adhesive layer (a) has the groove 4 in the vacuum forming sheet of the present invention, a release material having an emboss is attached thereto so that the adhesive layer (a) has a male surface structure. When stored for a long time, there is no difference in shrinkage between the surface film (A) and the release material. This is because the release material (not shown) is attached to the vacuum forming sheet so that the groove 4 is fixed by the male surface structure of the release material (this is called “anchor effect”). This is because shrinkage can be suppressed.

  In addition, as shown in FIG. 3, the reverse surface 100 further has a groove 5 that leads to the side surface of the adhesive layer (A).

By having both the groove 4 and the groove 5, it is possible to prevent the generation of drag lines (streak-like traces) on the surface of the three-dimensional coated molded product and to improve the heat resistant appearance and productivity (simplification of the process). be able to.
During vacuum forming, there is a problem in the contact between the vacuum forming sheet and the base material that is the adherend, and the contact and stretching are repeated step by step, resulting in a difference in the thickness of the vacuum forming sheet, and streak-like marks are formed. Appears on the surface of the product, and in some cases, air is mixed between the vacuum forming sheet and the base material at the streaks. This is called the drag line. In this invention, by having both the groove | channel 4 and the groove | channel 5, the mixing of the said air can be prevented and a drag line does not appear. In addition, deterioration of the appearance such as crushed skin due to blistering on the surface and roughening of the surface is prevented, and heat resistant appearance is improved. Conventionally, in order to eliminate the drag line, a square wall-shaped frame member or a mountain-shaped bank is disposed continuously or discontinuously at an appropriate distance on the outer periphery of the base material, and the vacuum forming sheet and the covering are covered. Although it was necessary to strictly adjust the contact state with the base material to be the adherend, in the present invention, it is possible to prevent the appearance of the drag line simply by providing the groove 4 and the groove 5 in the adhesive layer (a). There is no need to perform a special process using a jig, and productivity is improved. In addition, when only one of the groove | channel 4 and the groove | channel 5 is formed in an adhesive bond layer (I), although the reason is not certain, the said effect is not show | played.

  The groove in the present invention can be selected in an arbitrary shape, and preferably the cross section thereof is a rectangle (a), a trapezoid (b), a U-shape (c) or a triangle (d) as shown in FIG. , Having a width of 5-100 μm and a depth of 5-50 μm. In FIG. 3, w represents the width of the groove, and h represents the depth of the groove.

  Moreover, a groove | channel can have various shapes or patterns in the front view of the surface which has the groove | channel of an adhesive bond layer (I). Examples thereof are shown in FIGS. 4 and 5 are front views of the reverse surface 100 of the adhesive layer (A). In FIGS. 4 and 5, black portions are grooves.

  In the front view of the reverse surface 100 of the adhesive layer (a), the groove 4 not leading to the side surface is, for example, a straight line, a straight branch, a cross, a circle, an ellipse, or a polygon (triangle, square, six Each shape may be composed of a plurality of intermittent grooves. In FIG. 2 described above, the groove 4 has a cross shape. In FIG. 4, the groove 4 is hexagonal, and in FIG. 5, the groove 4 is circular. FIG. 6 is an example in which the linear groove 4 is constituted by a plurality of intermittent grooves.

The groove 4 is present in the adhesive layer (a) in one or more, preferably many, more preferably at a density of 1 × 10 to 3.7 × 10 ⁶ per cm ² , more preferably 1 × 10 ⁶ per cm ^2. A density of ^{2 to} 3.7 × 10 ⁵ exists.

  In addition, the groove 5 leading to the side surface is an adhesive layer (a) in which a plurality of grooves 5 are arranged in a striped pattern or separated by the grooves in the front view of the reverse surface 100 of the adhesive layer (a). ) May be arranged to be circular, elliptical or polygonal (triangular, square, hexagonal, etc.). In FIG. 2, the groove | channel 5 is arrange | positioned at the grid | lattice form, and each of the adhesive bond layer (I) demarcated by this groove | channel is a square. In FIG. 4, the grooves 5 are arranged so that the adhesive layer (a) delimited by the grooves is hexagonal, arranged in a circular shape in FIG. 5, and arranged in a rectangular shape in FIG. ing.

  The grooves 4 and 5 may be randomly arranged on the surface of the adhesive layer (a) or may be arranged in a regular pattern.

The vacuum forming sheet of the present invention can be prepared, for example, as follows. That is, a thermoplastic saturated copolymer polyester resin is dissolved in an organic solvent such as methyl ethyl ketone, a predetermined amount of a polyisocyanate compound is added thereto to form a paint, and the paint is applied on the surface film (a) by a known coating method. And it can prepare by bonding and hardening the peeling material provided with the male surface structure. In addition, the coating material is applied to a release material having a male surface structure, the grooves are formed in the adhesive layer (a), and the surface layer film (a) is bonded to the adhesive layer (a). You can also.
When the backer layer (c) is provided, the surface layer film (a) and the backer layer (c) are laminated by, for example, heat lamination or dry lamination, and the paint is provided on the backer layer (c) by the above method. Can do.
Needless to say, known additives such as weathering agents, antistatic agents and fillers can be added to the surface layer film (a), the adhesive layer (a) and the backer layer (c) as necessary.

  Next, the release material will be described. The release material has a base film and a polyolefin-based resin-containing layer on one or both sides thereof, and at least one of the polyolefin-based resin-containing layers is embossed on the surface opposite to the surface in contact with the base film. The thing which has is mentioned.

  Examples of the base film include paper, biaxially oriented polypropylene, polyethylene terephthalate, void-containing polyethylene terephthalate, phthalic acid isomer copolymerized polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyarylate, and polyether ether. Examples of the resin film include ketone, polyethersulfone, polylactic acid, triacetylcellulose, and polycarbonate. Examples of paper types include glassine paper, high-quality paper, and craft paper. In addition, when the sheet | seat for vacuum forming is for mirror surface finishing, it is preferable to use a resin film.

  The base film preferably has a bending strength by loop stiffness of 0.2 to 1.5 N / 25 mm and a yield point load of 50 to 200 N / 10 mm. When the above value is less than the lower limit, curling tends to occur at the end of the obtained release material, and the handleability is poor. If it exceeds the upper limit, it is too hard to be used as a release material.

  The base film is preferably biaxially stretched or contains a cavity in the film. Examples of the commercially available products include Emblict S125 manufactured by Unitika, Tetron (trademark) S100 manufactured by Teijin, and Crisper K1212 manufactured by Toyobo (cavity-containing biaxially stretched polyethylene terephthalate).

  The thickness of the base film is 50 to 150 μm, preferably 100 to 150 μm, and more preferably 100 to 125 μm. When it is thinner than 50 μm, the resulting release material is likely to curl. If it is larger than 150 μm, it is too thick to be suitable as a release material.

  In the polyolefin-based resin-containing layer provided on one or both surfaces of the base film, the polyolefin-based resin may be (co) heavy of one or more olefins, for example, one or more olefins selected from ethylene, propylene, butylene, butadiene and the like. Coalesced, except for ethylene-methacrylic acid copolymers and their ionomers. Preferably, it is selected from polyethylene resins and polypropylene resins, and specific examples include low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), and polypropylene (PP). Particularly preferably, the polyolefin resin is LDPE.

  The polyolefin resin preferably has a bigat softening point (JIS K 7206) of 80 to 150 ° C. When the bigat softening point is less than the lower limit, it is difficult to hold the emboss. When the upper limit is exceeded, embossing is difficult.

  The polyolefin resin preferably has heat resistant solvent resistance. The polyolefin resin is not affected by an organic solvent such as toluene or ethyl acetate under a normal temperature atmosphere, but may be cracked or wrinkled in an environment of 80 ° C. or higher.

  The polyolefin resin-containing layer can contain a heat stabilizer, a processing aid, and the like as necessary.

  The polyolefin resin-containing layer needs to have a thickness of 10 μm or more. Since the thickness of the polyolefin resin layer is not so high, if the thickness is less than 10 μm, unevenness due to thickness unevenness tends to occur on the surface, and as a result, sufficient surface smoothness of the release material cannot be obtained. Also, a thickness of 10 μm or more is necessary so that the embossment can have a height that fits the groove. In addition, the release material in which the polyolefin resin-containing layer is embossed tends to curl the edges. To prevent this, the upper limit of the thickness of the polyolefin resin-containing layer is based on the polyolefin resin-containing layer. When it is only on one side of the material film, it is 0.3 times the thickness of the base film, and when it is on both sides, it is 0.5 times the thickness of the base film in each of the above layers. . Moreover, when a polyolefin-type resin content layer exists in both surfaces of a base film, it is made for the mutual thickness ratio of the said layer to be 0.3-1. Preferably, when the polyolefin resin-containing layer has a polyolefin resin-containing layer only on one side of the base film, the thickness is 10 μm or more and 0.1 to 0.25 times the thickness of the base film. In the case of being on both surfaces, the thickness is 10 μm or more and 0.1 to 0.25 times the thickness of the base film, and the thickness ratio of each other is 0.5 to 1, more preferably 0.00. 6 to 1, more preferably 1. In a preferable release material of the present invention, the thickness of the base film is 100 to 125 μm, and the thickness of the polyolefin-based resin-containing layer is 15 to 25 μm (15 to 25 μm in the case of being on both sides).

  As described above, the release material may have a polyolefin resin layer on one side or both sides of the base film. It is preferable to have a polyolefin-based resin layer on both sides from the viewpoint that curling at the end of the release material can be further suppressed. However, from the viewpoint of cost, it is advantageous to have a polyolefin resin layer only on one side. In this case, curling is prevented by appropriately adjusting the thickness of the base film and the polyolefin resin layer within the above range. be able to.

  In the release material, at least one of the polyolefin-based resin-containing layers has an emboss on the surface opposite to the surface in contact with the base film. Preferably, the emboss is formed so as to fit into the groove on the surface of the adhesive layer (a). More preferably, the emboss is formed so as to have a male surface structure with respect to the adhesive layer (a), and the release material on which the emboss is formed in this way is advantageous with the vacuum forming sheet of the present invention. Can be combined.

  For the release material, the polyolefin resin-containing layer is bonded to one or both sides of the base film, at least one of the polyolefin resin-containing layers is embossed, and then the surface of the polyolefin resin-containing layer is silicone-coated as necessary. It can manufacture by processing with release agents, such as. The laminating can be performed by a method in which a polyolefin-based resin is melt-extruded on a base film and pressure-bonded with a cooling roll, or a method in which a polyolefin-based resin is formed into a film and then pressure-bonded while being heated with a heat-generating roll. . At this time, in order to improve the adhesion between the base film and the polyolefin resin-containing layer, an anchor coat is previously provided on the surface of the base film in contact with the polyolefin resin-containing layer, or treatment such as corona treatment or plasma treatment is performed. It is preferable to apply. Embossing can be performed by a conventionally known method, for example, by embossing under heating using an engraving roll or an engraving plate.

  The vacuum molding using the vacuum molding sheet of the present invention is not particularly limited, but is preferably molded by the methods described in Patent Documents 1 to 3, for example. That is, the vacuum forming sheet of the present invention and the laminated base material on which the vacuum forming sheet is laminated are arranged opposite to each other, and the first chamber on the laminated base material side and the second on the opposite side by the vacuum forming sheet. And the first chamber and the second chamber are depressurized and the vacuum forming sheet is heated and softened, and then the vacuum forming sheet and the laminated base material are brought into contact with each other. Then, the vacuum forming method of releasing the decompression of the second chamber and then laminating the vacuum forming sheet on the outer surface of the laminated substrate by the differential pressure between the first chamber and the second chamber. . Since this method is known, it will be briefly described below.

FIG. 7 is a diagram for explaining an example of the vacuum forming method.
As shown in FIG. 7, the vacuum forming sheet 10 from which the release material has been removed in the vacuum forming machine and the laminated base material 12 are disposed so as to face each other so that the adhesive layer (a) is in contact with the laminated base material 12. The first sheet 14 on the laminated substrate side and the second chamber 16 on the opposite side are hermetically partitioned by the sheet 10 for use. Subsequently, the first chamber 14 and the second chamber 16 are decompressed by the vacuum pump 18 and the vacuum forming sheet 10 is heated and softened. Heat softening is performed by turning on the heater 20.
Next, as shown in FIG. 8, the table 24 in the first chamber 14 is raised by the driving device 22, and the vacuum forming sheet 10 and the laminated base material 12 are brought into contact with each other. Next, the reduced pressure in the second chamber 16 is released, and the vacuum forming sheet is adhered and laminated on the outer surface of the laminated base material by the differential pressure between the first chamber 14 and the second chamber 16 to obtain a molded product. . Thereafter, the vacuum molding machine is opened by the driving device 26, and the molded product is taken out.

  In the present invention, the laminated substrate is preferably an ABS resin or a substrate made of an alloy of ABS resin and polycarbonate resin in terms of adhesion. The said base material can be obtained by injection molding etc., for example. In the alloy, the ratio of both is, for example, 2: 8 to 7: 3 as ABS resin: polycarbonate resin (mass ratio). In addition, the vacuum forming of the vacuum forming sheet and the laminated base material of the present invention is not limited to the above method.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these examples.

Example 1
Synthesis of Thermoplastic Saturated Copolyester Resin As an acid component, terephthalic acid, isophthalic acid, adipic acid, and glycol component as 1,4-butanediol so that the resulting resin has the resin composition (1) shown in Table 1 below 1,6-hexanediol was blended in an appropriate amount and heated in the presence of a catalyst (tetrabutyl titanate) to synthesize a thermoplastic saturated copolymer polyester resin (hereinafter sometimes simply referred to as a copolymer polyester resin). The above five monomer compositions in the thermoplastic saturated copolyester resin were confirmed by NMR. NMR confirmation was also performed in the following examples and comparative examples.

Preparation of paint for forming adhesive layer (ii) The thermoplastic saturated copolymer polyester resin obtained above was dissolved in a solvent (methyl ethyl ketone) to obtain a paint having a solid content of 30% by mass. Two equivalents of polyisocyanate (1) (manufactured by Nippon Polyurethane, “Coronate HX” (hexamethylene diisocyanate), solid content 100%) was added to this coating material to form an adhesive layer (A) coating material.

Preparation of vacuum forming sheet Acrylic resin film (1) (manufactured by Sumitomo Chemical Co., Ltd., “Technoloy S001”, polymethyl methacrylate, thickness 75 μm, tensile modulus 1300 MPa, pencil hardness H as surface layer film (a) ) Was used.
Also, as the backer layer (c), PET-G (1) (manufactured by Riken Technos Co., Ltd., product names “SET470, FZ25871”, unstretched amorphous polyethylene terephthalate resin film, acid component consisting of terephthalic acid, and ethylene glycol It was composed of a glycol component consisting of 70 mol% and cyclohexane dimethanol 30 mol% (thickness 150 μm).
Lamination of the surface layer film (a) and the backer layer (c) was performed by thermal lamination.

Engraving of a groove 5 (cross section is 20 μm wide and 10 μm deep U-shaped) leading to the side surface is applied in a lattice shape with a pitch of 500 μm so that the portion delimited by the groove is square (see FIG. 2). In addition, in the quadrangular portion delimited by the groove, a cross-shaped groove 4 that does not lead to the side surface (the cross-section is U-shaped with a width of 20 μm and a depth of 10 μm, and the cross-shaped vertical and horizontal lengths) of intervals 500 [mu] m (density sculpture is 250 [mu] m): the female embossing press plates subjected in 1 cm ² per 4.0 × 10 ² pieces), 20 seconds at 140 ° C., to pressurize the laminated film of the following Thus, the embossed shape was transferred to the laminated film to obtain a release material A having a male surface shape.
Laminated film: 100 μm thick polyethylene terephthalate film (Crisper K1212 (cavity-containing biaxially stretched polyethylene terephthalate) manufactured by Toyobo Co., Ltd.) is extruded on one side, and the LDPE is rolled and bonded to a thickness of 20 μm. It was. The embossed shape was transferred to the surface of the LDPE layer of this laminated film.

Next, the release layer A was coated with a knife coater so that the adhesive layer (A) forming coating material had a thickness after curing of 20 μm. Subsequently, the application surface of the paint and the backer layer (c) were bonded together to obtain a vacuum forming sheet with a release material.
Here, as shown in FIG. 9, the interval means the distance between the gravity center points of two adjacent grooves 4 in the front view of the reverse surface 100 of the adhesive (A). In FIG. 9, the darkly filled portion is a groove. The pitch means the shortest distance between the center points of the widths of two adjacent grooves 5 as shown in FIG.

Vacuum forming Vacuum forming was performed by the vacuum forming method shown in Figs. Table 2 shows the surface temperature (molding temperature) of the surface layer film (a) at the time of molding. Further, as the laminated substrate, a substrate made of an alloy of ABS resin and polycarbonate resin and being a molded product obtained by injection molding was used. In the alloy, the ratio of both is 3: 7 as ABS resin: polycarbonate resin (mass ratio).

Evaluation The following evaluation was performed.
Vacuum moldability: NMF-0912 type manufactured by Fuse Vacuum Co., Ltd. The vacuum moldability was evaluated under the molding temperature conditions described in the tables of Examples and Comparative Examples using a double-sided vacuum molding machine.
(Double-circle): The followable | trackability to a base-material shape is favorable and an edge part winding property is also favorable.
◯: The followability to the substrate shape is good, but the end wrapping property is poor.
(Triangle | delta): The followable | trackability to a base-material shape and edge part winding property are sweet, and a float may be seen.
X: The sheet is torn and cannot be sufficiently molded.

Initial tackiness: The initial tackiness was evaluated based on the feeling when the finger was pressed firmly against the cured adhesive layer surface and then peeled off.
○: There is a sticky feeling.
Δ: Feels somewhat sticky.
×: No stickiness.

Initial adhesion: Initial adhesion was evaluated by forcibly peeling the sheet immediately after vacuum forming.
A: Sheet material breaks.
○: The sheet is peeled while being stretched.
(Triangle | delta): It peels, maintaining some peeling resistance, without a sheet | seat being extended.
X: The sheet is not stretched and peeled without sufficient peeling resistance.

Heat resistant adhesion (50 ° C. × 400 hours):
After the vacuum molded product was left in a gear oven set at 50 ° C. for 400 hours, peeling of the edge was confirmed and the sheet was forcibly peeled to evaluate the heat resistant adhesion.
(Double-circle): There is no peeling of an edge part and a sheet material breaks by forced peeling.
◯: There is no peeling at the edge, and peeling is performed while the sheet is stretched by forced peeling.
Δ: Slight peeling at the edge is observed, and the sheet is not stretched by forced peeling, but is peeled while maintaining some peeling resistance.
X: The peeling of the edge is clearly recognized, or the sheet is peeled off without sufficient peeling resistance by forced peeling.

Heat resistant adhesiveness (80 ° C. × 400 hours):
After the vacuum molded product was left in a gear oven set at 80 ° C. for 400 hours, peeling of the end portion was confirmed and the sheet was forcibly peeled to evaluate the heat resistant adhesion.
(Double-circle): There is no peeling of an edge part and a sheet material breaks by forced peeling.
◯: There is no peeling at the edge, and peeling is performed while the sheet is stretched by forced peeling.
Δ: Slight peeling at the edge is observed, and the sheet is not stretched by forced peeling, but is peeled while maintaining some peeling resistance.
X: The peeling of the edge is clearly recognized, or the sheet is peeled off without sufficient peeling resistance by forced peeling.

Drag line: NGF-0912 type made by Fuse Vacuum Co., Ltd. In a double-sided vacuum forming machine, molding is performed under the molding temperature conditions described in the tables of Examples and Comparative Examples without placing a frame material or bank on the outer periphery of the substrate. It was evaluated by. The evaluation criteria are as follows.
A: There is no drag line at all.
○: There are a few weak drag lines.
Δ: A weak drag line exists.
X: A strong drag line exists.

Heat-resistant appearance (50 ° C. × 400 hours): The vacuum molded product was evaluated by observing the appearance after leaving it in a gear oven set at 50 ° C. for 400 hours. The evaluation criteria are as follows.
A: There is no crusty skin due to swelling or rough surface.
○: There is no bulge, but there is slight skin damage due to rough surface.
Δ: Slightly crumpled or rough skin due to rough surface is observed.
×: Obvious skin due to blistering and rough surface is observed.

Heat-resistant appearance (80 ° C. × 400 hours): The vacuum molded product was evaluated by observing the appearance after leaving it in a gear oven set at 80 ° C. for 400 hours. The evaluation criteria are as follows.
A: There is no crusty skin due to swelling or rough surface.
○: There is no bulge, but there is slight skin damage due to rough surface.
Δ: Slightly crumpled or rough skin due to rough surface is observed.
×: Obvious skin due to blistering and rough surface is observed.

Productivity (simplification of the process): Fabrication products without drag lines are produced in the NGF-0912 double-sided vacuum molding machine manufactured by Fuse Vacuum Co., Ltd. under the molding temperature conditions described in the tables of Examples and Comparative Examples. It was evaluated by doing. The evaluation criteria are as follows.
○: A molded product without a drag line could be obtained without using a frame material or the like.
(Triangle | delta): The molded product without a drag line was able to be obtained using frame materials etc.
X: Even if a frame material or the like was used, a molded product without a drag line could not be obtained.

Shrinkage test: Performed based on JIS K 7133 “Plastics-Films and Sheets—Measurement of Heated Dimensional Change”. First, a vacuum forming sheet with a release material is cut out to a size of 250 mm × 250 mm. Next, as shown in FIG. 10, two vertical and horizontal straight lines are drawn at the center of each surface of the cut-out vacuum forming sheet on the surface film (A) side and the release material side, and the two straight lines are drawn. A test line is prepared by drawing a marked line (4 lines) at a position 100 mm away from the crossing line.
For each of the surface film (a) surface and release material surface of the test piece, measure the distance between the two marked lines on the vertical and horizontal straight lines with a scale ruler that can measure to a unit of 0.5 mm. The average value of the distance between the vertical and horizontal marked lines is L _f0 , and the average value of the distance between the marked lines of the release material is L _s0 . Next, store at room temperature for 1 week, at 80 ° C for 1 week, and at room temperature for 3 months. The average value of the distance between the vertical and horizontal marked lines of the surface layer film (a) is L _f , and the average value of the distance between the vertical and horizontal marked lines of the release material is L _s . The shrinkage rate ΔL _f of the surface layer film (a) and the shrinkage rate ΔL _s of the release material are calculated by the following formula (1). Further, the shrinkage rate ΔL _f of the resin film is subtracted from the shrinkage rate ΔL _s of the release material to obtain a shrinkage rate difference ΔL = ΔL _s −ΔL _f .
ΔL _x = (L _x -L _x0 ) / L _x0 × 100… (1)
L _x0 : Distance between marked lines before storage (mm)
L _x : Distance between marked lines after storage (mm)
(However, x = f or s)

Appearance of vacuum forming sheet with release material during long-term storage:
The sheet for vacuum forming with a release material was rolled and wound for 3 months at room temperature, then taken out and evaluated by visually observing the unwinding appearance of the sheet. The evaluation criteria are as follows.
○: Tarmi and wrinkles are not observed on the sheet.
×: Tarmi and wrinkles are observed on the sheet.

  The results are shown in Table 2.

Example 2
In Example 1, PVC (1) (manufactured by Riken Technos Co., Ltd., product name “S12040, FC13477”, polyvinyl chloride resin, thickness 150 μm) was used as the backer layer (c) at the molding temperature shown in Table 2. Example 1 was repeated except that vacuum forming was performed. The results are shown in Table 2.

Example 3
In Example 1, copolymerized PET (1) (Teijin DuPont Films, Teflex FT, terephthalic acid as an acid component, naphthalenedicarboxylic acid, ethylene glycol as a glycol component, as a surface layer film (a) Example 1 was repeated except that a biaxially stretched copolymer polyethylene terephthalate resin film (thickness 50 μm) was used and vacuum molding was performed at the molding temperature shown in Table 2. The results are shown in Table 2.

Example 4
In Example 1, as the surface layer film (a), PC (1) (product name: Asahi Glass, trade name: Lexan film 8010, 112 clear, polycarbonate film, thickness: 100 μm) was used, and an ABS resin was used as the laminated substrate. Example 1 was repeated except that vacuum molding was performed at the molding temperature shown in FIG. The results are shown in Table 2.

Example 5
In Example 1, as the surface layer film (a), PET-G (2) (manufactured by Riken Technos Co., Ltd., trade name: SET241 FZ025, unstretched amorphous polyethylene terephthalate resin film, acid component composed of terephthalic acid, and ethylene It was composed of a glycol component consisting of 70 mol% of glycol and 30 mol% of cyclohexanedimethanol (thickness: 100 μm), and ABS resin was used as a laminate substrate, and vacuum forming was performed at the molding temperatures shown in Table 2. Example 1 was repeated except that. The results are shown in Table 2.

Examples 6-9
In Example 1, Example 1 was repeated except that the surface layer film (a), the laminated base material, and the molding temperature were changed as shown in Table 3 or 4 without providing the backer layer (c). The results are shown in Table 4.
In Table 3, acrylic (2) is manufactured by Sumitomo Chemical Co., Ltd., trade name: Technoloy S001, acrylic resin film, and thickness: 125 μm.
PET-G (3) is manufactured by Riken Technos Co., Ltd., trade name SET329 FZ93266, unstretched amorphous polyethylene terephthalate resin film, acid component consisting of terephthalic acid, 70 mol% of ethylene glycol and 30 mol of cyclohexanedimethanol % Glycol component, and has a thickness of 150 μm.
PVC (2) is manufactured by Riken Technos Co., Ltd., trade name S12138 FC25847, a polyvinyl chloride resin film, and a thickness of 150 μm.
PC (2) is manufactured by Asahi Glass, trade name Lexan film FR765 black, polycarbonate resin film, thickness 180 μm.

Example 10
Engraving the groove 5 (cross section is 30 μm wide and 15 μm deep U-shaped) leading to the side surface at a pitch of 500 μm so that the part delimited by the groove is a hexagon (see FIG. 4) Furthermore, the hexagonal portion delimited by the groove is a hexagonal groove 4 that does not lead to the side surface (the cross section is a U-shape with a width of 30 μm and a depth of 15 μm, and the length of one side of the hexagon is 144 μm) interval 500 [mu] m (density carvings in a): the female embossing press plates subjected in 1 cm 4.6 × 10 ² per ^2), 20 seconds at 140 ° C., pressurized to the stacking film used in example 1 Thus, the embossed shape was transferred to the laminated film to obtain a release material B having a male surface shape. Using this release material, a vacuum forming sheet with a release material was obtained in the same manner as in Example 1, and each evaluation was performed. Table 6 shows molding temperatures and results.

Example 11
Engraving the groove 5 (cross section is 20 μm wide and 10 μm deep U-shaped) leading to the side surface at a pitch of 300 μm so that the portion delimited by the groove is triangular, and further delimited by the groove 300 mm (density) of triangular sculptures that are not connected to the side surfaces (the cross section is U-shaped with a width of 20 μm and a depth of 10 μm, and the length of one side of the triangle is 100 μm). : The embossed press plate of a female mold applied at 1.1 × 10 ³ per cm ² ) is pressed against the laminated film used in Example 1 at 140 ° C. for 20 seconds to transfer the embossed shape to the laminated film Thus, a release material C having a male surface shape was obtained. Using this release material, a vacuum forming sheet with a release material was obtained in the same manner as in Example 1, and each evaluation was performed. Table 6 shows molding temperatures and results.

Example 12
Engraving a groove 5 (cross section is U-shaped with a width of 50 μm and a depth of 20 μm) leading to the side surface at a pitch of 700 μm so that the portion delimited by the groove is circular (see FIG. 5), In addition, the circular portion defined by the groove is spaced by a circular groove 4 that does not lead to the side surface (the cross section is U-shaped with a width of 50 μm and a depth of 20 μm, and the circular diameter is 350 μm). 700 .mu.m: the female embossing press plates subjected by (density 1 cm 2.4 × 10 ² per ^2), 20 seconds at 140 ° C., by pressurizing the laminated film used in example 1, embossing the laminated film The shape was transferred to obtain a release material D having a male surface shape. Using this release material, a vacuum forming sheet with a release material was obtained in the same manner as in Example 1, and each evaluation was performed. Table 6 shows molding temperatures and results.

Examples 13-14
In Example 10, Example 10 was repeated except that the structure of the surface layer film (a) and the backer layer (c) and the molding temperature were changed as shown in Table 5 or 6. The results are shown in Table 6.

Examples 15-18
In Example 1, Example 1 was repeated except that the resin structures (2) to (5) shown in Table 7 were employed instead of the resin structure (1). Molding temperatures and results are shown in Table 8.

Examples 19-21
In Example 1, Example 1 was repeated except that the amount or type of polyisocyanate was changed as shown in Table 7 or 9. Molding temperatures and results are shown in Tables 8 and 10.
In addition, polyisocyanate (2) is Nippon Polyurethane Co., Ltd. product name Coronate L, Compound name Tolylene diisocyanate.

Example 22
In Example 1, Example 1 was repeated except that A-PET (1) was used as the backer layer (c). Molding temperatures and results are shown in Table 10.
A-PET (1) is Teijin Chemicals, trade name A-PET sheet general type, compound name unstretched polyethylene terephthalate sheet, thickness 150 μm.

Example 23
In Example 7, Example 7 was repeated except that A-PET (2) was used as the surface layer film (a). Molding temperatures and results are shown in Table 10.
A-PET (2) is Teijin Chemicals, trade name A-PET sheet black, compound name unstretched polyethylene terephthalate sheet, thickness 150 μm.

Example 24
In Example 1, Example 1 was repeated except that the laminated base material was changed to polypropylene (PP). Molding temperatures and results are shown in Table 10.

Comparative Example 1
In Example 1, biaxial PET (1) (trade name: Emblet S50, biaxially stretched polyethylene terephthalate film, thickness: 50 μm, manufactured by Unitika Co., Ltd.) was used as the surface layer film (a). Example 1 was repeated except that the changes were made as shown in FIG. The results are shown in Table 12.

Comparative Example 2
In Example 1, without providing a backer layer (C), a PBT (1) (polybutylene terephthalate resin [trade name Toraycon 1200S, manufactured by Toray Industries, Inc.] is mounted as a surface layer film (A) with a 600 mm wide T-die. Using a 40 mm extruder (made by Ikegai Co., Ltd.), embossed pattern 200 mesh, temperature conditions were cylinder temperature 270 ° C., die temperature 270 ° C., film forming speed 10 m / min. Example 1 was repeated except that the molding temperature was changed as shown in Table 12. The results are shown in Table 12.

Comparative Example 3
Example 1 was repeated except that the release material was not provided with grooves 4 and 5. Molding temperatures and results are shown in Table 12.

Comparative Example 4
Example 1 was repeated except that the release material was not provided with the groove 5. Molding temperatures and results are shown in Table 12.

Comparative Example 5
Example 14 was repeated except that the release material was not provided with the groove 5. Molding temperatures and results are shown in Table 12.

Comparative Example 6
Example 1 was repeated except that the release material was not provided with the grooves 4. Molding temperatures and results are shown in Table 14.

Comparative Example 7
Example 14 was repeated except that the release material was not provided with the groove 4. Molding temperatures and results are shown in Table 14.

Comparative Examples 8-12
In Example 1, Example 1 was repeated except that the resin structures (6) to (10) shown in Tables 13 and 15 were employed instead of the resin structure (1). Molding temperatures and results are shown in Tables 14 and 16.

Comparative Examples 13-14
In Example 1, Example 1 was repeated except that the amount of polyisocyanate was changed as shown in Table 15. Molding temperatures and results are shown in Table 16.

Comparative Example 15
In Example 1, Example 1 was repeated except that the adhesive layer (I) was changed to the pressure-sensitive adhesive (1) and the groove 4 was not provided in the release material. The results are shown in Table 16.
In addition, an adhesive (1) is the Big technos Co., Ltd. make, brand name liquidin AR-2037, and coating composition: acrylate ester copolymer.

From the results of Tables 1 to 16, the following matters are derived.
-Example 1 specifies the kind of surface layer film (a), sets the composition of the thermoplastic saturated copolymer polyester resin and the amount of polyisocyanate used in the adhesive layer (a) within a specific range, and Since a predetermined groove is formed on a specific surface of the adhesive layer (a), no dragline (streak-like trace) is generated on the surface of the three-dimensional coated molded product, and heat resistant appearance (50 ° C. × 400 hours, 80 C. x 400 hours). Moreover, it is not necessary to use a special jig or the like for preventing the generation of the drag line, and the productivity (simplification of the process) is excellent. Furthermore, since the difference in shrinkage between the surface layer film (a) and the release material is also small, the appearance of the sheet does not deteriorate when stored for a long time with the release material. In addition, the initial tackiness and initial adhesion are excellent, and by providing a backer layer (c), the vacuum moldability can be improved, and the heat-resistant adhesiveness in a three-dimensional coated molded product (50 ° C. × 400 hours) , 80 ° C. × 400 hours) can be provided. Further, it has been proved that the vacuum molded product of the vacuum molding sheet of the present invention and a base material made of an alloy of ABS resin and polycarbonate resin is particularly excellent in adhesion.
Example 2 was an example in which the backer layer was PVC (1), and showed the same performance as Example 1.
Example 3 was an example in which the surface layer film (a) was copolymerized PET (1), and showed the same performance as Example 1.
Example 4 is an example in which the surface layer film (A) is PC (1) and the laminated base material is ABS, and shows the same performance as Example 1.
Example 5 is an example in which the surface layer film (A) is PET-G (2) and the laminated base material is ABS, and the same performance as in Example 1 is shown.
Example 6 is an example in which the surface layer film (a) is acrylic (2) and the backer layer (c) is not provided, and the same as in Example 1 except that the vacuum formability is ◯ evaluation. Showed performance.
-Example 7 is an example in which the surface layer film (a) is PET-G (3) and the backer layer (c) is not provided. Similar performance was demonstrated.
-Example 8 is an example in which the surface layer film (a) is PVC (2), the backer layer (c) is not provided, and the laminated base material is ABS, except that the vacuum moldability is ◯ evaluation. The same performance as in Example 1 was exhibited.
-Example 9 is an example in which the surface layer film (a) is PC (2) and the backer layer (c) is not provided, and the vacuum formability is the same as that of Example 1 except that the evaluation is ○ evaluation. Showed performance.
Example 10 was an example in which the type of release material was B, and showed the same performance as Example 1.
Example 11 was an example in which the type of release material was C, and showed the same performance as Example 1.
Example 12 was an example in which the type of release material was D, and showed the same performance as Example 1.
Example 13 is an example in which the surface layer film (A) is PET-G (2) and the type of release material is B, and the same performance as in Example 1 is shown.
Example 14 is an example in which the surface layer film (a) is PET-G (3), the backer layer (c) is not provided, and the type of release material is B, and the vacuum formability is evaluated as good. Except for this, the same performance as in Example 1 was exhibited.
-Example 15 was the example which made the copolyester resin the resin structure (2), and showed the same performance as Example 1.
-Example 16 is the example which made the copolymer polyester resin the resin structure (3), and heat-resistant adhesiveness (50 degreeC x 400 hours) and heat-resistant external appearance property (50 degreeC x 400 hours) are (circle) evaluation, heat-resistant adhesiveness ( 80 ° C. × 400 hours) and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
Example 17 is an example in which the copolymerized polyester resin has a resin configuration (4), and the initial tackiness and initial adhesion are Δ evaluated, heat resistant adhesiveness (50 ° C. × 400 hours), heat resistant adhesiveness (80 ° C. × 400 hours), heat-resistant appearance (50 ° C. × 400 hours), and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as ○. Otherwise, the same performance as in Example 1 was exhibited.
-Example 18 was the example which made the copolyester resin the resin structure (5), and showed the same performance as Example 1.
Example 19 is an example in which the amount of polyisocyanate (1) added was 1.7 equivalents, with heat resistance adhesion (50 ° C. × 400 hours) and heat appearance appearance (50 ° C. × 400 hours) evaluated as good, heat resistance Adhesiveness (80 ° C. × 400 hours) and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
Example 20 is an example in which the amount of polyisocyanate (1) added was 2.3 equivalents, and the initial tackiness and initial adhesion were evaluated as Δ, heat-resistant adhesiveness (50 ° C. × 400 hours), heat-resistant appearance ( 50 ° C. × 400 hours) was evaluated as “Good”, heat resistant adhesiveness (80 ° C. × 400 hours), and heat resistant appearance (80 ° C. × 400 hours) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
-Example 21 is an example which uses polyisocyanate (2), initial tack property, heat-resistant adhesiveness (50 degreeC x 400 hours), heat-resistant adhesiveness (80 degreeC x 400 hours), heat-resistant appearance (50 degreeC x 400) Time) and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
Example 22 is an example in which A-PET (1) is used for the backer layer. The vacuum formability is Δevaluation, the heat-resistant adhesiveness (50 ° C. × 400 hours), and the heat-resistant appearance (50 ° C. × 400 hours). O Evaluation, heat-resistant adhesiveness (80 ° C. × 400 hours), heat-resistant appearance (80 ° C. × 400 hours) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
Example 23 is an example in which A-PET (2) was used for the surface layer film (a) and no backer layer (c) was provided. The vacuum formability was evaluated as Δ, heat-resistant adhesiveness (50 ° C. × 400 hours) ), Heat-resistant appearance (50 ° C. × 400 hours) was evaluated as ◯, heat-resistant adhesiveness (80 ° C. × 400 hours), and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
Example 24 is an example in which PP is used for the laminated base material. The initial adhesiveness is evaluated as Δ, the heat-resistant adhesiveness (50 ° C. × 400 hours), and the heat-resistant appearance (50 ° C. × 400 hours) are evaluated as ○. Adhesiveness (80 ° C. × 400 hours) and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.

-Comparative Example 1 is an example in which the surface layer film (a) is biaxial PET (1), and is outside the scope of the present invention, so vacuum formability, initial adhesion, and heat resistant adhesiveness (50 ° C x 400 hours) The heat-resistant adhesiveness (80 ° C. × 400 hours), the heat-resistant appearance (50 ° C. × 400 hours), and the heat-resistant appearance (80 ° C. × 400 hours) were evaluated as x.
Comparative Example 2 is an example in which the surface layer film (a) is PBT (1) and the backer layer (c) is not provided, and is outside the scope of the present invention. Therefore, vacuum formability, initial adhesion, heat-resistant adhesion Evaluation (50 ° C. × 400 hours), heat-resistant adhesiveness (80 ° C. × 400 hours), heat-resistant appearance (50 ° C. × 400 hours), and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as x.
Comparative Example 3 is an example in which the type of release material is E (not having grooves 4 and 5), and is outside the scope of the present invention, so drag line, heat resistant appearance (50 ° C. × 400 hours), Heat-resistant appearance (80 ° C. × 400 hours), productivity (simplification of process), appearance of sheet with release material during long-term storage × evaluation, difference in shrinkage after 1 week, 80 ° C., normal temperature, 3 The difference in shrinkage after months was large and the evaluation was inferior.
Comparative Example 4 is an example in which the type of release material is F (without the groove 5), and is outside the scope of the present invention. Therefore, drag line, heat resistant appearance (50 ° C. × 400 hours), heat resistant appearance (80 ° C. × 400 hours), productivity (simplification of the process) was evaluated as x.
Comparative Example 5 is an example in which the surface layer film (A) is PET-G (3), the backer layer (U) is not provided, and the type of the release material is G (the groove 5 is not provided). Therefore, the drag line, heat resistant appearance (50 ° C. × 400 hours), heat resistant appearance (80 ° C. × 400 hours), and productivity (simplification of the process) were evaluated as x.
Comparative Example 6 is an example in which the type of release material is H (without the groove 4), and is outside the scope of the present invention, so it is a drag line, heat resistant appearance (50 ° C. × 400 hours), heat resistant appearance (80 ° C. × 400 hours), productivity (simplification of process) is Δ evaluation, appearance of sheet with release material during long-term storage is X evaluation, difference in shrinkage after 1 week, 80 ° C., normal temperature, 3 The difference in shrinkage after months was large and the evaluation was inferior.
Comparative Example 7 is an example in which the type of release material is I (without the groove 4), and is outside the scope of the present invention. Therefore, drag line, heat resistant appearance (50 ° C. × 400 hours), heat resistant appearance (80 ° C. × 400 hours), productivity (simplification of process) is Δ evaluation, appearance of sheet with release material during long-term storage is X evaluation, difference in shrinkage after 1 week, 80 ° C., normal temperature, 3 The difference in shrinkage after months was large and the evaluation was inferior.
Comparative Example 8 is an example in which a copolymerized polyester resin is used as the resin composition (6), and is outside the scope of the present invention. Therefore, heat resistant adhesiveness (50 ° C. × 400 hours), heat resistant adhesiveness (80 ° C. × 400 hours) ), Heat-resistant appearance (50 ° C. × 400 hours) and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as x.
Comparative Example 9 is an example in which a copolymerized polyester resin is used as the resin composition (7), and is outside the scope of the present invention. Therefore, initial tackiness and initial adhesion are evaluated as x evaluation, heat resistant adhesiveness (50 ° C. × 400 hours) ), Heat-resistant adhesiveness (80 ° C. × 400 hours), heat-resistant appearance (50 ° C. × 400 hours), and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as Δ.
Comparative Example 10 is an example in which a copolymerized polyester resin is used as the resin configuration (8), and is outside the scope of the present invention. Therefore, heat resistant adhesiveness (50 ° C. × 400 hours), heat resistant adhesiveness (80 ° C. × 400 hours) ), Heat-resistant appearance (50 ° C. × 400 hours) and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as x.
Comparative Example 11 is an example in which the copolymerized polyester resin has a resin configuration (9), and is outside the scope of the present invention, and therefore, the initial tackiness and initial adhesion were evaluated as x.
Comparative Example 12 is an example in which the copolymerized polyester resin has a resin configuration (10), and is outside the scope of the present invention. Therefore, heat resistant adhesiveness (50 ° C. × 400 hours), heat resistant adhesiveness (80 ° C. × 400 hours) ), Heat-resistant appearance (50 ° C. × 400 hours) and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as x.
Comparative Example 13 is an example in which the amount of polyisocyanate (1) added is 1 equivalent, and is outside the scope of the present invention, so heat resistant adhesiveness (50 ° C. × 400 hours), heat resistant appearance (50 ° C. × 400) Time) was evaluated as Δ, heat-resistant adhesiveness (80 ° C. × 400 hours), and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as ×.
Comparative Example 14 is an example in which the amount of polyisocyanate (1) added is 3 equivalents, and is outside the scope of the present invention. Therefore, the initial tackiness is evaluated as x, the initial adhesion is evaluated as Δ, and the heat resistant adhesion (50 (° C. × 400 hours), heat-resistant appearance (50 ° C. × 400 hours) were evaluated as Δ, heat-resistant adhesiveness (80 ° C. × 400 hours), and heat-resistant appearance (80 ° C. × 400 hours) were evaluated as ×.
Comparative Example 15 is an example in which the pressure-sensitive adhesive (1) is used for the adhesive layer (A) and the type of the release material is H (no groove 4), and is outside the scope of the present invention. Line, productivity (simplification of process) △ evaluation, heat resistant adhesiveness (50 ° C x 400 hours), heat resistant adhesiveness (80 ° C x 400 hours), heat resistant appearance (50 ° C x 400 hours), heat resistant appearance (80 ° C. × 400 hours), evaluation of the appearance of the sheet with a release material during long-term storage, evaluation at 80 ° C., difference in shrinkage after 1 week, room temperature, difference in shrinkage after 3 months is large and inferior Became.

  The vacuum forming sheet of the present invention is useful for obtaining a three-dimensional coated molded product for automobile interior use, home appliance use, and the like.

It is sectional drawing for demonstrating the structure of the sheet | seat for vacuum forming of this invention. It is a perspective view of one embodiment of the sheet for vacuum forming of the present invention seen from the reverse side. It is the sketch which expanded a part of groove | channel of the adhesive sheet of this invention, (a) is the cross-sectional shape of a groove | channel, (b) is the cross-sectional shape of a groove | channel, and (c) is a cross-section of a groove | channel. The shape is U-shaped, and (d) shows the case where the cross-sectional shape of the groove is a triangle. w indicates the width and h indicates the depth. It is the front view which expanded a part of adhesive bond layer of the sheet | seat for vacuum forming of this invention. It is the front view which expanded a part of adhesive bond layer of the sheet | seat for vacuum forming of this invention. It is the front view which expanded a part of adhesive bond layer of the sheet | seat for vacuum forming of this invention. It is a figure for demonstrating an example of the vacuum forming method applied suitably for the sheet | seat for vacuum forming of this invention. It is a figure for demonstrating an example of the vacuum forming method applied suitably for the sheet | seat for vacuum forming of this invention. It is a figure explaining the space | interval and pitch of a groove | channel, (a)-(c) respond | corresponds to the front view of the adhesive bond layer of FIG. It is a figure explaining a shrinkage rate test.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Vacuum forming sheet 4 Groove 5 Groove A Surface layer film B Adhesive layer C Backer layer 10 Vacuum forming sheet 12 Laminated substrate 14 First chamber 16 Second chamber 18 Vacuum pump 20 Heater 22, 26 Drive device 24 Table 100 reverse side

Claims (14)

It is a sheet for vacuum forming having an adhesive layer (I) on the lower surface of the surface layer film (A),
The surface layer film (a) is an acrylic resin film (A), a biaxially stretched copolymer polyethylene terephthalate film (B), an unstretched amorphous polyethylene terephthalate resin film (C), a polyvinyl chloride resin film ( D) or a polycarbonate-based resin film (E), and the adhesive layer (A) is obtained by blending 1.5 to 2.5 equivalents of polyisocyanate in the following thermoplastic saturated copolymer polyester resin and curing. And has one or more grooves on the surface opposite to the surface bonded to the surface film (a), and the grooves are present only on the inner side of the opposite surface of the adhesive layer (a). And a groove that does not communicate with the side surface of the adhesive layer (a) and a groove that communicates with the side surface on the opposite surface.
Thermoplastic saturated copolyester resin: an acid component composed of 20 to 40 mol% terephthalic acid, 20 to 40 mol% isophthalic acid and 25 to 50 mol% adipic acid (however, the total of the acid components is 100 mol%); The glycol component is composed of 10 to 50 mol% of 1,4-butanediol and 50 to 90 mol% of 1,6-hexanediol (however, the total of the glycol components is 100 mol%).   The sheet for vacuum forming according to claim 1, wherein the thermoplastic saturated copolymer polyester resin has a softening temperature of 55 to 85 ° C.   The vacuum forming sheet according to claim 1, further comprising a backer layer (c) between the surface layer film (a) and the adhesive layer (a).   4. The vacuum forming sheet according to claim 3, wherein the backer layer (c) is an unstretched amorphous polyethylene terephthalate resin film (F) or a polyvinyl chloride resin film (G).   The said polyisocyanate is polyisocyanate which consists of hexamethylene diisocyanate, The sheet | seat for vacuum forming in any one of Claims 1-4 characterized by the above-mentioned.   The unstretched amorphous polyethylene terephthalate resin film (C) comprises an acid component composed of terephthalic acid, and a glycol component composed of 60 to 90 mol% ethylene glycol and 10 to 40 mol% cyclohexanedimethanol (however, the glycol component) The total of (100 mol%) is comprised from these. The sheet | seat for vacuum forming in any one of Claims 1-5 characterized by the above-mentioned.   The unstretched amorphous polyethylene terephthalate resin film (F) comprises an acid component composed of terephthalic acid, and a glycol component composed of 60 to 90 mol% ethylene glycol and 10 to 40 mol% cyclohexanedimethanol (however, the glycol component) The sheet for vacuum forming according to claim 4, wherein the total is 100 mol%.   The vacuum forming sheet according to claim 1, wherein the groove has a width of 5 to 100 μm and a depth of 5 to 50 μm.   In the front view of the opposite surface of the adhesive layer (a), the grooves not leading to the side surface are linear, linearly branched, cruciform, circular, elliptical or polygonal, and each shape is intermittent. The sheet | seat for vacuum forming of Claim 1 or Claim 8 which may be formed by the several groove | channel which is various. In the front view of the opposite surface of the adhesive layer (a), grooves that do not lead to the side surface are present at a density of 1 × 10 to 3.7 × 10 ⁶ per cm ^2. Item 10. The vacuum forming sheet according to any one of Items 8 to 9.   In the front view of the opposite surface of the adhesive layer (a), the plurality of grooves leading to the side surface are arranged in a striped pattern, or each of the adhesive layers separated by the grooves is circular, The vacuum forming sheet according to any one of claims 1 and 8 to 10, wherein the vacuum forming sheet is disposed so as to be elliptical or polygonal.   The sheet for vacuum forming according to claim 9 or 11, wherein the polygon is a triangle, a quadrangle, or a hexagon. The sheet | seat for vacuum forming in any one of Claims 1-12 used in order to perform vacuum forming with the following vacuum forming method.
Vacuum forming method: The vacuum forming sheet according to any one of claims 1 to 12 and a laminated base material on which the vacuum forming sheet is laminated are arranged opposite to each other, and the vacuum forming sheet is arranged on the laminated base material side. One chamber, the second chamber on the opposite side are hermetically separated from each other, the first chamber and the second chamber are depressurized, and the vacuum forming sheet is heated and softened, and then the vacuum forming The sheet is brought into contact with the laminated base material, and then the decompression of the second chamber is released, and the vacuum forming sheet is removed from the laminated base material by the differential pressure between the first chamber and the second chamber. Vacuum forming method that adheres and laminates to the surface.   A molded article comprising the vacuum forming sheet according to any one of claims 1 to 13 and a base material made of an ABS resin or an alloy of an ABS resin and a polycarbonate resin, which is laminated by vacuum molding.

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