WO2010058705A1

WO2010058705A1 - Sheet for vacuum molding

Info

Publication number: WO2010058705A1
Application number: PCT/JP2009/068961
Authority: WO
Inventors: 智章高木
Original assignee: リケンテクノス株式会社
Priority date: 2008-11-18
Filing date: 2009-11-06
Publication date: 2010-05-27
Also published as: JP2010120208A; JP5286042B2

Abstract

Disclosed is a sheet for vacuum molding (1) having excellent heat-resistant appearance, which prevents air inclusion in a three-dimensional coated molded article caused by recesses and projections in the back surface. The sheet for vacuum molding (1) has an adhesive layer (ii) on the lower surface of a surface layer film (i) which has an embossed surface layer. The surface layer film (i) is composed, for example, of an acrylic resin film (A), and the adhesive layer (ii) is obtained by blending 1.5-2.5 equivalent weights of a polyisocyanate into a specific thermoplastic saturated copolymer polyester resin and curing the resulting blend. The adhesive layer (ii) has one or more grooves in a surface (100), which is the surface on the reverse side of the surface that is in contact with the surface layer film (i), and the grooves include those ranging within the surface (100) and not reaching the lateral surface of the adhesive layer, and those extended in the surface (100) and reaching the lateral surface of the adhesive layer.

Description

Vacuum forming sheet

The present invention relates to a vacuum forming sheet, and more specifically, there is no air mixing due to back surface unevenness of a three-dimensional coated molded product, and the heat resistant appearance (50 ° C. × 400 hours, 80 ° C. × 400 hours) is excellent. It relates to a vacuum forming sheet with a release material that does not deteriorate the appearance of the sheet when stored for a long period of time, and has excellent heat-resistant adhesiveness (50 ° C. × 400 hours, 80 ° C. × 400 hours) in a three-dimensional coated molded product Is.

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.

As a method of obtaining the above-mentioned coated molded product by employing the vacuum molding method, for example, the following patent documents 1 to 3 are disclosed.

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, which is provided with an adhesive layer of 20 to 150 μm.
However, the three-dimensional coated molded product molded using the embossed surface of the molded decorative sheet for molded article of the patent document has a problem that air due to unevenness on the back surface is mixed, and heat resistant appearance There is a problem that it is inferior to (50 ° C. × 400 hours, 80 ° C. × 400 hours). 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 surface of the synthetic resin sheet of the patent document is embossed and stored for a long time with a release material, there is a problem that the appearance deteriorates due to the difference in shrinkage between the synthetic resin sheet and the release material. is there. 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). . In addition, there is room for improvement in air mixing caused by unevenness on the back surface of a three-dimensional coated molded product molded using an embossed surface of the synthetic resin sheet of the patent document.

Japanese 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 that there is no air mixing due to the unevenness of the back surface of the three-dimensional coated molded product, it has excellent heat resistant appearance (50 ° C. × 400 hours, 80 ° C. × 400 hours), and is stored for a long time with a release material. An object of the present invention is to provide a sheet for vacuum forming that does not deteriorate the appearance of the sheet and is excellent in heat-resistant adhesiveness (50 ° C. × 400 hours, 80 ° C. × 400 hours) in a three-dimensional coated molded product.

The present invention is as follows.
1. A sheet for vacuum forming having an adhesive layer (I) on the lower surface of a surface layer film (A) embossed on the surface layer,
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 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 comprising 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%); A glycol component 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 as described in 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) 6. The vacuum forming sheet as described in any one of 1 to 5 above, wherein the total is 100 mol%).
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 (provided that the glycol component described above) (5) is a sheet for vacuum forming as described in (4) above.
8). 8. The vacuum forming sheet according to any one of 1 to 7 above, wherein the embossed pattern is a conduit grain, a hairline, an abstract pattern, or a satin texture.
9. 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.
10. 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. 10. The sheet for vacuum forming as described in 1 or 9 above, which may be formed by a plurality of grooves.
11. 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 1 cm ^2. The vacuum forming sheet according to any one of 1 to 10.
12 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, 12. The vacuum forming sheet according to any one of 1 or 9 to 11, which is arranged so as to be elliptical or polygonal.
13. 13. The vacuum forming sheet according to 10 or 12, wherein the polygon is a triangle, a quadrangle, or a hexagon.
14 14. The vacuum forming sheet as described in any one of 1 to 13 above, 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 13 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.
15. 15. A molded product comprising the vacuum molding sheet according to any one of 1 to 14 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) whose surface layer is embossed is specified, and the composition of the thermoplastic saturated copolymer polyester resin and the amount of polyisocyanate used in the adhesive layer (a) are within a specific range. In addition, since a predetermined groove was formed on the specific surface of the adhesive layer (a), there was no air mixing due to the back surface unevenness of the three-dimensional coated molded product, and heat resistant appearance (50 ° C. × 400 hours, 80 ° C. × 400 hours), and when it is stored for a long time with a release material, the appearance of the sheet does not deteriorate, and the heat-resistant adhesiveness (50 ° C. × 400 hours, 80 ° C. × 400 hours) in a three-dimensional coated molded product An excellent vacuum forming sheet 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.

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. FIG. 6 is a diagram for explaining the interval and pitch of grooves, and (a) to (c) correspond to the front views of the adhesive layer of FIGS. 2, 4 and 5, respectively. It is a figure explaining a shrinkage rate test. It is sectional drawing of the sheet | seat for vacuum forming for demonstrating the phenomenon of air mixing by back surface unevenness | corrugation.

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. The surface layer 101 of the surface layer film (a) is embossed (not shown).

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.

A biaxially stretched copolymer polyethylene terephthalate film (B) is a resin film obtained by using two or more kinds of acid components and / or glycol components. For example, the dicarboxylic acid component is terephthalic acid. A neopentyl glycol copolymerized amorphous polyethylene terephthalate resin having a glycol component of 60 to 90 mol% of ethylene glycol and 10 to 40 mol% of neopentyl glycol, and a dicarboxylic acid component of 60 to 98 mol% of terephthalic acid and isophthalic acid 2 An isophthalic acid copolymerized amorphous polyethylene terephthalate resin having a glycol component of ˜40 mol% and ethylene glycol can be mentioned.
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 mainly composed of a known vinyl chloride resin 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-based polycarbonate-polyorganosiloxane copolymer can also be used as a polycarbonate-based resin with improved impact resistance and flame retardancy.

The thickness of the surface layer film (a) is preferably 25 μm to 250 μm, 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 comprising 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%); A glycol component 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 comprising 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 consisting of 20 to 40 mol% 1,4-butanediol and 60 to 80 mol% 1,6-hexanediol (provided that 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 with 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.

The softening temperature of the thermoplastic saturated copolyester resin is preferably 55 to 85 ° C. 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 of the present inventors, when the softening temperature of the thermoplastic saturated copolymer polyester resin is 55 to 85 ° C., the thermoplastic saturated copolymer polyester 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 (b). 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.

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

By having both the groove | channel 4 and the groove | channel 5, generation | occurrence | production of the air by the back surface unevenness | corrugation of a three-dimensional coating molded product can be prevented, and heat-resistant external appearance property can be improved.
Here, the above-described “air mixing due to unevenness on the back surface” will be described with reference to FIG. FIG. 11 is a cross-sectional view of a vacuum forming sheet for explaining the phenomenon of air mixing due to back surface irregularities. As shown to (a), the sheet | seat 1 for vacuum forming of FIG. 11 has an adhesive layer (I) on the lower surface of a surface layer film (A), and a surface layer film (A) and an adhesive layer (I) It is the structure which has a backer layer (c) in between. Emboss E is applied to the surface layer 101 of the surface layer film (a). The vacuum forming sheet 1 is subjected to embossing after laminating the surface layer film (a) and the backer layer (c), and then the adhesive layer (a) is laminated. When the vacuum forming sheet 1 having such a configuration is heated by a heater at the time of vacuum forming and is in a semi-molten state, the portion of the adhesive layer (A) corresponding to the lower surface of the emboss E has a thickness as shown in FIG. Since the deformation is performed so as to maintain the balance of the direction, a phenomenon that the concave portion C is formed toward the inner direction of the sheet occurs. When the vacuum forming sheet 1 is stuck and laminated on the laminated base material 200 by vacuum forming in this state, as shown in (c), the concave portion C causes the air on the back surface of the adhesive layer (A). A is mixed. When the obtained vacuum molded product is subjected to a heat resistant appearance test, as shown in (d), the surface layer of the surface layer film (A) swells B due to the influence of air A, and the appearance is remarkably impaired.
In the present invention, by having both the groove 4 and the groove 5, it is possible to prevent the “air mixing due to the unevenness of the back surface”. 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 to 100 μm and a depth of 5 to 50 μm. In FIG. 3, w represents the width of the groove, and h represents the depth of the groove.

Further, the groove may have various shapes or patterns in the front view of the surface having the groove of the adhesive layer (A). 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.

One or more, preferably many, grooves 4 are present in the adhesive layer (a), more preferably at a density of 1 × 10 to 3.7 × 10 ⁶ per cm ² , more preferably 1 × 10 ⁶ per cm ^2. ^{There are 2} to 3.7 × 10 ⁵ densities.

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 copolyester 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 embossed on the surface layer film (A) It can be prepared by applying the above by a known coating method, bonding a release material having a male surface structure, and curing it. 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.
The embossing can be performed using a conventionally known method, for example, a drum heating embosser, a multi-cylinder embosser, or the like. As the embossed pattern, from the viewpoint of the effect of the present invention, for example, a conduit grain, a hairline, an abstract pattern, a satin pattern or the like is preferable. You may give an embossing with respect to the laminated body of a surface layer film (a) and a backer layer (c).
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 a 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.

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. When the upper limit is exceeded, it is too hard to be used as a release material.

The base film is preferably paper, biaxially stretched, or contains cavities 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, 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. Examples include ethylene-methacrylic acid copolymer and its ionomer. 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.

Further, the polyolefin resin preferably has a heat-resistant solvent property. 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 may 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 uneven thickness is likely 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 emboss can have a height that fits the groove. In addition, the release material in which the polyolefin resin-containing layer is embossed is likely 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. . When the polyolefin-based resin-containing layers are on both sides of the base film, the thickness ratio of the above layers is set to 0.3 to 1. Preferably, the polyolefin resin-containing layer has a thickness of 10 μm or more and 0.1 to 0.25 times the thickness of the substrate film when the polyolefin resin-containing layer is only on one side of the substrate film. In the case of being on both sides, the thickness is 10 μm or more and 0.1 to 0.25 times the thickness of the base film, and the thickness ratio to each other is 0.5 to 1, more preferably 0. 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 for each of both surfaces).

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.

The release material has an emboss on the surface opposite to the surface in which at least one of the polyolefin resin-containing layers is 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 forming using the vacuum forming sheet of the present invention is not particularly limited, but is preferably formed 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, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to these examples.

Example 1
Synthesis of Thermoplastic Saturated Copolyester Resin As the acid component is terephthalic acid, isophthalic acid, adipic acid, and 1,4-butanediol as the glycol component 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 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 comprising 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.
Moreover, embossing was performed with respect to the laminated body of the said surface layer film (a) and a backer layer (c). That is, an embossing machine composed of a metal engraving roll having a temperature of 140 ° C. and a pressure roll coated with semi-hard rubber is installed between a heating drum having a temperature of 140 ° C. and a cooling drum, and embossing is performed, whereby the surface film ) Was embossed with a conduit wood grain pattern.

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 at a) 250 [mu] m is: a 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: LDPE melted on one side of a high-quality paper having a basis weight of 110 g / m ² was extruded, and the LDPE was rolled with a roll so as to have a thickness of 20 μm and bonded together. 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 forming property: NGF-0912 type manufactured by Fuse Vacuum Co., Ltd. The vacuum forming property was evaluated under the surface temperature film forming temperature conditions described in the tables of Examples and Comparative Examples.
(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.

Air mixing due to unevenness on the back surface: NGF-0912 type manufactured by Fuse Vacuum Co., Ltd. Using a double-sided vacuum forming machine, vacuum forming was performed at the forming temperature conditions of the surface layer film described in the table of Examples and Comparative Examples, and the sheet was removed from the substrate. Forced peeling was performed and the peeled surface was visually observed and evaluated. The evaluation criteria are as follows.
A: The trace of air mixing is not seen at all on the peeling surface on the substrate side, and the gloss has disappeared uniformly.
○: No trace of air mixing is seen on the peeling surface on the base material side, but a slight shading is seen along the embossed shape.
(Triangle | delta): The air mixing trace along the embossed shape of the sheet | seat surface is sparsely seen on the peeling surface at the side of a base material.
X: The air mixing trace along the embossed shape of the sheet | seat surface is clearly seen in the peeling surface at the side of a base material.
* Traces of air contamination: The peeling surface on the substrate side where the adhesive layer and the substrate are in close contact with each other is in a state where the gloss has disappeared. On the other hand, when air is mixed between the adhesive layer and the base material, the base material substrate is exposed only in that portion, so that it can be identified as an air mixed trace by visual observation.

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.

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 . Subsequently, store at room temperature for 1 week, at 80 ° C for 1 week, and at room temperature for 3 months. After each storage and after leaving at room temperature for 1 hour, the distance between the marked lines is the same as above. 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.
X: 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 consisting 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 Examples 8 and 9, the embossing applied to the surface layer of the surface layer film (a) was changed to a hairline and a satin pattern, respectively.
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 a product name A-PET sheet general type, compound name, unstretched polyethylene terephthalate sheet, 150 μm in thickness, manufactured by Teijin Chemicals.

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.
The pressure-sensitive adhesive (1) is a trade name “Liquidyne AR-2037” manufactured by Big Technos Co., Ltd., paint composition: acrylate copolymer.

From the results in 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 the specific surface of the adhesive layer (a), air mixing due to the back surface unevenness of the three-dimensional coated molded product does not occur, and heat resistant appearance (50 ° C. × 400 hours, 80 ° C. × 400 hours) 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 was an example in which the surface layer film (a) was PET-G (2) and the laminated base material was ABS, and showed the same performance as Example 1.
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) was PET-G (3) and the backer layer (c) was not provided. Except that the vacuum formability was evaluated as ○, 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, the laminated base material is ABS, and the embossed pattern is a hairline. A performance similar to that of Example 1 was shown except that it was an evaluation.
-Example 9 is an example in which the surface layer film (a) is PC (2), the backer layer (c) is not provided, and the embossed pattern is satin-finished. Exhibited the same performance as in Example 1.
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 was an example in which the surface layer film (a) was PET-G (2) and the type of release material was B, and showed the same performance as Example 1.
Example 14 is an example in which the surface layer film (a) is made of PET-G (3), the backer layer (c) is not provided, and the type of the 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, and the vacuum formability is evaluated as Δ, heat-resistant adhesiveness (50 ° C x 400 hours), and heat-resistant appearance (50 ° C x 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 the backer layer (c) was not provided, and 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 (not having grooves 5), and is outside the scope of the present invention, so air mixing due to unevenness on the back surface, heat resistant appearance (50 ° C. × 400 hours), The heat appearance (80 ° C. × 400 hours) was evaluated as x.
Comparative Example 5 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 G (no groove 5). Therefore, the air contamination due to the unevenness on the back surface, the heat resistant appearance (50 ° C. × 400 hours), and the heat resistant appearance (80 ° C. × 400 hours) 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. ), 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 three-dimensional coated molded products for automobile interior use, home appliance use, and the like.

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 surface 200 Laminated substrate

Claims

A sheet for vacuum forming having an adhesive layer (I) on the lower surface of a surface layer film (A) embossed on the surface layer,
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 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 comprising 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%); A glycol component 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 vacuum forming sheet according to claim 1, wherein the thermoplastic saturated copolymer polyester resin has a softening temperature of 55 to 85 ° C.
3. 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).
The sheet for vacuum forming 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 vacuum forming sheet according to any one of claims 1 to 4, wherein the polyisocyanate is a polyisocyanate composed of hexamethylene diisocyanate.
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 vacuum forming sheet according to any one of claims 1 to 5, wherein the total is 100 mol%.
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 (provided that the glycol component described above) The sheet for vacuum forming according to claim 4, wherein the total is 100 mol%.
The vacuum forming sheet according to any one of claims 1 to 7, wherein the embossed pattern is a conduit grain, a hairline, an abstract pattern or a satin.
2. 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 vacuum forming sheet according to claim 1, which may be formed of a plurality of grooves.
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 11. The vacuum forming sheet according to any one of Items 9 to 10.
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 to 9 or 11, wherein the vacuum forming sheet is arranged so as to be elliptical or polygonal.
The vacuum forming sheet according to claim 10 or 12, wherein the polygon is a triangle, a quadrangle, or a hexagon.
The vacuum forming sheet according to any one of claims 1 to 13, which is used for vacuum forming by the following vacuum forming method.
Vacuum forming method: The vacuum forming sheet according to any one of claims 1 to 13 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 disposed on the side of the laminated base material. 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.
15. A molded product comprising the vacuum forming sheet according to claim 1 and a base material made of an ABS resin or an alloy of an ABS resin and a polycarbonate resin, laminated by vacuum molding.