WO2010122826A1

WO2010122826A1 - Sheet for vacuum molding

Info

Publication number: WO2010122826A1
Application number: PCT/JP2010/050802
Authority: WO
Inventors: 豊関根; 陸男清水
Original assignee: リケンテクノス株式会社
Priority date: 2009-04-23
Filing date: 2010-01-22
Publication date: 2010-10-28
Also published as: JP5351597B2; JP2010253740A

Abstract

Provided is a sheet for vacuum molding, which is excellent in terms of vacuum moldability, initial tackiness, and initial close adhesion, and is excellent in terms of the heat-resistant adhesion of a three-dimensional coated molded article. The sheet for vacuum molding has an adhesive layer (b) on the bottom surface of a surface film (a), wherein (a) is, for instance, acrylic resin film (a) and (b) is obtained by adding 0.1 to 5.0 parts by mass of a nitrogen-containing heterocyclic compound and 2 to 15 parts by mass of talc to 100 parts by mass of the thermoplastic saturated copolyester resin represented below and then adding 0.5 to 2.0 equivalents with respect to the thermoplastic saturated copolyester resin and curing. The polyester resin comprises an acid component having 40 to 70 mol% of terephthalic acid and 30 to 60 mol% of sebacic acid, and a glycol component having 40 to 90 mol% of 1,4-butanediol and 10 to 60 mol% of ethylene glycol.

Description

Vacuum forming sheet

The present invention relates to a sheet for vacuum forming, and more specifically, it is excellent in vacuum formability, initial tackiness, and initial adhesion, and the laminated substrate is also three-dimensional even in a metal substrate such as magnesium or aluminum. The present invention relates to a vacuum forming sheet excellent in heat-resistant adhesiveness (85 ° C. × 5 days) in a coated molded product.

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.

Patent Document 4 below discloses a vehicle window frame panel in which a surface of an aluminum window frame panel is coated with a synthetic resin sheet having a pressure-sensitive adhesive layer having a mesh-like 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 in a substantially vacuum state, and softening the synthetic resin decorative sheet by heating 2nd process, 3rd process of covering the softened synthetic resin decorative sheet on the aluminum window frame panel disposed in the second molding chamber, and increasing the pressure in the first molding chamber to increase the pressure of the aluminum window frame panel. A vehicle window frame panel manufacturing method is disclosed, comprising a fourth step of pressurizing the synthetic resin decorative sheet so as to conform to the shape.

Further, in Patent Document 5 below, a synthetic resin sheet is formed by laminating a surface sheet having abrasion resistance on the surface of a base material sheet made of a polyolefin sheet laminated in two to three layers, and on the back surface of the base material sheet. There is disclosed a surface plate structure in furniture, which is provided with an adhesive, and the synthetic resin sheet is integrally adhered over the surface side and side surface side of a base member in furniture such as a table.

However, the heat resistance of 85 ° C. × 5 days required for home appliance use, automotive interior use, etc., for the three-dimensional coated decorative molded product created using an adhesive or adhesive as described in the above prior art When the test is performed, there is a problem that the adhesive layer is drowned and does not have heat-resistant adhesiveness. In particular, when the laminated base material is a metallic base material such as magnesium or aluminum, it is inferior to the above-mentioned heat-resistant adhesiveness, and a sufficiently satisfying one has not been obtained. There was also room for improvement in vacuum moldability, initial tackiness, and initial adhesion.

Japanese Patent Publication No. 56-45768 Japanese Patent No. 3016518 Japanese Patent No. 3733564 JP 2004-237510 A JP 2000-157346 A

Therefore, the object of the present invention is excellent in vacuum moldability, initial tackiness, and initial adhesion, and even when the laminated substrate is a metal substrate such as magnesium or aluminum, The object is to provide a vacuum forming sheet excellent at 85 ° C. × 5 days).

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 added to 100 parts by mass of the following thermoplastic saturated copolymer polyester resin, 0.1 to 5.0 mass of a nitrogen-containing heterocyclic compound. Part and talc 2 to 15 parts by mass, and 0.5 to 2.0 equivalents of polyisocyanate is blended and cured with respect to the thermoplastic saturated copolymer polyester resin, and the sheet for vacuum forming .
Thermoplastic saturated copolyester resin: an acid component composed of 40 to 70 mol% terephthalic acid and 30 to 60 mol% sebacic acid (however, the total of the acid components is 100 mol%), 1,4-butanediol 40 A glycol component composed of ˜90 mol% and ethylene glycol 10-60 mol% (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 copolyester resin has a peak top melting point of 85 to 115 ° 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). 2. The vacuum according to 1 above, wherein the adhesive layer (a) is obtained by further blending 0.5 to 2.0 equivalents of a carbodiimide compound or an oxazoline compound with the thermoplastic saturated copolyester resin. Molding sheet.
6). 2. The sheet for vacuum forming according to 1 above, wherein the nitrogen-containing heterocyclic compound is a triazole compound or an imidazole compound.
7). The sheet for vacuum forming as described in 6 above, wherein the triazole compound is benzotriazole and the imidazole compound is imidazole.
8). 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) 8. The vacuum forming sheet as described in any one of 1 to 7 above, wherein the total is 100 mol%).
9. 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.
10. 10. The vacuum forming sheet as described in any one of 1 to 9 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 9 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.
11. 11. A molded product obtained by laminating the vacuum forming sheet according to any one of 1 to 10 above and a magnesium base material or an aluminum base material by vacuum forming.
12 12. The molded article according to 11 above, wherein the surface of the magnesium base is subjected to a phosphate surface treatment.
13. The vacuum forming sheet according to any one of 1 to 10 above and a laminated base material on which the vacuum forming sheet is laminated are arranged to face each other, and the first chamber is formed on the laminated base material side by the vacuum forming sheet. A second chamber is partitioned airtightly on the opposite side, 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 The material is brought into contact, and then the reduced pressure in the second chamber is released, and the vacuum forming sheet is adhered and laminated on the outer surface of the laminated substrate by the differential pressure between the first chamber and the second chamber. A vacuum forming method,
A vacuum forming method comprising heating the laminated base material to 60 ° C. to 100 ° C. during the step of bringing the vacuum forming sheet into contact with the laminated base material.
14 14. The vacuum forming method according to 13, wherein the laminated base material is a magnesium base material or an aluminum base material.

In the present invention, the type of the surface layer film (a) is specified, the composition of the thermoplastic saturated copolymer polyester resin in the adhesive layer (A), and the amounts of nitrogen-containing heterocyclic compound, talc and polyisocyanate used are specified. Therefore, it is excellent in vacuum formability, initial tackiness, and initial adhesion. Furthermore, even when the laminated base material is a metal base material such as magnesium or aluminum, the heat-resistant adhesiveness in the three-dimensional coated molded product ( A sheet for vacuum forming excellent in (85 ° C. × 5 days) can be provided. In addition, the vacuum formed product of the vacuum forming sheet of the present invention and a magnesium base material or an aluminum base material has good adhesion between them. In particular, in the vacuum molding method of the present invention, when the laminated base material is heated to 60 ° C. to 100 ° C. and both are adhered and laminated, the adhesion can be further enhanced.

It is sectional drawing for demonstrating the structure 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.

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).

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 viewpoint of biaxial stretchability, three-dimensional formability, 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)
In the adhesive layer (a) in the present invention, 0.1 to 5.0 parts by mass of a nitrogen-containing heterocyclic compound and 2 to 15 parts by mass of talc are blended with 100 parts by mass of the following thermoplastic saturated copolymer polyester resin. In addition, 0.5 to 2.0 equivalents of polyisocyanate is blended and cured with respect to the thermoplastic saturated copolyester resin.
Thermoplastic saturated copolyester resin: an acid component composed of 40 to 70 mol% terephthalic acid and 30 to 60 mol% sebacic acid (however, the total of the acid components is 100 mol%), 1,4-butanediol 40 A glycol component composed of ˜90 mol% and ethylene glycol 10-60 mol% (however, the total of the glycol components is 100 mol%).

If any one of the above acid components falls outside the above range, all of the initial tackiness, initial adhesion, and heat resistant adhesion cannot be satisfied at the same time.

A more preferable thermoplastic saturated copolymer polyester resin includes an acid component composed of 45 to 65 mol% terephthalic acid candy and 35 to 55 mol% sebacic acid (the total of the acid components is 100 mol%), 1,4- A glycol component comprising 50 to 80 mol% of butanediol and 20 to 50 mol% of ethylene glycol (however, the total of the glycol components is 100 mol%).

The peak top melting point of the thermoplastic saturated copolyester resin is preferably 85 to 115 ° C. Within this melting point range, there is an effect of improving all of initial tackiness, initial adhesion, and heat-resistant adhesion.
The peak top melting point refers to a peak top position in a melting curve drawn when a differential scanning calorimeter (DSC) is used and the measurement sample is heated at a rate of 20 ° C. per minute according to JIS K7122.
The peak top melting point can be adjusted by changing the blending ratio of the acid component.

In the adhesive layer (a) in the present invention, 0.1 to 5.0 parts by mass of a nitrogen-containing heterocyclic compound and 2 to 15 parts by mass of talc are blended with the thermoplastic saturated copolymer polyester resin, and This is one obtained by blending 0.5 to 2.0 equivalents of polyisocyanate with respect to the plastic saturated copolyester resin and curing.

Examples of the nitrogen-containing heterocyclic compound include a compound having a triazole ring, a compound having a pyrrole ring, a compound having a pyrazole ring, a compound having a thiazole ring, and a compound having an imidazole ring. Among them, a triazole compound which is a compound having a triazole ring or an imidazole compound which is a compound having an imidazole ring is preferable because it is excellent in the effect of improving adhesion to a metal laminate substrate, particularly a magnesium substrate. More preferably, the triazole compound is benzotriazole and the imidazole compound is imidazole. In the present specification, the oxazoline compound is not included in the nitrogen-containing heterocyclic compound described above.
The nitrogen-containing heterocyclic compound is presumed to be excellent in the ability to form a complex with a metal, particularly magnesium, in a metal laminate substrate, and to enhance the adhesion.

The talc may be natural talc, synthetic talc or modified talc, and the particle size thereof is, for example, 1 to 10 μm.
By adding talc, the stress applied to the adhesive layer (a) is dispersed, the adhesion on the surface is increased, and the adhesive strength is improved. When talc is not added, the stress applied to the adhesive layer (a) is concentrated at one point, the interface is easily broken, and the adhesive strength is reduced.

Polyisocyanates 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-hexamethylene triisocyanate, Bicycloheptane triisocyanate etc. are mentioned. Of these, hexamethylene diisocyanate is preferably used in terms of excellent initial tackiness, initial adhesion, and heat-resistant adhesiveness.

As described above, the adhesive layer (I) in the present invention comprises 0.1 to 5.0 parts by mass of a nitrogen-containing heterocyclic compound and 2 to 15 parts by mass of talc in 100 parts by mass of a thermoplastic saturated copolymer polyester resin. Blended, and 0.5 to 2.0 equivalents of polyisocyanate is blended with the thermoplastic saturated copolyester resin and cured.
When the nitrogen-containing heterocyclic compound is less than 0.1 parts by mass or more than 5.0 parts by mass, the initial adhesion and the heat resistant adhesiveness are deteriorated.
When the talc is less than 2 parts by mass, the initial adhesiveness and the heat-resistant adhesiveness are deteriorated. Conversely, when it exceeds 15 parts by mass, the heat-resistant adhesiveness is deteriorated and the initial tackiness and initial adhesiveness tend to be lowered.
When the polyisocyanate is less than 0.5 equivalent, the heat resistant adhesiveness deteriorates. Conversely, when it exceeds 2.0 equivalents, initial tackiness, initial adhesion, and heat-resistant adhesiveness all deteriorate.
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, 0.5 to 3.5 parts by mass of a nitrogen-containing heterocyclic compound and 5 to 10 parts by mass of talc are blended with 100 parts by mass of the thermoplastic saturated copolymer polyester resin, and the thermoplastic saturated copolymer polyester is used. More preferably, 0.8 to 1.6 equivalents of polyisocyanate is added to the resin.

In addition, in the adhesive layer (a) of the present invention, 0.5 to 2.0 equivalents of a carbodiimide compound or an oxazoline compound is further added to the thermoplastic saturated copolymer polyester resin on the metal laminate substrate, particularly on the surface. It is excellent in the effect of improving the adhesiveness with the magnesium base material which the phosphate surface treatment was performed, and is preferable.
Further, the blending ratio of the carbodiimide compound or oxazoline compound is preferably 0.7 to 1.6 equivalents.

Examples of the carbodiimide compound include compounds represented by the formula — (N═C═N—R—) n—.
In the formula, n represents an integer of 1 or more, and R represents an organic bond unit. For example, R can be either aliphatic, alicyclic, or aromatic. In addition, n is usually an appropriate integer selected from 1 to 50.

Specifically, bis (dipropylphenyl) carbodiimide, poly (4,4′-diphenylmethanecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylphenylene) Carbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), and the like, and monomers thereof are listed as carbodiimide compounds. These carbodiimide compounds may be used alone or in combination of two or more. As what is marketed as a carbodiimide compound, "Carbodilite series" (made by Nisshinbo Industries, Inc.) etc. can be used conveniently.

Examples of the oxazoline compound used in the present invention include 1,2-ethylenebisoxazoline, 2-cyclohexyl-2-oxazoline, 2- (2′-cyclohexenyl) -2-oxazoline, 2-oxazoline, 2-methyl-2- Examples include oxazoline, 2-ethyl-2-oxazoline, 2-isopropyl-2-oxazoline, and 2-n-propyl-2-oxazoline. These oxazoline compounds may be used alone or in combination of two or more. Moreover, the polymer of the said oxazoline compound may be sufficient. As what is marketed as an oxazoline compound, "Epocross series" (made by Nippon Shokubai Co., Ltd.) etc. can be used conveniently.
In addition, the equivalent of the carbodiimide compound and oxazoline compound as referred to in the present invention can be determined from the number of carbodiimide groups or oxazoline groups with respect to the number of carboxyl groups of the thermoplastic saturated copolymer polyester resin.

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 mainly composed of a known vinyl chloride resin can be used.

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

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, and a predetermined amount of a nitrogen-containing heterocyclic compound, talc and polyisocyanate compound, and a carbodiimide compound or an oxazoline compound as necessary are added to the paint. The coating material can be prepared by applying the coating material on the surface layer film (a) by a known coating method and curing it.
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 applied to the backer layer (c) by a known coating method. It can be prepared by applying and curing.
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.

The vacuum forming using the vacuum forming sheet of the present invention is not particularly limited, but it is preferable to form 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. 2 is a diagram for explaining an example of the vacuum forming method.
As shown in FIG. 2, the vacuum forming sheet 10 and the laminated base material 12 are arranged opposite to each other so that the adhesive layer (a) is in contact with the laminated base material 12 in the vacuum forming machine, and are laminated by the vacuum forming sheet 10. A first chamber 14 is partitioned on the substrate side, and a second chamber 16 is partitioned airtightly on the opposite side. 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. 3, 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 a metal substrate, particularly a magnesium substrate or an aluminum substrate in terms of adhesion.
Further, according to the present invention, in the step of bringing the vacuum forming sheet into contact with the laminated substrate, the laminated substrate is heated to 60 ° C. to 100 ° C., preferably 70 to 90 ° C. The adhesion between the sheet and the laminated substrate can be further enhanced. In particular, this effect is further enhanced when a magnesium base or an aluminum base is used.
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 resulting resin has the resin composition (1) shown in Table 1 below, the acid component is terephthalic acid, sebacic acid, the glycol component is 1,4-butanediol, ethylene glycol Was added 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). In addition, the said 4 types of monomer composition in a thermoplastic saturated copolyester resin was 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. Nitrogen-containing heterocyclic compound (1) (benzotriazole manufactured by Three Bond Co., Ltd.), talc (manufactured by Nippon Talc Co., Ltd., P-6, particle size D50 = 4.0 μm), carbodiimide compound (Nisshinbo Co., Ltd.) ), Carbodilite V-03), polyisocyanate (manufactured by Nippon Polyurethane, “Coronate HX” (hexamethylene diisocyanate), solid content 100%) is added in the amounts shown in Table 1, and the adhesive layer (A) forming coating is added. It was.

Preparation of Vacuum Forming Sheet As a surface layer film (a), acrylic resin film (1) (manufactured by Sumitomo Chemical Co., Ltd., “Technoloy S001”, polymethyl methacrylate, thickness 50 μm, tensile elastic modulus 1300 MPa, pencil hardness H ) 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, the adhesive layer (ii) forming coating material was coated on the backer layer (iii) with a knife coater, and the thickness after curing was 20 μm.

Vacuum forming Vacuum forming was performed by the vacuum forming method shown in FIGS. Table 1 shows the surface temperature (molding temperature) of the surface layer film (a) during molding. In addition, as the laminated base material, Mg (1) (magnesium casing, phosphoric acid surface treatment (chemical conversion treatment) has been completed. In the process of contacting the vacuum forming sheet and the magnesium casing during vacuum forming, The body was warmed to 70 ° C).
In the following examples and comparative examples, the size of the casing is a rectangle having a height of 5 mm, a depth of 200 mm, and a width of 280 mm.

Evaluation The following evaluation was performed.
Vacuum formability: NGF-0912 type manufactured by Fuse Vacuum Co., Ltd. The vacuum formability was evaluated using a double-sided vacuum forming 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 adhesiveness (85 ° C x 5 days):
After the vacuum molded product was left in a gear oven set at 85 ° C. for 5 days, the swelling and edge peeling were confirmed, and the sheet was forcibly peeled to evaluate the heat resistant adhesion.
(Double-circle): There is no swelling and peeling of an edge part, and it becomes a sheet material breakage by forced peeling.
○: There is no swelling and peeling of the edge, and peeling is performed while the sheet is stretched by forced peeling.
Δ: Slight swelling or peeling at the end is observed, and the sheet is peeled while maintaining some peeling resistance without being stretched by forced peeling.
X: Swelling or peeling of the edge is clearly observed, or the sheet peels off without sufficient peeling resistance by forced peeling.

The results are shown in Table 1.

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 1. Example 1 was repeated except that vacuum forming was performed. The results are shown in Table 1.

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 1. The results are shown in Table 1.

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 vacuum forming was performed at the molding temperature shown in Table 1. Example 1 was repeated except that. The results are shown in Table 1.

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 is composed of a glycol component composed of 70 mol% of glycol and 30 mol% of cyclohexanedimethanol. A thickness of 100 μm is used, and Al (1) (aluminum housing without chemical conversion treatment. Example 1 except that the aluminum molding was heated to 70 ° C. during the step of bringing the vacuum forming sheet into contact with the aluminum casing, and vacuum molding was performed at the molding temperature shown in Table 1. Was repeated. The results are shown in Table 1.

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 2 without providing the backer layer (c). The results are shown in Table 2.
In Table 2, 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.

Examples 10-13
In Example 1, Example 1 was repeated except that the resin structures (2) to (5) shown in Table 3 were employed instead of the resin structure (1). The results are shown in Table 3.

Examples 14-20
In Example 1, Example 1 was repeated except that the amount or type of the nitrogen-containing heterocyclic compound was changed as shown in Tables 4 and 5. The results are shown in Tables 4 and 5.
The nitrogen-containing heterocyclic compound (2) is Tolyltriazole manufactured by Three Bond Co., Ltd.
The nitrogen-containing heterocyclic compound (3) is imidazole manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
The nitrogen-containing heterocyclic compound (4) is 2-phenylimidazole manufactured by Shikoku Kasei.
The nitrogen-containing heterocyclic compound (5) is pyridine manufactured by Daicel Chemical Industries, Ltd.

Examples 21-22
In Example 1, Example 1 was repeated except that the blending ratio of talc was changed as shown in Table 6. The results are shown in Table 6.

Example 23
In Example 1, Example 1 was repeated except that 1.2 equivalent of the oxazoline compound was used instead of the carbodiimide compound. The results are shown in Table 6.
As the oxazoline compound, EPOCROS WS-500 manufactured by Nippon Shokubai Co., Ltd. was used.

Examples 24-25
In Example 1, Example 1 was repeated except that the blending ratio of the carbodiimide compound was changed as shown in Table 6. The results are shown in Table 6.

Examples 26-27
In Example 1, Example 1 was repeated except that the blending ratio of polyisocyanate was changed as shown in Table 7. The results are shown in Table 7.

Example 28
In Example 1, Example 1 was repeated except that A-PET (1) was used as the backer layer (c). The results are shown in Table 7.
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 29
In Example 7, Example 7 was repeated except that A-PET (2) was used as the surface layer film (a). The results are shown in Table 7.
A-PET (2) is Teijin Chemicals, trade name A-PET sheet black, compound name unstretched polyethylene terephthalate sheet, thickness 150 μm.

Examples 30-33
In Example 1, Example 1 was repeated except that the laminated base material was changed as shown in Table 8. The results are shown in Table 8.
Mg (2) to (5) are as follows.
Mg (2): Magnesium case, phosphoric acid surface treatment (chemical conversion treatment) completed. At the time of vacuum forming, the magnesium casing is not heated during the step of bringing the vacuum forming sheet into contact with the magnesium casing.
Mg (3): Magnesium case, phosphoric acid surface treatment (chemical conversion treatment) completed. During the vacuum forming, the magnesium casing was heated to 55 ° C. during the step of bringing the vacuum forming sheet and the magnesium casing into contact with each other.
Mg (4): Magnesium housing, phosphoric acid surface treatment (chemical conversion treatment) completed. During vacuum forming, the magnesium casing was heated to 65 ° C. during the step of bringing the vacuum forming sheet and the magnesium casing into contact with each other.
Mg (5): Magnesium case, phosphoric acid surface treatment (chemical conversion treatment) finished. During the vacuum molding, the magnesium casing was heated to 90 ° C. during the step of bringing the vacuum forming sheet and the magnesium casing into contact with each other.

Example 34
In Example 5, the laminated base material was made of Al (2) (aluminum casing. No chemical conversion treatment. During the vacuum forming, the aluminum casing was heated during the process of contacting the vacuum forming sheet and the aluminum casing. Example 5 was repeated except that the changes were made as shown in Table 8. The results are shown in Table 8.

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), and the molding temperature was set in Table 9. Example 1 was repeated except that the changes were made as shown in FIG. The results are shown in Table 9.

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 9. The results are shown in Table 9.

Comparative Examples 3-5
In Example 1, Example 1 was repeated except that the resin structures (6) to (8) shown in Table 9 were used instead of the resin structure (1). The results are shown in Table 9.

Comparative Examples 6-7
In Example 1, Example 1 was repeated except that the blending ratio of the nitrogen-containing heterocyclic compound (1) was changed as shown in Table 10. The results are shown in Table 10.

Comparative Examples 8-9
In Example 1, Example 1 was repeated except that the blending ratio of talc was changed as shown in Table 10. The results are shown in Table 10.

Comparative Examples 10-11
In Example 1, Example 1 was repeated except that the blending ratio of polyisocyanate was changed as shown in Table 11. The results are shown in Table 11.

Comparative Example 12
In Example 1, Example 1 was repeated except that the adhesive layer (I) was changed to the pressure-sensitive adhesive (1). The results are shown in Table 11.
The pressure-sensitive adhesive (1) is a product name of Liquidine AR-2037 manufactured by Big Technos Co., Ltd., paint composition: acrylate copolymer.

From the results in Tables 1 to 11, the following matters are derived.
-Example 1 specifies the type of surface layer film (a), the composition of the thermoplastic saturated copolymer polyester resin in the adhesive layer (a), and the amounts of nitrogen-containing heterocyclic compound, talc and polyisocyanate used. Is set to a specific range, so it has excellent vacuum formability, initial tackiness, and initial adhesion, and even when the laminated base material is a metal base material such as magnesium, the heat-resistant adhesiveness in a three-dimensional coated molded product A vacuum forming sheet excellent in (85 ° C. × 5 days) could be provided. Moreover, the vacuum formability could be improved by providing the backer layer (c).
Example 2 was an example in which the backer layer (c) 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 was an example in which the surface layer film (a) was PC (1), and showed the same performance as Example 1.
Example 5 was an example in which the surface layer film (a) was made of PET-G (2) and the laminated base material was made of Al (1), and showed the same performance as in Example 1.
-Example 6 is an example in which the surface layer film (a) is made of acrylic (2) and the backer layer (c) is not provided, and the same performance as in Example 1 except that the vacuum formability was evaluated as o. showed that.
-Example 7 is an example in which the surface layer film (a) was made of PET-G (3) and the backer layer (c) was not provided, and was the same as Example 1 except that the vacuum moldability was good. Showed the performance. 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 Al (1). Except this, 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 same performance as in Example 1 except that the vacuum formability was evaluated as ◯. showed that.
-Example 10 was the example which made the copolymer polyester resin into the resin structure (2), and showed the same performance as Example 1.
-Example 11 is the example which made the copolymer polyester resin the resin structure (3), and heat-resistant adhesiveness (85 degreeC x 5 days) became (triangle | delta) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
Example 12 is an example in which the copolymerized polyester resin has a resin configuration (4). The initial tackiness and initial adhesion were evaluated as Δ, and the heat resistance (85 ° C. × 5 days) was evaluated as ○. Otherwise, the same performance as in Example 1 was exhibited.
-Example 13 was the example which made the copolyester resin the resin structure (5), and showed the same performance as Example 1.
-Example 14 is the example which made the compounding ratio of the nitrogen-containing heterocyclic compound (1) 0.2 mass part, and initial stage adhesiveness and heat-resistant adhesiveness (85 degreeC x 5 days) became (triangle | delta) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 15 is the example which made the mixture ratio of nitrogen-containing heterocyclic compound (1) 1.0 mass part, and initial stage adhesiveness and heat-resistant adhesiveness (85 degreeC x 5 days) became (circle) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
Example 16 was an example in which the blending ratio of the nitrogen-containing heterocyclic compound (1) was 4.5 parts by mass, and the initial adhesion and heat-resistant adhesion (85 ° C. × 5 days) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
-Example 17 is an example which uses a nitrogen-containing heterocyclic compound (2), and initial stage adhesiveness and heat-resistant adhesiveness (85 degreeC x 5 days) became (circle) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 18 is an example using a nitrogen-containing heterocyclic compound (3), and showed the same performance as Example 1.
-Example 19 is an example using a nitrogen-containing heterocyclic compound (4), and initial adhesiveness and heat-resistant adhesiveness (85 degreeC x 5 days) became (circle) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 20 is an example which uses a nitrogen-containing heterocyclic compound (5), and initial adhesiveness and heat-resistant adhesiveness (85 degreeC x 5 days) became (triangle | delta) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 21 is the example which made the blending ratio of talc 3 mass parts, and initial adhesiveness and heat-resistant adhesiveness (85 degreeC x 5 days) became (triangle | delta) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 22 is the example which made the blending ratio of talc 13 mass parts, and initial tack property and heat-resistant adhesiveness (85 degreeC x 5 days) became (triangle | delta) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 23 was the example which used the oxazoline compound instead of the carbodiimide compound, and showed the same performance as Example 1.
-Example 24 is the example which made the compounding ratio of the carbodiimide compound 0.3 equivalent, and initial stage adhesiveness and heat-resistant adhesiveness (85 degreeC x 5 days) became (circle) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 25 is the example which made the mixing | blending ratio of the carbodiimide compound 2.2 equivalent, and initial stage adhesiveness and heat-resistant adhesiveness (85 degreeC x 5 days) became (circle) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 26 is the example which made the blending ratio of polyisocyanate 0.7 equivalent, and heat-resistant adhesiveness (85 degreeC x 5 days) became (DELTA) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
-Example 27 is the example which made the compounding ratio of polyisocyanate 1.8 equivalent, and initial stage tack property, initial stage adhesiveness, and heat-resistant adhesiveness (85 degreeC x 5 days) became (triangle | delta) evaluation. Otherwise, the same performance as in Example 1 was exhibited.
Example 28 was an example in which A-PET (1) was used for the backer layer (c), and the vacuum formability and heat resistant adhesiveness (85 ° C. × 5 days) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
Example 29 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 and heat resistant adhesiveness (85 ° C. × 5 days) were Δ It became evaluation. Otherwise, the same performance as in Example 1 was exhibited.
Example 30 was an example in which the base material was Mg (2), and the initial adhesion and heat-resistant adhesion (85 ° C. × 5 days) were evaluated as Δ. Otherwise, the same performance as in Example 1 was exhibited.
Example 31 was an example in which the base material was Mg (3), and the initial adhesion and heat-resistant adhesion (85 ° C. × 5 days) were evaluated as “good”. Otherwise, the same performance as in Example 1 was exhibited.
-Example 32 was the example which made the base material Mg (4), and showed the same performance as Example 1.
-Example 33 was the example which made the base material Mg (5), and showed the same performance as Example 1.
In Example 34, the base material was Al (2), and the initial adhesion and heat-resistant adhesion (85 ° C. × 5 days) 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, heat resistant adhesiveness (85 ° C. × 5 days) Became x evaluation.
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 The property (85 ° C x 5 days) was evaluated as x.
Comparative Example 3 is an example in which a copolymerized polyester resin is used as the resin configuration (6), and is outside the scope of the present invention, so that the heat resistant adhesiveness (85 ° C. × 5 days) was evaluated as x.
Comparative Example 4 is an example in which the copolymerized polyester resin has a resin configuration (7), and is outside the scope of the present invention, so that the initial tackiness, initial adhesion, and heat resistant adhesiveness (85 ° C. × 5 days) are × It became evaluation. Comparative Example 5 is an example in which the copolymerized polyester resin is made into a resin configuration (8) and is outside the scope of the present invention, so that the heat resistant adhesiveness (85 ° C. × 5 days) was evaluated as x.
Comparative Example 6 is an example in which the blending ratio of the nitrogen-containing heterocyclic compound (1) is 0.05 parts by mass, and is outside the scope of the present invention. Therefore, the initial adhesion and heat-resistant adhesiveness (85 ° C. × 5 days ) Became x evaluation.
Comparative Example 7 is an example in which the blending ratio of the nitrogen-containing heterocyclic compound (1) is 5.5 parts by mass, and is outside the scope of the present invention. Therefore, the initial adhesion and heat-resistant adhesiveness (85 ° C. × 5 days) ) Became x evaluation.
Comparative Example 8 is an example in which the blending ratio of talc is 1 part by mass, and is outside the scope of the present invention, so the initial adhesion and heat-resistant adhesiveness (85 ° C. × 5 days) were evaluated as x.
Comparative Example 9 is an example in which the blending ratio of talc is 17 parts by mass, and is outside the scope of the present invention, so that the initial tackiness and initial adhesion are Δ evaluated, and the heat resistant adhesiveness (85 ° C. × 5 days) is × Evaluated.
Comparative Example 10 was an example in which the blending ratio of polyisocyanate was 0.3 equivalent and was outside the scope of the present invention, so the heat resistant adhesiveness (85 ° C. × 5 days) was evaluated as x.
Comparative Example 11 is an example in which the blending ratio of the polyisocyanate is 2.2 equivalents, and is outside the scope of the present invention, so that the initial tackiness, initial adhesion, and heat resistant adhesiveness (85 ° C. × 5 days) are × Evaluated.
Comparative Example 12 was an example in which the pressure-sensitive adhesive (1) was used for the adhesive layer (I), and was outside the scope of the present invention, so the heat resistant adhesiveness (85 ° C. × 5 days) was evaluated as x.

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

DESCRIPTION OF SYMBOLS 1 Vacuum forming sheet 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

Claims

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 added to 100 parts by mass of the following thermoplastic saturated copolymer polyester resin, 0.1 to 5.0 mass of a nitrogen-containing heterocyclic compound. Part and talc 2 to 15 parts by mass, and 0.5 to 2.0 equivalents of polyisocyanate is blended and cured with respect to the thermoplastic saturated copolymer polyester resin, and the sheet for vacuum forming .
Thermoplastic saturated copolyester resin: an acid component composed of 40 to 70 mol% terephthalic acid and 30 to 60 mol% sebacic acid (however, the total of the acid components is 100 mol%), 1,4-butanediol 40 A glycol component composed of ˜90 mol% and ethylene glycol 10-60 mol% (however, the total of the glycol components is 100 mol%).
2. The vacuum forming sheet according to claim 1, wherein a peak top melting point of the thermoplastic saturated copolyester resin is 85 to 115 ° 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).
2. The adhesive layer (a) according to claim 1, wherein 0.5 to 2.0 equivalents of a carbodiimide compound or an oxazoline compound is further added to the thermoplastic saturated copolymer polyester resin. Vacuum forming sheet.
The vacuum forming sheet according to claim 1, wherein the nitrogen-containing heterocyclic compound is a triazole compound or an imidazole compound.
The vacuum forming sheet according to claim 6, wherein the triazole compound is benzotriazole, and the imidazole compound is imidazole.
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 7, 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 9, 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 9 and a laminated base material on which the vacuum forming sheet is laminated are arranged opposite to each other, and the vacuum forming sheet causes 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 product comprising the vacuum forming sheet according to any one of claims 1 to 10 and a magnesium base material or an aluminum base material laminated by vacuum forming.
The molded article according to claim 11, wherein a phosphate surface treatment is applied to the surface of the magnesium substrate.
The vacuum forming sheet according to any one of claims 1 to 10 and a laminated base material on which the vacuum forming sheet is laminated are arranged to face each other, and the first chamber is provided on the laminated base material side by the vacuum forming sheet. The second chamber is separated from each other in an airtight manner, 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 laminate A base material is brought into contact, and then the reduced pressure in the second chamber 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 and the second chamber. A vacuum forming method,
A vacuum forming method comprising heating the laminated base material to 60 ° C. to 100 ° C. during the step of bringing the vacuum forming sheet into contact with the laminated base material.
The vacuum forming method according to claim 13, wherein the laminated base material is a magnesium base material or an aluminum base material.