JP5254766B2 - LAMINATED SHEET, PARTS HAVING THE SAME AND ITS MANUFACTURING METHOD - Google Patents

Description

  The present invention relates to a laminated sheet, a component to which the laminated sheet is attached, and a method for producing the same, and more specifically, a laminated sheet that can be attached to a base material using a vacuum thermocompression bonding method and the base material to the base material. The manufactured parts and the manufacturing method thereof.

  As a method of decorating the surface of a three-dimensional base material such as an automobile interior part or exterior part, a method of attaching a decorative film or sheet to the surface of the base material is known. A typical decorative sheet attaching method includes an insert molding method. This is because an insert sheet having a pattern layer or the like formed on a base sheet is directly or pre-molded and then set in an injection molding die, and a three-dimensional molded product is injection-molded at the same time. This is a method for performing decoration by integrally bonding to the substrate.

  As described above, the decorative sheet to be attached to the surface of the molded article simultaneously with the injection molding is required to have stretchability in order to follow the shape of the substrate surface at the time of molding. In addition, it is desired to use a material having high scratch resistance, chemical resistance, and the like for the outermost surface layer of the decorative sheet.

  Patent Document 1 describes a decorative sheet that has scratch resistance, chemical resistance, and the like, and does not cause breakage abnormality even when stretched at a surface magnification of 170% or more. A transparent thermoplastic resin sheet (B1), a thermoplastic resin sheet (C) containing a colorant, an adhesive layer (D) and a base sheet (E) are laminated in this order, and a transparent thermoplastic resin sheet (B1) ) A decorative sheet on which a transparent cured resin layer (A) is provided, the transparent cured resin layer (A) comprising a coating film made of urethane (meth) acrylate, and a transparent thermoplastic resin sheet (B1) ) And a thermoplastic resin sheet (C) containing a coloring agent are made of a thermoplastic acrylic polymer. Further, when the cured resin layer (A) is formed, the content of the hydroxyl group-containing (meth) acrylate contained in the hydroxyl group-containing (meth) acrylate copolymer is preferably 5 to 40% by mass, and more preferably 10 to 10%. It is described that it is preferably 100% by mass, and if it is less than 5% by mass, a sufficient cross-linked structure cannot be obtained, and surface properties having excellent chemical resistance and scratch resistance cannot be obtained. Further, this decorative sheet is thermoformed by vacuum forming or the like to prepare a preform, and after this preform is inserted into an injection mold, a thermoplastic resin is melt-injected into the mold and decorated. A method for producing a molded article to which a sheet is attached is described.

  Patent Document 2 discloses a laminated film that can be used to form a wear-resistant and chemical-resistant surface protective layer on the surface of a deep-drawn three-dimensional insert-molded product, and has a (meth) acrylic equivalent of 100 to A surface protective layer comprising a thermal reactant of a thermal and active energy ray-curable resin composition containing, as active ingredients, a polymer having 300 g / eq, a hydroxyl value of 20 to 500, and a weight average molecular weight of 5000 to 50000 and a polyfunctional isocyanate is described. Has been.

Japanese Patent No. 3957716, claim 1, paragraphs [0006] and [0048] to [0050] Japanese Patent No. 3137618, paragraph [0005]

  In the conventional decorative sheet and laminated film described above, an insert method for attaching a decorative sheet to the surface of a base material at the same time as the base material of a component that is a molded body is formed using an injection molding method. On the other hand, a vacuum thermocompression bonding method is also known as a method for attaching a decorative sheet to a base material different from the insert molding method. In general, the insert molding method described above may also be used in the case of producing a decorative sheet preform, but the affixing method here is a method used for directly affixing to a component base material. It is.

  In the vacuum thermocompression bonding method, a sheet is heated and stretched with respect to a preformed base material, and is attached to the base material using a pressure difference. Since the component is attached to the substrate surface by a separate operation from molding, the decorative sheet can be attached to the substrate of various shapes with a single vacuum thermocompression bonding apparatus. Further, the vacuum thermocompression bonding method can be applied to the unevenness of the substrate surface with good followability. Continuous coating from the front surface to the back surface at the end of the base material, which is difficult with the pasting method of the decorative sheet using a conventional mold, that is, entrainment coating is also possible. Therefore, this is an affixing method that can be expected to provide a decoration with excellent covering properties for complex three-dimensional parts having various shapes.

  However, many of the conventional decorative sheets are premised on pasting by an insert molding method or the like, and are not necessarily suitable for pasting using a vacuum thermocompression bonding method. In particular, when carrying out covering covering of the decorative sheet at the edge part of the base material, the decorative sheet in contact with the edge part of the base material is applied with other pasting methods that locally exceed 300% by area or 400% by area. Compared to the case where it is used, a remarkably large stretch may occur, and therefore breakage and cracks are likely to occur.

  On the other hand, the decorative sheet that is attached to the surface of the base material is required to have an aesthetic appearance, and the stretching that occurs during application does not cause cracks or breakage, but also causes marks and scratches caused by objects and human nails. Although it is difficult and chemical resistance is required, it is difficult for these properties to be compatible with high stretchability.

  Then, in view of the present state of the prior art described above, the problem of the present invention is that it has high stretchability suitable for attachment to a substrate using a vacuum thermocompression bonding method, and the outermost surface layer has good scratch resistance. It is to provide a laminated sheet having chemical resistance. Moreover, it is providing the component using this, and its manufacturing method.

The laminated sheet of one embodiment of the present invention is affixed to a substrate,
Including a surface layer (A) disposed on the outermost surface, a thermoplastic resin layer (B), and an adhesive layer (C) adhered to the substrate;
The surface layer (A)
A (meth) acrylic copolymer (I) obtained by copolymerizing a (meth) acrylate monomer containing a hydroxyl group-containing monomer of 0.5% by mass or more and less than 5% by mass, and having two or more isocyanate groups in one molecule The glass transition point (Tg) formed by mixing the isocyanate compound (II) with a mixing ratio of 3 to 16 mmol of the isocyanate group with respect to 100 g of the (meth) acrylic copolymer (I) is 80 ° C. or higher. (Meth) acrylic resin compound as a main component.

  The method for producing a component according to one embodiment of the present invention includes a step of attaching the above-described laminated sheet of the present invention to the surface of a substrate of the component by a vacuum thermocompression bonding method.

  The component of one embodiment of the present invention is obtained by attaching the above-described laminated sheet of the present invention to the surface of a base material of the component.

  According to the laminated sheet of the present invention, it is possible to provide scratch resistance and chemical resistance, as well as surface stretchability suitable for application to a substrate by a vacuum thermocompression bonding method.

  Moreover, according to the manufacturing method of this invention, the components by which the favorable entrainment coating without the crack etc. in not only the base material surface but a base-material edge part with the laminated sheet of this invention was given can be provided.

  Furthermore, according to the component of the present invention, a good appearance component is provided which has a good entrainment coating without cracks or the like not only at the substrate surface but also at the edge of the substrate, and has scratch resistance and chemical resistance. Can provide.

  The laminated sheet which is an embodiment of the present invention (hereinafter referred to as “this embodiment”) is a laminated sheet used by being attached to a substrate, and at least a surface layer (A) disposed on the outermost surface, and heat It includes a plastic resin layer (B) and an adhesive layer (C) bonded to the substrate. Here, the surface layer (A) of the laminated sheet is composed of (meth) acrylic copolymer (I) obtained by copolymerizing a (meth) acrylate monomer containing 1 to 5% by mass of a monomer containing a hydroxyl group, and one molecule. Formed from a mixed solution of an isocyanate compound (II) having two or more isocyanate groups at a mixing ratio of 3 to 16 mmol of isocyanate groups with respect to 100 g of (meth) acrylic copolymer (I) The transition point (Tg) is mainly composed of a (meth) acrylic resin compound of 80 ° C. or higher.

  The laminated sheet of the present embodiment provides the heat resistance and stretchability of the surface layer (A) having scratch resistance and chemical resistance and suitable for being attached to a substrate using a vacuum thermocompression bonding method. Can do. In other words, when using the vacuum thermocompression bonding method, it is possible to suppress the occurrence of cutting and cracking even for large stretching at high temperatures locally generated in the laminated sheet when the laminated sheet is wrapped around the edge of the substrate. . Therefore, it can be used as a laminated sheet suitable for coating on various substrates using a vacuum thermocompression bonding method. In addition, although the lamination sheet of this embodiment is especially suitable for the sticking using a vacuum thermocompression bonding method, it cannot be overemphasized that it can apply also to other sticking methods including an insert molding method. Absent.

  The laminated sheet of the present embodiment is suitable for use as a decorative sheet for decorating the substrate surface, but is not limited to decoration purposes, for example, for preventing scratches and contamination of the substrate. The purpose of attaching to the surface of the substrate including other purposes such as a protective sheet is not limited.

  Hereinafter, the laminated sheet of the present embodiment will be specifically described with reference to the drawings. In this specification, the concept of “sheet” is a laminated body having flexibility, and is called a “film”. It shall also include a laminate.

  In the present specification, the acrylate monomer and the methacrylate monomer are collectively referred to as “(meth) acrylate monomer”. Acrylic polymers and methacrylic polymers are collectively referred to as “(meth) acrylic polymers”. The (meth) acrylic polymer may be a copolymer arbitrarily combined with other non- (meth) acrylate monomers other than (meth) acrylic monomers, for example, vinyl unsaturated monomers.

  In this specification, the “wrap-around coating” is typically based on a continuous edge from the substrate surface, for example, at the edge of the substrate when a laminated sheet is attached to the substrate surface by a vacuum thermocompression bonding method. The coating aspect which coat | covers with a laminated sheet over the material back surface. Here, the “back surface” includes a surface that is normally invisible when observed from the front surface side of the component.

  FIG. 1 is a cross-sectional view illustrating a laminated sheet 100 according to an embodiment. FIG. 2 is a cross-sectional view showing an example of the component 400 in which the laminated sheet 100 is attached to the base material 410, and an example in which the laminated sheet 100 is wrapped around and covered with the base material.

  As shown in FIG. 1, the laminated sheet 100 includes at least a surface layer (A) 110, a thermoplastic resin layer (B) 120, and an adhesive layer (C) 130 that is bonded to a base material. In the laminated sheet 100 before being affixed to the base material 410, the release sheet 200 is usually affixed to the exposed surface of the adhesive layer (C) as shown in FIG. In addition, if necessary, the peelable support sheet 300 used at the time of manufacture is often placed on the exposed surface of the surface layer (A) 110.

  A surface layer (A) has an acrylic resin compound as a main component. This acrylic resin compound is obtained by a polymerization addition reaction using a mixed solution in which the (meth) acrylic copolymer (I) and the isocyanate compound (II) as a crosslinking agent are mixed. The (meth) acrylic copolymer (I) is obtained by copolymerizing a (meth) acrylate monomer containing 0.5% by mass or more and less than 5% by mass of a monomer containing a hydroxyl group. The isocyanate compound (II) having two or more isocyanate groups per molecule was formed by crosslinking reaction of 100 g of (meth) acrylic copolymer (I) so that the isocyanate groups were 3 to 16 mmol. The main component is an acrylic resin compound. The glass transition point (Tg) of the obtained acrylic resin compound is adjusted to 80 ° C. or higher.

  In the case where an acrylic resin layer is used as a surface layer in a conventional decorative sheet, in general, in order to obtain a sufficient crosslinked structure, at least 5% by mass or more of a hydroxyl group-containing monomer added at the time of preparing a (meth) acrylic copolymer, Although preferably 10% by mass or more is recommended (see Patent Document 1), in this embodiment, the hydroxyl group-containing monomer is intentionally suppressed to less than 5% by mass and used. In addition, it is good also as 4 mass% or less or 3 mass% or less. Thus, by setting the ratio of the hydroxyl group-containing monomer to less than 5% by mass, the progress of the degree of crosslinking of the (meth) acrylic copolymer can be suppressed, and the film can be more easily stretched. Therefore, it is possible to improve the formability accompanied with the stretching at the time of sticking to the base material.

  Furthermore, in the surface layer (A) of this embodiment, 16 mmol or less of isocyanate groups are mixed with 100 g of the (meth) acrylic copolymer (I) of the isocyanate compound (II) as a crosslinking agent. This also suppresses the progress of cross-linking, gives high stretchability, and can improve the formability accompanied by stretching at the time of pasting. It may be 12 mmol or less, or 10 mol or less. A laminated sheet free from breakage and cracks can be provided in the case of a large stretching of 300% by area or more or 400% by area or more that is locally generated when the coating is performed on the edge of the substrate using the vacuum thermocompression bonding method. In addition, 100 area% here refers to the area of the sheet | seat before extending | stretching, and the sheet | seat area after extending | stretching is 300 area%. The lamination sheet is extended | stretched about 1.73 times in the vertical and horizontal direction, and is about 3 times. The state which becomes the area of.

  As described above, the surface layer (A) of the present embodiment is prepared by adjusting the amount of the hydroxyl group-containing monomer to less than 5% by mass when forming the (meth) acrylic copolymer (I), and the isocyanate compound (II). By adjusting the mixing ratio, the progress of crosslinking is suppressed and the stretchability is improved, while the glass transition point (Tg) of the acrylic resin compound is adjusted to a relatively high temperature of 80 ° C. or higher. By adjusting the glass transition point, the structure of the acrylic copolymer itself is made more honeyed and prevents the intrusion of chemicals. It is possible to increase the impression recovery power, which is the power to prevent the remaining.

  In addition, when sticking a decoration sheet etc. to a base material using a vacuum thermocompression bonding method etc., considering the heat resistance of the base material, the sticking temperature is 110 ° C. to 150 ° C., most commonly about 120 ° C. Adjusted. The glass transition point (Tg) of the acrylic resin compound is desirably in a range that does not exceed at least the pasting temperature, and may be, for example, 90 ° C. or higher, or 105 ° C. or higher as long as it is lower than the pasting temperature.

  Thus, by setting the glass transition point of the acrylic resin compound to 80 ° C. or higher, the amount of the hydroxyl group-containing monomer when forming the (meth) acrylic copolymer (I) is at most 0.5% by mass or When the mixing ratio of isocyanate groups to 100 g of (meth) acrylic copolymer (I) is 3 mmol or more, or 5 mmol or more, practical chemical resistance and scratch resistance can be achieved with the surface layer (A ).

  Adjustment of the glass transition point (Tg) of the acrylic resin compound is performed by adjusting the kind and mixing ratio of the (meth) acrylate monomer used when the (meth) acrylic copolymer (I) is produced.

  In this embodiment, the (meth) acrylate monomer that can be used for the preparation of the (meth) acrylic copolymer (I) is mainly composed of a (meth) acrylate monomer having a glass transition temperature (Tg) of 80 ° C. or higher. Is mentioned. Here, the glass transition temperature (Tg) refers to the glass transition temperature of a homopolymer obtained when a (meth) acrylate monomer is polymerized. Examples of such monomers include methyl methacrylate (Tg = 105 ° C.), tertiary butyl methacrylate (Tg = 107 ° C.), cyclohexyl methacrylate (Tg = 83 ° C.), isobornyl methacrylate (Tg = 155 ° C.), iso Examples include bornyl acrylate (Tg = 94 ° C.), dicyclopentenyl acrylate (Tg = 120 ° C.), dicyclopentanyl acrylate (Tg = 120 ° C.), dicyclopentanyl methacrylate (Tg = 175 ° C.), and the like. Of these, it is particularly preferable to use a methyl (meth) acrylate (MMA) monomer.

  It should be noted that the glass transition temperature (Tg) of the (meth) acrylate monomer having a glass transition point of 80 ° C. or higher as described above is provided on condition that the glass transition point (Tg) of the acrylic resin compound can be 80 ° C. or higher. One or more (meth) acrylate monomers having a temperature of 80 ° C. or less may be mixed and used. Examples of such (meth) acrylate monomers having a glass transition temperature (Tg) of 80 ° C. or lower include methyl acrylate (Tg = 8 ° C.), ethyl acrylate (Tg = −22 ° C.), and butyl acrylate (Tg = −56). ° C), isobutyl acrylate (Tg = −26 ° C.), tertiary butyl acrylate (Tg = 41 ° C.), isoamyl acrylate (Tg = −45 ° C.), cyclohexyl acrylate (Tg = 15 ° C.), 2-ethylhexyl acrylate (Tg = -70 ° C), lauryl acrylate (Tg = -3 ° C), ethyl methacrylate (Tg = 65 ° C), butyl methacrylate (Tg = 20 ° C), isobutyl methacrylate (Tg = 48 ° C), 2-ethylhexyl methacrylate (Tg = -10 ° C.), lauryl methacrylate (Tg = −65 ° C.), etc. Acrylate, 2-methoxyethyl acrylate (Tg = −50 ° C.), ethyl carbitol acrylate (Tg = −67 ° C.), tetrahydrofurfuryl acrylate (Tg = −12 ° C.), tetrahydrofurfuryl methacrylate (Tg = 60 ° C.), Other (meth) acrylates such as benzyl acrylate (Tg = 6 ° C.), benzyl methacrylate (Tg = 54 ° C.), and phenoxyethyl acrylate (Tg = −22 ° C.) can be mentioned.

  Moreover, in this embodiment, although the hydroxyl-containing monomer amount at the time of forming (meth) acrylic copolymer (I) is prepared to less than 5 mass%, as a hydroxyl-containing (meth) acrylate monomer used here, Is, for example, a hydroxyalkyl (meth) acrylate having 2 to 8 carbon atoms such as hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate; hydroxyalkyl vinyl ether such as hydroxyethyl vinyl ether; ethylene glycol, 1,6-hexane Hydroxyl group-containing (meth) acrylates obtained by esterification of diol compounds such as diol, neopentyl glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol and the like and carboxyl group-containing unsaturated monomers such as (meth) acrylic acid. Rate: Monomers such as hydroxyl group-containing (meth) acrylates obtained by reacting glycidyl (meth) acrylate with acids such as acetic acid, propionic acid, p-tert-butylbenzoic acid, fatty acids, or monoamines such as alkylamines Can be mentioned.

  Furthermore, what used the side chain hydroxyl group of the hydroxyl-containing (meth) acrylate mentioned above extended the side chain length, and introduce | transduced the hydroxyl group into the terminal can also be used. The structure of the side chain and the introduction method are not particularly limited. For example, a structure having a hydroxyl group at the end can be easily introduced by ring-opening addition of a lactone ring closed from a hydroxyl group and a carboxyl group. it can. The degree of polymerization of the lactone introduced into the side chain may be 1 or more, preferably the degree of side chain polymerization is 1 to 10, more preferably the degree of polymerization of side chain is 1 to 5. When the degree of polymerization of the side chain exceeds 10, the hydroxyl group concentration in the resin is diluted, so that the reactivity with isocyanate becomes low, and it takes time until complete curing. Curability, surface physical properties and molding The problem is likely to occur in terms of sex.

  In addition, you may use these hydroxyl-containing (meth) acrylates in mixture of 2 or more types.

  For the preparation of the (meth) acrylic copolymer (I), a solution polymerization method such as a solution radical polymerization method, a non-aqueous dispersion polymerization method or a bulk polymerization method can be used. For example, in a solvent such as ethyl acetate, a hydroxyl group-containing (meth) acrylate monomer and another predetermined (meth) acrylate monomer are mixed together with a polymerization initiator and heated to a predetermined temperature for polymerization.

  As the isocyanate compound (II) used for forming the acrylic resin compound used for the surface layer (A) of the present embodiment, one or more isocyanate compounds having two or more isocyanate groups in one molecule are used. Can be used as a mixture.

  Examples of the isocyanate compound (II) used herein include aliphatic diisocyanates such as hexamethylene diisocyanate; cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate; tolylene diisocyanate, naphthalene diisocyanate, and the like. Aromatic diisocyanates; aliphatic triisocyanates such as 2,4,6-triisocyanatocycloheptane and 1,2,5-triisocyanatocyclooctane; 1,3,5-triisocyanatobenzene, 2,4,6 -Aromatic triisocyanates such as triisocyanatonaphthalene can be used.

  The polyisocyanate compound having three or more isocyanate groups is a dimer or trimer of a divalent or higher polyisocyanate, a divalent or trivalent polyisocyanate and a polyhydric alcohol, or a hydroxyl group at the terminal. An adduct formed by reacting a polyester resin having an isocyanate group with excess isocyanate group, a free isocyanate group of an isocyanate compound having a free isocyanate group, such as phenols, oximes, lactams, alcohols, mercaptans, etc. Examples include blocked polyisocyanates blocked with a blocking agent, and polyisocyanates having a biuret structure obtained by reacting water with a polyisocyanate having a free isocyanate group, alone or mixed with two or more isocyanate compounds. May be used.

  Furthermore, it is also possible to use a polyfunctional polyisocyanate in which one isocyanate group residue of the polyfunctional polyisocyanate as described above is linked using various polyol compounds. In addition, a curing catalyst may be used as necessary to react and cure the hydroxyl group-containing (meth) acrylate copolymer and the isocyanate compound. These may be any known and commonly used curing catalyst and are not particularly limited.

  The surface layer (A) contains an acrylic resin compound as a main component, but besides that, an additive may be added within a range in which the effect of the laminated sheet of the present invention can be exhibited. Examples of such additives include antifriction agents, surface conditioners (leveling agents, antifoaming agents, antiblocking agents, etc.), light resistant additives (ultraviolet absorbers, stabilizers, etc.), plasticizers, pigments, Examples thereof include an antioxidant, an antistatic agent, a flame retardant, a lubricant, an antifungal agent, an antibacterial agent, a non-reactive resin, a synthetic rubber, and a dispersant.

  In particular, in order to improve scratch resistance and chemical resistance while maintaining the transparency of the surface layer (A), organic solvent dispersible metal oxide fine particles may be added. Examples of these organic solvent-dispersible metal oxides include titanium oxide, tin oxide, zirconia oxide, silicon oxide (silica), aluminum oxide, and zinc oxide.

  Although the thickness of the surface layer (A) of this embodiment is not specifically limited, For example, in order to acquire sufficient scratch resistance, it is preferable that it is 20 micrometers or more, or 30 micrometers or more, and also 50 micrometers or more may be sufficient. Moreover, in order to show favorable stretchability at the time of affixing a base material, it is preferable to set it as 100 micrometers or less or 80 micrometers or less.

  The acrylic resin compound constituting the surface layer (A) is prepared by various methods by mixing a solution obtained by mixing the above-described (meth) acrylic copolymer (I) and the isocyanate compound (II) together with a polymerization initiator and a solvent. It can be formed by coating and heating. The thickness of the surface layer (A) can be adjusted by the viscosity of the solution, the coating method, the number of coating repetitions, and the like.

  The surface layer (A) is not limited to a single layer, and may be formed of two or more layers. Components other than the main component may be different for each layer. Further, at least one layer may be a surface layer to which decorativeness is added. For example, as shown in FIG. 4, the surface layer 100 may have a laminated structure of a surface layer a1 and a surface layer a2 having a three-dimensional structure on the exposed surface. For example, the exposed surface of the surface layer a1 may be embossed. A matt appearance can be obtained by fine irregularities, and a stripe-shaped groove having a design such as a hairline pattern can be formed. In addition, according to demand, the surface layer (A) can be provided with a pattern such as geometric, satin, sand, sand pattern, background pattern, texture, character or the like. Alternatively, bead particles, metal oxide particles, and the like may be included in the surface layer a1.

  The method for forming the three-dimensional structure on the surface layer a2 is not particularly limited, but typically, the support sheet 300 having an uneven surface is used, and the surface layer a2 is formed thereon by coating. Thus, a method of easily transferring the unevenness of the support sheet to the surface layer a2 can be used. Since the unevenness formed on the surface layer a2 by this method has a small residual stress generated at the time of formation, the shape retainability is high, and the uneven shape is not easily deformed or lost by heating or stretching at the time of application.

  Or as shown in FIG. 5, it is good also as a printed layer which formed the decoration pattern by the gravure as surface layer a1. For example, you may form the printing pattern containing a bead and a pigment as a printing layer. Furthermore, although not illustrated, a decorative layer in which coloring or a pattern is arranged by gravure printing or the like can be formed between the surface layer a1 and the surface layer a2. Due to the presence of these various decorative layers, a variety of decorations such as a wood grain pattern, a leather pattern, and a three-dimensional pattern can be applied alone or in combination.

  Thus, as for the lamination sheet of this embodiment, as a result of the surface layer (A) adjusting the cross-linking degree of the acrylic resin compound, the application of the component to the substrate surface is performed at a high area of, for example, 120 ° C. with a 300 area. %, Or even 400% by area or more can be applied to a substrate having a good appearance without causing breakage or cracks. In addition, this stretchability is such that when using a general vacuum thermocompression bonding method, the end surface portion of a plate-like base material or a base material having a three-dimensional structure as shown in FIG. When performing so-called enveloping coating, the surface layer does not crack or break even for large stretches that occur on the end face, and the laminated sheet has a good appearance within the range of not only the surface of the substrate but also the back surface. Allows pasting. Further, the surface layer (A) has scratch resistance, chemical resistance, and heat resistance, and also exhibits a good resilience to the marks generated by pressing nails and objects. Since the acrylic resin compound that constitutes the surface layer (A) has a glass transition point (Tg) of 80 ° C. or higher, it has good heat resistance and is used as a laminated sheet to be attached to the substrate surface of various parts. In particular, it can be suitably used as a decorative sheet in automobile interior parts that require high temperature reliability.

  Next, the thermoplastic resin layer (B) of this embodiment will be described. As shown in FIG. 1, the thermoplastic resin layer (B) 120 is disposed between the surface layer (A) 110 and the adhesive layer (C) 130. As shown in the figure, the thermoplastic resin layer (B) 120 may be a layer that is in direct contact with the surface layer (A) and the adhesive layer (C) 130. In addition to the decorative layer by printing or coloring, or an adhesive layer, a primer layer or the like may be provided.

  The thermoplastic resin constituting the thermoplastic resin layer (B) is not particularly limited. For example, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-acrylic rubber-styrene (AAS) resin, acrylonitrile-ethylene rubber-styrene (AES). ) Resin, Polyolefin resin such as polyethylene (PE), Polypropylene (PP), Polyester resin such as polyethylene terephthalate (PET), Acrylic resin, PVC resin (PVC) resin, Styrene resin, Urethane It is possible to use a thermoplastic resin such as a resin based on polyamide or a polyamide based resin alone or in a single layer in which two or more types are mixed, or by laminating two or more types of layers.

  However, more preferably, when the laminated sheet is attached to the surface of the base material, it is desired to exhibit a stretchability at least equal to or higher than that of the surface layer (A). For example, it is desirable to have stretchability of 300 area% or more, more preferably 400 area% or more, or 600 area% at the temperature at the time of attachment, that is, 100 ° C. to 150 ° C., generally 120 ° C. For example, it is desirable to give good moldability that does not cause breakage or cracking even when stretching at an area ratio of 600% at 120 ° C. As such a thermoplastic resin layer (B), polyurethane resin or polyester Resins can be mentioned.

  Examples of the polyurethane resin include resins formed by a polymerization addition reaction between a polyhydroxy compound and a polyisocyanate compound. Here, specific polyhydroxy compounds include polybasic acids such as phthalic acid, isophthalic acid, adipic acid, maleic acid, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylolpropane, glycerin, pentaerythritol, etc. Polyester polyols comprising condensation reaction products with polyhydroxy compounds, and lactone polyester polyols such as polycaprolactone, polycarbonates such as polyhexylene carbonate diol, polynonylene carbonate diol, polycyclohexylene carbonate diol, and polydimethylcyclohexyl carbonate diol Polyol, polyoxypropylene glycol, polyoxyethylene-polyoxypropylene glycol, poly Alkoxy polyether polyols such as polytetramethylene glycol. Further examples include acrylic polyols and castor oil derivatives. In addition, hydroxy compounds such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and cyclohexanedimethanol, and carboxyl group-containing hydroxy compounds such as dimethylolpropionic acid and dimethylolbutanoic acid are also included.

  Examples of the polyisocyanate compound include toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, and bis (isocyanate methyl) cyclohexane.

  Polyester resins include condensation of polybasic acids such as phthalic acid, isophthalic acid, adipic acid, and maleic acid with polyhydroxy compounds such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, trimethylolpropane, glycerin, and pentaerythritol. The thing which consists of a reaction material is mentioned.

  The thickness of the thermoplastic resin layer (B) is not particularly limited as long as it can maintain sufficient flexibility and ensure moldability when the laminated sheet is attached to a substrate. For example, it is 300 μm or less, or 200 μm or less. Further, when the laminated sheet is pasted to the base material, a thickness that can function as a kind of stress relieving layer that relaxes the stress generated in the laminated sheet is desirable, for example, 10 μm or more, 20 μm or more, or 30 μm or more. It is preferable.

  The thermoplastic resin layer (B) can be formed, for example, by coating a resin dispersed in a solvent or an aqueous solution. The film thickness can be adjusted by the viscosity of the coating solution, the coating method, the number of coatings, and the like.

  Next, the adhesive layer (C) used in this embodiment will be described. As shown in FIG. 1, the adhesive layer (C) 130 is a layer exposed on the back surface of the laminated sheet 100, and the exposed surface is usually covered with a release sheet 300 before being attached to a base material. As shown in FIG. 2, when the laminated sheet 100 of this embodiment is attached to the base material 410, it is a layer that directly contacts the base material 410 and fixes the laminated sheet 100 to the base material 400.

  The material of the adhesive layer (C) is not particularly limited, and examples thereof include general-purpose pressure-sensitive adhesives and adhesives such as acrylic, polyester-based, urethane-based, rubber-based, and silicone-based pressure-sensitive adhesives. Among these, acrylic adhesives are preferred for reasons of heat resistance and durability.

  When affixing to a substrate, it is often exposed to high temperatures. For example, when pasting to a substrate using a vacuum thermocompression bonding method, extremely large surface stretching of 300 area% or more occurs locally at a high temperature of 100 ° C. or higher or 120 ° C. or higher on the laminated sheet. Therefore, an extremely large stress is also applied to the adhesive layer (C) at a high temperature. Therefore, it is desirable that the adhesive layer (C) can maintain a good adhesive force to the substrate even under these conditions.

  In consideration of the above conditions, as the adhesive layer (C), (a) the ratio of the number of repeating units containing a carboxyl group to the total number of repeating units in the polymer is 4.0 to 25%, 25 ° C. or less. The carboxyl group-containing (meth) acrylic polymer having a glass transition point (Tg) of (b) and (b) the ratio of the number of repeating units containing amino groups to the total number of repeating units of the polymer is 3.5 to 15%. And an amino group-containing (meth) acrylic polymer having a glass transition point (Tg) of 75 ° C. or higher, and the mixing ratio of the component (a) and the component (b) is 62:38 to 75:25 by mass ratio. It is desirable to use an acrylic adhesive.

  For example, when a laminated sheet is attached to a base material using a vacuum thermocompression bonding method, stretching exceeding 300 area% occurs locally at a high temperature, and residual stress remains in the stretched portion during cooling after pasting. When the acrylic adhesive is used as the adhesive layer (C) that is directly adhered to the base material, the adhesive force is maintained even in the presence of residual stress, and can be firmly fixed to the base material.

The monoethylenically unsaturated monomer constituting the (meth) acrylic polymer generally has the formula CH ₂ ═CR ₁ COOR ₂ (wherein R ₁ is hydrogen or a methyl group, and R ₂ is linear, branched or cyclic) Alkyl group, phenyl group, alkoxyalkyl group, and phenoxyalkyl group.), And other aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, and vinyl acetate. Vinyl esters such as these are also included. Examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, n -Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, decyl ( Alkyl (meth) acrylates such as meth) acrylate and dodecyl (meth) acrylate, phenoxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate There are alkoxyalkyl (meth) acrylates such as rate and 2-methoxybutyl (meth) acrylate, and in order to obtain the desired glass transition point, adhesiveness, hot adhesiveness and hot holding power, depending on the purpose 1 type (s) or 2 or more types are used suitably. The monoethylenically unsaturated monomer is preferably a (meth) acrylic acid alkyl ester (the alkyl group preferably has 1 to 12 carbon atoms).

  Component (a) is a (meth) acrylic polymer having a glass transition point (Tg) of 25 ° C. or lower, and is a soft component. The soft component (a) itself has adhesiveness at room temperature, but the composition mixed with the component (b) in the above amount shows almost no adhesiveness at ordinary temperature. However, when this soft component (a) is not contained or small, the adhesive has low developability on the adherend surface and low wettability, and when the laminated sheet is cooled to room temperature after thermocompression bonding. The adhesive layer is easy to peel from the substrate.

  A (meth) acrylic polymer having a glass transition point (Tg) of 25 ° C. or lower can be easily provided by using a monomer whose homopolymer has a glass transition point (Tg) of 25 ° C. or lower as a main component. Examples of such monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, isoamyl acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, and dodecyl (meth) acrylate. it can. Considering the adhesiveness at room temperature and the cohesive strength at high temperature, the Tg of the preferred range of the (meth) acrylic polymer is 0 ° C to -50 ° C.

  Furthermore, component (a) is a (meth) acrylic polymer containing a carboxyl group. When component (a) contains a carboxyl group and component (b) contains an amino group, the compatibility between component (a) and component (b) is improved, and component (a ) And component (b) can be avoided. When the component (a) and the component (b) are phase-separated, even if the component (a) and the component (b) are mixed, neither desired adhesiveness nor holding power at high temperature can be obtained. In order to obtain this desired compatibility, the amount of carboxyl groups contained in the (meth) acrylic polymer of component (a) is such that the ratio of the number of repeating units containing carboxyl groups to the total number of repeating units in the polymer is 4 It is preferably from 0 to 25% (also expressed as carboxy group amount mol%).

  By copolymerizing an unsaturated monomer containing a carboxyl group with the monoethylenically unsaturated monomer, the (meth) acrylic polymer can contain a carboxyl group. Examples of such monomers include acrylic acid, methacrylic acid, maleic acid, itaconic acid, ω-carboxypolycaprolactone mono (meth) acrylate, phthalate monohydroxyethyl (meth) acrylate, and β-carboxyethyl (meth) acrylate. Examples include 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and the like. In view of yellowing resistance, the unsaturated monomer containing a carboxyl group is preferably (meth) acrylic acid, ω-carboxypolycaprolactone mono (meth) acrylate, or β-carboxyethyl (meth) acrylate.

  The molecular weight of the carboxyl group-containing (meth) acrylic polymer of component (a) is not particularly limited, but in general, the weight average molecular weight is preferably about 100,000 to about 1,000,000, more preferably about 200,000 to about 800,000. . If the weight average molecular weight is small, the cohesiveness tends to decrease, and if it is large, the compatibility tends to decrease. However, the polymer is not particularly limited as long as the polymer satisfies the component (a) conditions.

  Component (b) is a (meth) acrylic polymer having a glass transition point (Tg) of 75 ° C. or higher, and is a hard component. If this hard component (b) is not contained or little, the component (a) alone is an adhesive (at room temperature), has low heat resistance, and lacks hot adhesiveness and hot holding power. By including the component (b) having a glass transition point (Tg) of 75 ° C. or higher, the adhesive can exhibit tackiness during heat bonding. As a result, when the laminated sheet is attached to the base material, the adhesive layer (C) can withstand the stretching force even if it is stretched at a high temperature and then stretched due to residual stress. It is possible to prevent peeling. The glass transition point (Tg) of component (b) is preferably 75 ° C. or higher. The higher the Tg, the higher the high-temperature adhesive strength in the vicinity of Tg. However, if the Tg is too high, the adhesion at room temperature may be reduced and the film may be easily peeled off. Is preferably 250 ° C. or lower. More preferably, it is the range of 80-120 degreeC.

  A (meth) acrylic polymer having a glass transition point (Tg) of 75 ° C. or higher can be easily provided by using as a main component a monomer having a homopolymer Tg of 75 ° C. or higher. Examples of such monomers include methyl methacrylate, ethyl methacrylate, tertiary butyl methacrylate, cyclohexyl methacrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.

  Component (b) is a (meth) acrylic polymer containing amino groups. This is because the compatibility between the component (a) and the component (b) is improved so that the component (a) and the component (b) do not undergo phase separation. Desirable heat-adhesiveness, hot-adhesiveness, and hot-holding force can be effectively obtained by the good compatibility of component (a) and component (b). In order to obtain this desired compatibility effect, the amount of amino groups contained in the (meth) acrylic polymer of component (b) is the ratio of the number of repeating units containing amino groups to the total number of repeating units of the polymer. Is preferably 3.5 to 15% (also expressed as mol amount of amino group).

  Specific examples of unsaturated monomers containing amino groups that are copolymerized with the above monoethylenically unsaturated monomers to form amino group-containing (meth) acrylic polymers include N, N-dimethylaminoethyl acrylate (DMAEA). ), Dialkylaminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl methacrylate (DM), dialkylaminoalkyls such as N, N-dimethylaminopropylacrylamide (DMAPAA), N, N-dimethylaminopropylmethacrylamide ( Mention may be made of monomers having a tertiary amino group typified by vinyl monomers having a nitrogen-containing heterocycle such as (meth) acrylamide and vinylimidazole.

  The molecular weight of the amino group-containing (meth) acrylic polymer of component (b) is not particularly limited, but in general, the weight average molecular weight is preferably about 10,000 to about 200,000, more preferably about 40,000 to about 150,000. . Those having a small weight average molecular weight are inferior in hot adhesiveness and hot holding power, and if large, the compatibility tends to decrease. However, if the polymer can produce a polymer that satisfies the condition of component (b), the average molecular weight is particularly It is not limited.

  In order to acquire said effect, the quantity of a component (a) and a component (b) is an quantity from which the compounding ratio of a component (a) and a component (b) will be 62: 38-75: 25 by weight ratio. When the amount of the component (a) is less than this, the room temperature adhesiveness and the heat adhesiveness are insufficient, and when it is more than this, the component (b) is insufficient, and the hot adhesiveness / hot holding force tends to be insufficient. If the component (b) is less than this, the hot adhesiveness / hot holding power is insufficient, and if it is more than this, the wettability of the adhesive with respect to the adherend surface decreases, and room temperature adhesion and heat adhesion It is easy to run out. A more preferable blending ratio of the component (a) and the component (b) is in the range of 65:35 to 70:30 by weight.

  The (meth) acrylic polymer can be produced by a radical polymerization method, and a known method such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method or a bulk polymerization method can be used as the production method. Examples of the polymerization initiator include organic peroxides such as benzoyl peroxide, lauroyl peroxide, bis (4-tertiarybutylcyclohexyl) peroxydicarbonate, 2,2′-azobisisobutyronitrile, 2'-azobis-2-methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis (2-methylpropionic acid) dimethyl, azobis 2,4-dimethylvaleronitryl (AVN) An azo polymerization initiator such as) is used. The amount of the initiator used is preferably 0.05 to 5 parts by weight per 100 parts by weight of the monomer mixture.

  In addition to the adhesive of the adhesive layer (C) of the present embodiment, a plasticizer, a crosslinker (for example, a crosslinker having an epoxy, aziridine, isocyanate, or bisamide functional group, a metal chelate, if necessary. System crosslinking agents), antioxidants, ultraviolet absorbers, pigments, fillers and other additives.

  Although the thickness of an adhesive layer (C) is not limited, 5-100 micrometers is preferable and can also be 10-80 micrometers.

  The laminated sheet of the present embodiment includes at least a surface layer (A) disposed on the outermost surface, a thermoplastic resin layer (B), and an adhesive layer (C) bonded to the base material. In order to raise the adhesiveness between the respective layers, another second adhesive layer 140 may be added between the surface layer (A) and the thermoplastic resin layer (B) as shown in FIG. Furthermore, as shown in FIG. 7, for the purpose of adding decorativeness and design to the laminated sheet, a decorative layer 150 such as a printed layer or a colored layer, or a metal layer 160 is formed with a surface layer (A) and an adhesive layer (C). It may be added in between. Moreover, in order to raise the adhesiveness between each layer, you may apply | coat a primer as needed.

  Such a decorative layer 150 is, for example, a normal printing method such as a gravure direct printing method, a gravure offset printing method, a screen printing method, a gravure coating method, a roll coating method, a comma coating method, etc. It can be formed using a coating method. The decorative layer 150 may be colored by printing or the like, or various decorative patterns and colors such as a wood grain pattern, a geometric pattern, and a leather pattern may be added.

  The metal layer 160 can be formed by a vacuum deposition method, a sputtering method, an ion plating method, a plating method, or the like. Aluminium, nickel, gold, platinum, chromium, iron, copper, tin, indium, silver, titanium, lead, zinc, germanium, and other metals, alloys and compounds such as zinc sulfide, and oxidation, depending on the metal color required Silicon, magnesium fluoride, tin oxide, ITO, etc. can be used. In addition, for example, by using a vapor deposition layer of indium or tin with a thickness of 10 to 100 nm, more preferably 40 to 60 nm, even for local stretching that occurs in the laminated sheet when the laminated sheet is attached to the substrate, Generation of cracks can be suppressed.

  In addition, the decorative layer and the metal layer described above are only provided when they are provided as independent layers. As already described, as in the case where the surface layer (A) itself is used as the decorative layer, a thermoplastic resin is used. It is also possible to add a pigment or a bead to the layer (B) or the adhesive layer (C) and decorate it by itself. Or the decoration layer and metal layer which were mentioned above can also be arrange | positioned as an intermediate | middle layer of a thermoplastic resin layer (B). Thus, you may include a decoration layer and a metal layer in each layer of a surface layer (A), a thermoplastic resin layer (B), and an adhesion layer (C).

  It does not specifically limit about the manufacturing method of the lamination sheet of this embodiment. Each layer can be manufactured according to the method for manufacturing each layer already described. In the production of the laminated sheet, for example, a surface sheet (A) formed on a support sheet or a release sheet such as a PET film whose surface has been subjected to a release treatment, a structure in which a thermoplastic resin layer (B) is formed, and adhesion A layered sheet can be formed by preparing each layer (C) and then bonding them together. Alternatively, on one release sheet (support sheet), the coating process and the curing process are repeated, and the surface layer (A), the thermoplastic resin layer (B), and other decorative layers are sequentially laminated. You may form a lamination sheet by bonding together with the contact bonding layer (C) formed on another peeling sheet. Further, when the layers are bonded together, an adhesive layer may be formed between the surface layer (A) and the thermoplastic resin layer (B). Or you may form a primer layer in order to raise the adhesiveness between each layer. Moreover, you may form a decoration layer between each layer. The support sheet and release sheet used here are not limited in material as long as they can easily peel off the layer formed on the sonosheet at the time of use. Plastic film can be used.

  FIG. 2 is a cross-sectional view showing a schematic structure of a component according to the present embodiment. As shown in FIG. 2, a component 400 according to the present embodiment is obtained by attaching the laminated sheet 100 of the present embodiment described above to the surface of a base material 410. In particular, the vacuum thermocompression bonding method is preferably used as the attaching method. The shape of the base material 410 is not limited to a plate shape as shown in FIG. 2, and may be a molded body having a more complicated three-dimensional structure. The material of the molded body is not particularly limited as long as it has heat resistance at the bonding temperature, and plastic, metal, wood, or the like can be used.

  Moreover, as shown in FIG. 2, in the component of this embodiment, when the laminated sheet of this embodiment is used and pasted by the vacuum thermocompression bonding method, the end portion of the base material covers from the front surface to the back surface. , Can be entrained. In the place where the wrapping coating is performed in this manner, the coated laminated sheet is often stretched locally to about 300 area% or 400 area% or more, but when the laminated sheet of this embodiment is used, It is affixed to the substrate with a good appearance without being cracked or broken.

  Below, the manufacturing method of the component of this embodiment using the vacuum thermocompression bonding method, that is, the method of attaching the laminated sheet using the vacuum thermocompression bonding machine 510 will be described with reference to FIG.

  As shown in FIG. 8A, a typical vacuum thermocompression bonding machine 510 has first and second vacuum chambers 511 and 512 above and below, and an adherend between the upper and lower vacuum chambers. A jig for setting a laminated sheet to be attached to a certain base material is provided. The lower first vacuum chamber 511 is provided with a lifting platform 515 that can be moved up and down, and a base material 514 of a component is set on the lifting platform 515. In addition, as such a vacuum thermocompression bonding machine, a commercially available thing, for example, a double-sided vacuum molding machine (made by Fuse Vacuum Co., Ltd.) etc. can be used.

  As shown in FIG. 8A, first, in a state where the first vacuum chamber 511 and the second vacuum chamber 512 of the vacuum thermocompression bonding machine 510 are released to atmospheric pressure, the laminated sheet 513 is placed between the upper and lower vacuum chambers. set. In the first vacuum chamber 511, the base material 514 is set on the lifting platform 515.

  Next, as shown in FIG. 8B, the first vacuum chamber 511 and the second vacuum chamber 512 are closed and evacuated, and the inside of each chamber is evacuated (for example, 1 MPa). Next, as illustrated in FIG. 8C, the base material 514 is pushed up to the second vacuum chamber 512 by the lifting platform 515 while heating the laminated sheet 513. Heating can be performed by, for example, a lamp heater incorporated in the ceiling of the second vacuum chamber 512. The heating temperature of the laminated sheet 513 is 80 ° C. to 160 ° C., more preferably 90 ° C. to 140 ° C., for example, adjusted to about 120 ° C.

  The heated laminated sheet 513 is pressed against the surface of the substrate 514 and stretched. On the other hand, the first vacuum chamber 511 and the second vacuum chamber 512 are partitioned by a partition plate 517. Thereafter, as shown in FIG. 8D, the inside of the second vacuum chamber 512 is pressurized to an appropriate pressure (for example, 2 MPa to atmospheric pressure) while the heating of the laminated sheet 513 is maintained. Due to the pressure difference, the laminated sheet 513 adheres to the exposed surface of the base material 515 and stretches following the uneven shape of the exposed surface to form a coating that adheres to the base material surface. At this time, the laminated sheet 513 can be entrained and wrapped around the back surface 518 at the end of the substrate 514 to cover the exposed surface cleanly.

  Thereafter, the upper and lower first and second vacuum chambers 511 and 512 are opened again to return to the atmospheric pressure, and the base material 514 covered with the laminated sheet 513 is taken out. As shown in FIG. 8E, if the edge of the laminated sheet 513 that is in close contact with the surface of the base material 514 is trimmed, the vacuum press-bonding process is completed, and a component that is satisfactorily covered is completed. In addition, the vacuum thermocompression bonding process by the vacuum thermocompression bonding machine 510 is not limited to this, it is needless to say that deformation is possible and heating and pressurization conditions can be changed.

  In this way, the component to which the laminated sheet is attached using the vacuum thermocompression bonding method includes a portion that has been stretched to reach about 300 area% or more or 400 area% near the edge of the base material. However, in the component using the above-described laminated sheet of the present embodiment, it is possible to obtain a good appearance without cracks and breakage of the laminated sheet even with such stretching.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

<Example 1>
In the laminated sheet of Example 1, first, a sheet A including a surface layer (A), a sheet B including a thermoplastic resin layer (B), and a sheet C including an adhesive layer (C) are subjected to the following conditions. It was prepared by attaching these together.

(Preparation conditions for sheet A)
Methyl methacrylate (MMA) (manufactured by Mitsubishi Rayon Co., Ltd., product name: Acryester M) 99 parts by weight, as a monomer containing a hydroxyl group, 2-hydroxyethyl methacrylate (HEMA) (manufactured by Mitsubishi Rayon Co., Ltd., product name: Acryester HISS) 1 part by weight, 150 parts by weight of ethyl acetate as solvent, and dimethyl-2,2′-azobis (2-methylpropionate) as a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., product name: V -601) 0.6 parts by weight were mixed and subjected to a polymerization reaction at a temperature of 65 ° C. for 24 hours under a nitrogen atmosphere to prepare an ethyl acetate solution of an acrylate copolymer.

  Isocyanate (NCO) (product name: Duranate TPA-100, manufactured by Asahi Kasei Co., Ltd.) was mixed with the resulting acrylate copolymer solution so that the solid weight ratio was 7.69 mmol per 100 g. It apply | coated by the knife coat | court on the surface of a certain flat transparent PET film (product name T-60 by Toray Industries, Inc.) of about 50 micrometers thickness. This was dried at 90 ° C. for 3 minutes and then at 130 ° C. for 5 minutes for a total of 8 minutes in an oven (a thermostat PV-221 manufactured by Espec Corp.) to form an acrylic resin compound layer having a thickness of about 60 μm. Thus, a sheet A having the surface layer (A) formed on the PET film was produced.

  In Table 1, the mass part ratio of MMA and HEMA used for producing the acrylate copolymer and the amount of isocyanate added to 100 g of the acrylate copolymer are shown in mmol units. The glass transition point (Tg) of the acrylic resin compound is also shown. The glass transition point (Tg) is a loss at Rheometric Scientific, RSA-III, Mode: Tension, Frequency: 10.0 Hz, Temperature: 30 ° C. to 150 ° C. ((5.0 ° C./min)) Although it can be determined by measuring the peak temperature of tangent (tan δ) (loss elastic modulus E ″ / storage elastic modulus E ′), in this example and the comparative example, Tg is determined using the following calculation formula. In addition, the catalog value was used for the glass transition point (Tg) of the monomer (homopolymer).

<Calculation formula of Tg>
The glass transition temperature (Tg) of the polymer is set according to the following Fox formula (Fox, TG, Bull. Am. Phys. Soc., 1, in 1956, p.123). This was done by setting the weight ratio.

  In the formula, Tg represents the glass transition temperature of the polymer portion, and Tg1, Tg2,..., Tgm represent the glass transition temperature of each polymerization monomer. W1, W2,..., Wm represent the weight ratio of each polymerization monomer. Here, the glass transition temperature (Tg) of the polymer is the glass transition point of the acrylic resin compound, and the glass transition points of the homopolymers of MMA, HEMA, and BMA are Tg1, Tg2, and Tg3, respectively. Calculated as W1, W2, W3, m = 3.

(Preparation conditions for sheet B)
Using a water-based urethane resin (Daiichi Seika Kogyo Co., Ltd., product name: D-6260) as a support, a flat PET film (product name: T-60, manufactured by Toray Industries, Inc.) having a thickness of about 50 μm is coated with a knife coat. Applied. This is dried at 90 ° C. for 3 minutes and then at 160 ° C. for 5 minutes for a total of 8 minutes in an oven (a thermostatic device PV-221 manufactured by Espec Corp.), and a polyurethane resin layer having a thickness of about 30 μm, that is, a thermoplastic resin layer (B) Produced a sheet B formed on a PET film.

(Preparation conditions for sheet C)
N-butyl acrylate (Mitsubishi Chemical Co., Ltd.) and acrylic acid (Toagosei Co., Ltd.) are mixed at a mass part ratio of 94: 4, Tg = -21 ° C., carboxyl group content 10.2 mol%. A carboxyl group-containing acrylic polymer solution (component (a)) having an average molecular weight of 580,000 was obtained. On the other hand, methyl methacrylate (Mitsubishi Rayon, product name: Acryester M) and n-butyl methacrylate (Mitsubishi Rayon, product name: Acryester B) and dimethylaminoethyl methacrylate (Mitsubishi Rayon, Product name: acrylate ester DM) in a mass part ratio of 60: 34: 6, and an amino group-containing acrylic polymer solution (average molecular weight 96,000, Tg = 91 ° C., amino group content 4.4 mol%) Component (b)) was obtained. Thereafter, the carboxyl group-containing acrylic polymer solution (component (a)) and the amino group-containing acrylic polymer solution (component (b)) are mixed at a solid content mass ratio of 70:30, and epoxy crosslinking is further performed as a crosslinking agent. A material (manufactured by Soken Chemical Co., Ltd., product name: E-5XM) was added at a solid content ratio of 0.1 mass% with respect to the total solid content of the polymer to prepare an adhesive solution.

  As a release sheet, a 38 μm thick release-treated PET film (manufactured by Teijin Limited, product name: Purex (registered trademark) A-71) is prepared, and the above adhesive solution is applied thereon and heated at 100 ° C. for 20 minutes. The sheet C was dried and reheated at 150 ° C. for 30 minutes to obtain a sheet C on which a 40 μm-thick adhesive layer (C) was formed on the PET film.

(Production of laminated sheet)
The adhesive layer (C) of the sheet C is bonded to the surface of the polyurethane resin layer (thermoplastic resin layer (B)) of the sheet B at about 70 ° C., and the thermoplastic resin layer (B) and the adhesive layer (C) are laminated. The body was made.

  On the other hand, a polyester resin (manufactured by Dainichi Seika Kogyo Co., Ltd., product name: E-295NT) and polyisocyanate (manufactured by Dainichi Seika Kogyo Co., Ltd., product name: C-55) in a mass ratio of 10: 0.3. It mix | blended so that it might become, and adjusted the urethane type adhesive. This urethane adhesive was coated on the surface of the acrylic resin layer of the sheet A so as to have a thickness of 15 μm, thereby forming a second adhesive layer.

  One PET film is peeled off from the laminate of sheet B and sheet C obtained earlier, the urethane resin layer is exposed, and the exposed surface is bonded to the second adhesive layer formed on the sheet A. Thus, a laminated sheet having a laminated structure corresponding to FIG. 6 was obtained.

<Example 2 to Example 11>
The laminated sheet of each Example was produced in the same procedure as Example 1. However, in the preparation of the sheet A in each example, that is, the preparation of the surface layer (A), the mixing ratio of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) and the isocyanate ( The NCO) mixing ratio was set as shown in Table 1.

<Comparative Examples 1-15>
A laminated sheet was prepared in the same procedure as in Example 1. However, the mixing ratio of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) when producing the acrylate copolymer under the production conditions of the surface layer (A), and the isocyanate ( The conditions shown in Table 2 were used for the (NCO) mixing ratio. In Comparative Examples 7 to 15, n-butyl methacrylate (BMA) (product name: Acryester B, manufactured by Mitsubishi Rayon Co., Ltd.) was mixed together with MMA and HEMA when the acrylate copolymer was prepared.

<Example 12>
In Example 12, a laminated sheet with a woodgrain decoration was produced under the following conditions.
First, as a thermoplastic resin layer (B), a water-based urethane resin (manufactured by Dainichi Seika Kogyo Co., Ltd., product name: D-6260) is colored, and a flat PET film (Toray, approximately 50 μm thick) as a support. Product name T-60) Coated on the surface by knife coating. This is dried at 90 ° C. for 3 minutes and then at 160 ° C. for 5 minutes for a total of 8 minutes in an oven (a thermostatic device PV-221 manufactured by Espec Corp.), and a polyurethane resin layer having a thickness of about 30 μm, that is, a thermoplastic resin layer (B) Produced a sheet D formed on a PET film.

  On the water-based urethane resin of this sheet D, a print layer having a wood grain pattern was formed by three-color gravure printing. A solution was prepared by adding acrylic resin beads (laborolol 030, M10, average particle size 10 μm) manufactured by Daiichi Seika Co., Ltd. to a mixed solution of (meth) acrylic copolymer and isocyanate prepared under the same conditions as in Example 6. This was applied to the surface of the print layer with a wood grain pattern and dried to form a transparent resin layer having a thickness of about 20 μm, that is, the first layer of the surface layer (A).

  Next, on this transparent resin layer, a black colored acrylic resin system is used so that the volume ratio of the mixed solution of (meth) acrylic copolymer and isocyanate prepared under the same conditions as in Example 6 is 1: 1. Beads (Rabcoroll 020, M20 (F) black manufactured by Dainichi Seika Co., Ltd., average particle size 20 μm) were added, and a printed layer with a conduit pattern, that is, a second layer of the surface layer (A) was formed by gravure printing.

  The PET film used as a support for the water-based urethane resin layer was peeled from the above sheet, and the exposed surface of the urethane resin layer and the exposed surface of the adhesive layer (C) of the sheet C produced under the same conditions as in Example 1 were used. It bonded together at about 70 degreeC. Thus, a laminated sheet having a wood grain pattern was obtained.

<Example 13>
In Example 13, a laminated sheet having a hairline pattern formed on the surface of the surface layer with fine irregularities was produced. When forming the surface layer, as a support sheet, a support sheet (transparent PET film (manufactured by Toray Industries, Inc.) having a thickness of about 50 μm, which has been subjected to so-called hairline processing that forms a number of fine-line grooves like hair in a certain direction on the surface. Product name T-60)). On the surface of this support sheet, isocyanate (NCO) (product name: Duranate TPA-100) was prepared so that the acrylate copolymer solution prepared under the same conditions as in Example 6 had a solid weight ratio of 7.69 mmol per 100 g. , Manufactured by Asahi Kasei Co., Ltd.) was applied by knife coating and dried to form a surface layer of an acrylic resin compound having a thickness of about 60 μm. Other conditions were the same as in Example 1 to produce a laminated sheet.

<Evaluation method>
The laminated sheets of the examples and comparative examples were (1) surface stretchability, (2) scratch resistance, (3) chemical resistance, (4) hot stamp recoverability, and (5) adhesiveness by the following methods. And (6) the constant load peel test was evaluated.

(1) Surface stretchability After peeling off the PET sheet (support sheet) covering the surface layer (A) of the laminate sheet and the PET film (release sheet) covering the adhesive layer (C), this laminate sheet A 66 mm square sample was cut out. Using an automatic biaxial stretching apparatus, IMC-167D type (manufactured by Imoto Seisakusho Co., Ltd.), the sample was stretched at a speed of 200 mm / min. The case where there was no occurrence of tearing or cracking was judged as “good”.

(2) Scratch property After peeling the PET film (release sheet) covering the adhesive layer (C) of the laminated sheet, the adhesive layer surface is pasted on an ABS resin plate (made by Coating Tester Kogyo Co., Ltd.) with a thickness of 2 mm at 135 ° C. Then, after the PET film (support sheet) covering the surface layer (A) was peeled off, what was subjected to curing at 80 ° C. for 10 minutes and further at 100 ° C. for 10 minutes was used as a test sample. A pencil hardness test was performed on this test sample. That is, a pencil lead was pressed against the sample surface with a load of 7.5 N, and the sample was moved at a speed of 200 mm / min. The same test was performed with pencils having different hardnesses, and the highest pencil hardness at which no scars were confirmed on the surface layer (A) was the result. A hardness of H or higher was judged good.

(3) Chemical resistance A test sample was produced under the same conditions as the test sample for evaluation of scratch resistance. Various chemicals shown below were dropped onto this sample and left at room temperature for 48 hours, followed by curing at 80 ° C. for 48 hours. It was taken out after curing and the degree of appearance was confirmed. The case where there was no crack in the appearance was judged good.
a. 10% ethanol aqueous solution
b. Wax for leather (Honda Access Co., Ltd., trade name: car polish wax)
c. Armor All (Napolex Corporation, trade name: Armor All Protectant 300mL)
d. Citrus fragrance (Dia Chemical Co., Ltd., trade name: Gracement Poppy)

(4) Hot stamp recoverability:
A test sample was prepared under the same conditions as the test sample for evaluation of scratchability. Five sheets of pharmacy gauze were stacked on the sample in a 60 ° C. environment, a 1 kg weight was placed, and it was visually confirmed whether or not a gauze imprint was left on the sample surface for 1 hour. The results were evaluated at the following ABC3 stage, and the state of A was judged to be good.
A No trace of gauze is confirmed.
B Partial transcription is confirmed.
C Transfer is confirmed on the entire surface.

(5) Adhesion test:
A test sample was prepared under the same conditions as the test sample for evaluation of scratchability. A test sheet, a laminated sheet attached to an ABS resin plate, was cut to a width of 25 mm, and the substrate was adhered at 25 ° C. and 100 ° C. under conditions of a peeling angle of 180 degrees and a peeling speed of 300 mm / min. The force required when peeling the laminated sheet from a certain ABC resin plate, that is, the adhesive force was measured using Tensilon (ORIENTEC, UCT-100).

(6) Constant load peel test:
A test sample was prepared under the same conditions as the test sample for evaluation of scratchability. The laminated sheet attached to the ABS resin plate, which is a test sample, is cut to a width of 25 mm and a length of 50 mm, and a 100 g weight is applied to the end of the laminated sheet so that a load is applied in the direction of 90 degrees in an atmosphere of 100 ° C. When lowered to the part, the peel length after 24 hours was measured.

<Evaluation results>
Tables 1 and 2 show the evaluation results of (1) surface stretchability, (2) scratch resistance, (3) chemical resistance, and (4) hot stamp recoverability in each example and comparative example. . The laminated sheets of the examples all showed good results.

  About (5) adhesive force test and (6) constant load peeling test, it measured about Example 1. FIG. The results are shown below. It was confirmed that the adhesive force could be maintained even at a high temperature condition of 100 ° C.

Adhesive strength test results: 50.7 N / 25 mm (25 ° C.), 11.2 N / 25 mm (25 ° C.)
Constant load peel test result: 30.1 mm

  The laminated sheet of the present embodiment is suitable for a part that is rolled up and covered at the end of the base material using a base material that needs to be stretched at a high temperature, in particular, a vacuum thermocompression bonding method. It can be used as a part to which a laminated sheet is attached for various purposes such as decoration on the substrate surface, protection, and marking. In addition to stretchability at high temperatures, it has scratch resistance, chemical resistance, and impression recovery, so it can be used for building materials, decorative panels, washstands, electrical appliances, motorcycle and automobile exterior parts and interior parts, etc. Although it can be suitably used for decoration, protection, etc. of a three-dimensional shape product, since high temperature durability and aesthetics are required particularly for automobile interior parts, the laminated sheet of this embodiment can be suitably used for automobile interior parts. .

Sectional drawing of the lamination sheet of this embodiment is shown. It is sectional drawing which shows the structure of the components by which the lamination sheet of this embodiment was affixed. It is sectional drawing which shows the lamination sheet structure of other embodiment of this invention. It is sectional drawing which shows the lamination sheet structure of other embodiment of this invention. It is sectional drawing which shows the lamination sheet structure of other embodiment of this invention. It is sectional drawing which shows the lamination sheet structure of other embodiment of this invention. It is sectional drawing which shows the lamination sheet structure of other embodiment of this invention. It is a schematic process drawing which shows the vacuum thermocompression bonding process used with the manufacturing method of components using the lamination sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Laminated sheet 110 Surface layer 120 Thermoplastic resin layer 130 Adhesive layer 200 Release sheet 300 Support sheet 400 Component 410 Base material 510 Vacuum thermocompression bonding apparatus

Claims (17)

A laminated sheet to be attached to a substrate,
Including a surface layer (A) disposed on the outermost surface, a thermoplastic resin layer (B), and an adhesive layer (C) bonded to the substrate;
The surface layer (A)
(Meth) acrylic copolymer (I) obtained by copolymerizing a (meth) acrylate monomer containing a hydroxyl group-containing monomer in an amount of 0.5% by mass or more and less than 5% by mass, and having two or more isocyanate groups in one molecule The glass transition point (Tg) formed by mixing the isocyanate compound (II) with 100 g of the (meth) acrylic copolymer (I) at a mixing ratio of 3 to 16 mmol of the isocyanate group is 80. A laminated sheet mainly composed of a (meth) acrylic resin compound at a temperature of ℃ or higher.   The laminated sheet according to claim 1, which has a stretchability of not less than 300 area% at 120 ° C.   The laminated sheet according to claim 1 or 2, wherein the (meth) acrylate monomer is methyl (meth) acrylate.   The said thermoplastic resin layer (B) is a lamination sheet of any one of Claims 1-3 which has a thermoplastic polyurethane resin as a main component.   The said adhesive layer (C) is a lamination sheet of any one of Claims 1-4 which has an acrylic adhesive as a main component. The acrylic adhesive is
(A) Carboxy group-containing (meta) having a glass transition point (Tg) of 25 ° C. or lower, wherein the ratio of the number of repeating units containing a carboxyl group to the total number of repeating units of the polymer is 4.0 to 25%. Acrylic polymer,
(B) Amino group-containing (meta) having a glass transition point (Tg) of 75 ° C. or higher, wherein the ratio of the number of repeating units containing an amino group to the total number of repeating units in the polymer is 3.5 to 15%. An acrylic polymer, the mixing ratio of the component (a) and the component (b) is 62:38 to 75:25 by mass ratio,
The laminated sheet according to claim 5.   The said surface layer (A) is a lamination sheet of any one of Claims 1-6 which has a three-dimensional structure on the surface.   The said surface layer (A) is a lamination sheet of any one of Claims 1-7 which has several layers from which a composition differs other than a main component.   Furthermore, it is added between the surface layer (A) and the thermoplastic resin layer (B), between the thermoplastic resin layer (B) and the adhesive layer (C), or in each layer. The laminated sheet according to any one of claims 1 to 8, comprising at least one of a decorative layer or a metal layer.   Furthermore, the lamination sheet of any one of Claims 1-9 which has at least 1 or more other contact bonding layers between the said surface layer (A) and the said thermoplastic resin layer (B).   The laminated sheet according to any one of claims 1 to 10, which is used for adhering to a base material by a vacuum thermocompression bonding method.   The manufacturing method of components including the process of affixing the lamination sheet of any one of Claims 1-11 on the base-material surface of components by a vacuum thermocompression bonding method.   The said vacuum thermocompression bonding method is a manufacturing method of the components of Claim 12 which encloses and coat | covers the at least one part edge part of the said base material with the said lamination sheet.   The method for producing a component according to claim 12 or 13, wherein the laminated sheet is stretched at least partially by 300 area% or more.   The component by which the lamination sheet of any one of Claims 1-10 was affixed on the base-material surface of components.   The component according to claim 15, wherein the laminated sheet includes and covers at least a part of the end of the base material.   The component according to claim 15 or 16, which is an automobile exterior product or an automobile interior product.

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