TW202100360A - Double-sided adhesive sheet for decorative molding, laminating adhesive sheet for decorative molding and laminate for decorative molding - Google Patents

Abstract

This invention addresses the problem of providing a double-sided adhesive sheet for decorative molding and a laminating adhesive sheet for decorative molding which exhibit excellent adhesion to an adherend that contains a polyolefin resin as a main component thereof. This invention pertains to a double-sided adhesive sheet which is for decorative molding and includes an olefinic elastomer. This invention also pertains to a laminating adhesive sheet which is for decorative molding and is equipped with: a surface-side layer; and a double-sided adhesive sheet for decorative molding including an olefinic elastomer.

Description

Double-sided adhesive sheet for decorative molding, laminated adhesive sheet for decorative molding, and decorative molded laminate

The present invention relates to a double-sided adhesive sheet for decorative molding, a laminated adhesive sheet for decorative molding, and a decorative molded laminate.

Previously, in the case of protecting or modifying (decorating) the surface of automotive interior and exterior decoration parts, home appliance parts, building materials parts, etc., after processing the molded body by injection molding or vacuum forming, spray coating, etc. The surface of the molded body is coated with paint, dried, and heated and hardened. However, in addition to the problem that the discharge of volatile organic solvents will worsen the working environment, this kind of coating also has the problem of poor coating yield due to the need for working steps and production equipment for molded parts, or overlapping coating of coatings. , The problem of low productivity.

In recent years, in order to reduce the weight of automotive interior and exterior decorative parts, home appliance parts, building materials, etc., the use of resin molded bodies is being promoted as molded bodies. In the decoration (decoration) of the resin molded body, spray coating is often not suitable, and various methods have been developed to decorate the surface of the resin molded body. Among them, the method of decorating the outermost surface of a molded body with a decorative film to obtain a decorative molded body has advantages such as a high degree of freedom in design and excellent productivity compared with a method of coating or printing on the surface using paint or the like. Furthermore, the decoration method using a decoration film can also decorate the surface of a molded body having three-dimensional unevenness, and therefore is used for various purposes.

For example, Patent Document 1 discloses a laminate for decorative molding, which has a base layer and an adhesive layer, and the adhesive layer has a silicone-based adhesive layer and an acrylic-based adhesive layer. Moreover, Patent Document 2 discloses a vacuum forming sheet having an adhesive layer on the lower surface of the surface layer film. Here, the adhesive layer is obtained by blending 1.5 to 2.5 equivalents of polyisocyanate in a thermoplastic saturated co-polyester resin and curing it. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-154410 [Patent Document 2] Japanese Patent Laid-Open No. 2010-120209

[The problem to be solved by the invention]

In the decorative molded body, it is of course required that the adherend and the decorative film are sufficiently closely adhered to each other so as not to be easily peeled off. However, when a polyolefin-based material is used for the adherend, if the conventional adhesive sheet for decorative molding (layered body for decorative molding) is used, the adhesion of the decorative film to the adherend cannot be fully exhibited. The problem.

Therefore, in order to solve such problems of the prior art, the present inventors provided a double-sided adhesive sheet for decorative molding and a laminate for decorative molding that exhibits excellent adhesion to an adherend containing polyolefin resin as a main component The adhesive sheet was studied for the purpose. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors have conducted intensive studies. As a result, the present inventors found that by forming an adhesive layer containing an olefin-based elastomer, it is possible to obtain excellent adhesion to an adherend containing a polyolefin-based resin as a main component. Two-sided adhesive sheet for decorative molding and laminated adhesive sheet for decorative molding. Specifically, the present invention has the following configuration.

[1] A double-sided adhesive sheet for decorative molding, containing an olefin-based elastomer. [2] The double-sided adhesive sheet for decorative molding as described in [1], which is used for bonding to an adherend containing a polyolefin resin as a main component. [3] The double-sided adhesive sheet for decorative molding as described in [1] or [2], wherein the olefin-based elastomer is a block copolymer. [4] The double-sided adhesive sheet for decorative molding according to any one of [1] to [3], wherein the olefin-based elastomer is a block copolymer, and the block copolymer has a styrene-based Blocks of polymers. [5] A laminated adhesive sheet for decorative molding, comprising: the double-sided adhesive sheet for decorative molding as described in any one of [1] to [4], and a surface side layer. [6] The laminated adhesive sheet for decorative molding as described in [5], wherein the laminated adhesive sheet for decorative molding is used for decorative molding under vacuum or reduced pressure. [7] A decorative molding laminate, which is formed by bonding the decorative molding laminate adhesive sheet as described in [5] or [6] to an adherend. [8] The decorative molded laminate according to [7], wherein the adherend contains a polyolefin resin as a main component. [9] The decorative molded laminate according to [7] or [8], wherein the adherend is a component of a vehicle, a component of an electronic device, or a building material. [Effects of the invention]

According to the present invention, a double-sided adhesive sheet for decorative molding and a laminated adhesive sheet for decorative molding that exhibit excellent adhesion to an adherend containing a polyolefin resin as a main component can be obtained.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In addition, the numerical range indicated by "-" in this specification means a range that includes the numerical values described before and after "-" as the lower limit and the upper limit.

(Double-sided adhesive sheet for decorative molding) The present invention relates to a double-sided adhesive sheet for decorative molding containing an olefin-based elastomer. Since the pressure-sensitive adhesive sheet of the present invention has the above-mentioned structure, it exhibits excellent adhesion to an adherend containing a polyolefin resin as a main component. Therefore, the double-sided pressure-sensitive adhesive sheet for decorative molding of the present invention can be preferably used for bonding applications to an adherend containing polyolefin resin as a main component.

Previously, polycarbonate resins or Acrylonitrile Butadiene Styrene (ABS) resins were used as adherends of decorative molded bodies. Therefore, detailed studies have not been conducted on adhesive sheets for decorating adherends containing polyolefin resins as main components. Therefore, the present inventors have found that when an adherend containing a polyolefin resin as the main component is used as an adherend, if it is a conventional decorative film, the adhesion to the adherend is insufficient. It is difficult to obtain a decorative molded body excellent in durability or design. Therefore, the present invention provides a double-sided pressure-sensitive adhesive sheet for decorative molding, which has an optimal structure for exhibiting excellent adhesion when an adherend containing a polyolefin resin as a main component is used.

The double-sided adhesive sheet for decorative molding is preferably a double-sided adhesive sheet composed of a single-layer adhesive layer, and may also be a multilayer double-sided adhesive sheet in which a support is laminated between the adhesive layer and the adhesive layer. When the double-sided adhesive sheet for decorative molding has a support, it is preferable to use a transparent support as the support.

The olefin-based elastomer contains units derived from α-olefins. The olefin-based elastomer used in the present invention may be a poly-α-olefin-based elastomer obtained by polymerizing an α-olefin. Examples of olefin-based elastomers include propylene/ethylene copolymer, propylene/ethylene/1-butene copolymer, 1-butene homopolymer, 1-butene/ethylene copolymer, 1-butene/propylene Copolymer, 4-methylpentene-1 homopolymer, 4-methylpentene-1/propylene copolymer, 4-methylpentene-1/1-butene copolymer, 4-methylpentene -1/propylene-1-butene copolymer, propylene/1-butene copolymer, etc. Furthermore, the olefin-based elastomer may be 2-methyl-1,3-butadiene homopolymer (polyisoprene), 2-methyl-1,3-butadiene copolymer, 1,3 -Butadiene homopolymer (polybutadiene) and other elastomers containing unsaturated bonds in the polymer chain. Furthermore, from the viewpoint of weather resistance, hydrogenated compounds of polyisoprene and polybutadiene can also be used.

The olefin-based elastomer is preferably a block copolymer. When the olefin-based elastomer is a block copolymer, as the block copolymer, for example, propylene/ethylene block copolymer, propylene/ethylene/1-butene block copolymer, 1-butene/ Ethylene block copolymer, 1-butene/propylene block copolymer, 4-methylpentene-1/propylene block copolymer, 4-methylpentene-1/1-butene block copolymer, 4-methylpentene-1/propylene/1-butene block copolymer, propylene/1-butene block copolymer, isoprene/butadiene copolymer, etc. Furthermore, from the viewpoint of weather resistance, an elastomer having an unsaturated bond in the polymer chain can also be used, and such elastomers can also be exemplified by their hydrogenated compounds.

When the olefin-based elastomer is a block copolymer, the block copolymer includes a block obtained by polymerizing an α-olefin and a block containing another polymer. In this case, as another block containing a polymer, for example, a block containing a styrene-based polymer, a block containing a (meth)acrylate-based polymer, and the like can be cited. Among them, the other block containing a polymer is preferably a block containing a styrene-based polymer. That is, when the olefin-based elastomer is a block copolymer, the block copolymer preferably has a block containing a styrene-based polymer in a part thereof.

The content of the olefin-based elastomer relative to the total mass of the double-sided adhesive sheet for decorative molding is preferably 30% by mass or more, and more preferably 40% by mass or more. By setting the content of the olefin-based elastomer within the above-mentioned range, the double-sided pressure-sensitive adhesive sheet for decorative molding of the present invention can exhibit more excellent adhesion with respect to an adherend containing a polyolefin-based resin as a main component.

The glass transition temperature (Tg) of the olefin-based elastomer is preferably 0°C or lower, more preferably -10°C or lower. By setting the glass transition temperature of the olefin-based elastomer to the above-mentioned range, the double-sided adhesive sheet for decorative molding of the present invention can exhibit more excellent adhesion with respect to an adherend containing a polyolefin-based resin as a main component.

In addition to the olefin-based elastomer, the double-sided adhesive sheet for decorative molding may contain additives. Examples of additives include silane coupling agents, thickeners, oil components, softeners, anti-aging agents, crosslinking agents, pigments, and dehydrogenation type initiators. Among them, the double-sided adhesive sheet for decorative molding preferably contains a silane coupling agent, a tackifier, an oil component, and a dehydrogenation type initiator. By containing these additives, the double-sided adhesive sheet for decorative molding can further improve the adhesiveness of the double-sided adhesive sheet, thereby improving durability or weather resistance.

As the silane coupling agent, for example, a mercapto-based silane coupling agent containing a mercapto group, an epoxy-based silane coupling agent having an epoxy group, a vinyl-based silane coupling agent having a vinyl group, and the like can be cited. Among these, it is preferable to use a mercapto-based silane coupling agent in the application of the present invention. As the mercapto-based silane coupling agent, for example, mercaptotrimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, triethoxy(2-mercaptoethyl)silane, 3-mercaptopropane Trimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 4-mercaptobutyltrimethoxysilane, 10-mercaptodecyltriethoxysilane , 11-mercaptoundecyltrimethoxysilane, 11-mercaptoundecyltriethoxysilane, etc. The content of the silane coupling agent is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more with respect to the total mass of the double-sided adhesive sheet for decorative molding. Furthermore, the content of the silane coupling agent is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less with respect to the total mass of the double-sided adhesive sheet for decorative molding.

Examples of the tackifier include petroleum resins such as styrene resins, terpene resins, rosin resins, C5 resins, C9 resins, and C5/C9 resins. Among them, styrene resins can be preferably used.

As the oil component, a paraffin-based or naphthenic-based system oil is preferable, and the paraffin-based system oil can be more preferably used for reasons such as less likely to cause deterioration of rubber.

Examples of the dehydrogenation-type initiator include benzophenone compounds such as methyl benzoate and 4-methylbenzophenone. The content of the dehydrogenation type initiator is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more with respect to the total mass of the double-sided adhesive sheet for decorative molding. Furthermore, the content of the silane coupling agent is preferably 5.0% by mass or less, and more preferably 3.0% by mass or less with respect to the total mass of the double-sided adhesive sheet for decorative molding. By setting the content of the dehydrogenation type initiator within the above-mentioned range, the double-sided adhesive sheet for decorative molding may also have active energy ray curability, and therefore, the cohesive force may be improved by pre-curing or post-curing.

The thickness of the double-sided adhesive sheet for decorative molding of the present invention is preferably 15 μm or more, more preferably 20 μm or more. Furthermore, the thickness of the double-sided adhesive sheet for decorative molding of the present invention is preferably 300 μm or less, more preferably 250 μm or less, still more preferably 200 μm or less, further preferably 150 μm or less, and particularly preferably 100 μm or less. By setting the thickness of the double-sided adhesive sheet for decorative molding within the above range, durability can be improved, and the adhesion to the adherend can be more effectively improved. Furthermore, by making the thickness of the double-sided adhesive sheet for decorative molding within the above-mentioned range, the production of the double-sided adhesive sheet becomes easy.

The surface of the double-sided adhesive sheet for decorative molding is preferably covered with a release sheet. That is, the present invention may also relate to a double-sided adhesive sheet for decorative molding with a release sheet. Fig. 1 is a cross-sectional view showing an example of the structure of a double-sided adhesive sheet 1 for decorative molding with a release sheet. The double-sided adhesive sheet 11 for decorative molding shown in FIG. 1 has peeling sheets (12a, 12b). In addition, the double-sided adhesive sheet 11 for decorative molding of FIG. 1 is a single-layer double-sided adhesive sheet of a baseless type.

Examples of the release sheet include a release laminate sheet having a substrate for a release sheet and a release agent layer provided on one side of the substrate for a release sheet, or a polyethylene film or polypropylene film as a low-polarity substrate. Polyolefin film. The base material for the release sheet in the release laminated sheet is paper or a polymer film. As the release agent constituting the release agent layer, for example, a general addition type or condensation type silicone release agent or a long-chain alkyl group-containing compound can be used. In particular, an addition type silicone release agent with high reactivity can be preferably used.

The double-sided adhesive sheet for decorative molding with a release sheet preferably has a pair of release sheets with different peeling forces on both surfaces of the double-sided adhesive sheet. That is, it is preferable to provide a first release sheet on one surface of the double-sided adhesive sheet and a second release sheet on the other surface of the double-sided adhesive sheet, and the first release sheet and the second release sheet have different peeling forces. In the example of FIG. 1, in order to peel a peeling sheet easily, it is preferable to make the peeling property of the peeling sheet 12a and the peeling sheet 12b different. That is, if the releasability from one is different from the releasability from the other, it is easy to peel only the peeling sheet 12 with high releasability first. In this case, what is necessary is just to adjust the peelability of the peeling sheet 12 of the peeling sheet 12a and the peeling sheet 12b according to the bonding method or bonding order.

(Method of manufacturing double-sided adhesive sheet for decorative molding) The manufacturing method of the double-sided adhesive sheet for decorative molding of this invention includes the process of hardening the adhesive composition containing an olefin type elastomer. In addition to the olefin-based elastomer, the adhesive composition may further contain a silane coupling agent, a tackifier, an oil component, a softening agent, an anti-aging agent, a crosslinking agent, a pigment, a dehydrogenation type initiator, and the like.

When producing the adhesive composition, it is preferably produced by dissolving an olefin-based elastomer in a solvent such as toluene, and mixing a silane coupling agent, a thickener, an oil component, and the like. In addition, it is also possible to adopt a method of heating a particulate rubber containing an olefin-based elastomer to soften it, and kneading a silane coupling agent, a tackifier, or an oil component with a kneader.

By applying the adhesive composition prepared as described above by an existing method, a double-sided adhesive sheet for decorative molding can be obtained. In the case of using an adhesive composition manufactured by dissolving in a solvent, it can be formed into a sheet by coating with a knife coater or the like and drying the solvent in a drying oven. On the other hand, in the case of using an adhesive produced by a heating-based kneading method, it is possible to form a sheet by using a hot melt encoder that can soften the adhesive composition by heating in advance.

The adhesive sheet is preferably formed on the first release sheet, and preferably the second release sheet is laminated after the adhesive sheet is formed on the first release sheet by the method described above. In this way, it is possible to manufacture a double-sided adhesive sheet for decorative molding with a release sheet in which the release sheet is layered on both areas of the adhesive sheet.

(Laminated adhesive sheet for decorative molding) The present invention relates to a laminated adhesive sheet for decorative molding provided with a double-sided adhesive sheet for decorative molding and a surface side layer. The double-sided adhesive sheet for decorative molding included in the laminated adhesive sheet for decorative molding is the above-mentioned double-sided adhesive sheet for decorative molding, and the preferred aspect is also as described above. In addition, in this specification, the laminated adhesive sheet for decorative molding may also be referred to as a decorative film.

Since the laminated pressure-sensitive adhesive sheet for decorative molding of the present invention has the above-mentioned structure, it exhibits excellent adhesion to an adherend containing a polyolefin resin as a main component. Therefore, the laminated pressure-sensitive adhesive sheet for decorative molding of the present invention can be preferably used for bonding to an adherend containing a polyolefin resin as a main component. Here, the adhesion between the laminated adhesive sheet for decorative molding and the adherend can be evaluated by measuring the adhesive force when the laminated adhesive sheet for decorative molding is peeled off from the adherend. Specifically, using a tensile testing machine, under the conditions of a peeling speed of 300 mm/min, a peeling angle of 180 degrees, a measurement temperature of 23°C, and a relative humidity of 50%, the surface of the adherend is covered for decorative molding. The surface side layer of the laminated adhesive sheet was peeled from the adherend, and the adhesive force at this time was measured. The adhesive force at this time is preferably 3.0 N/25 mm or more, more preferably 5.0 N/25 mm or more, and still more preferably 10.0 N/25 mm or more. As the adherend containing polyolefin resin as the main component, for example, an adherend made of polypropylene or an adherend made of polyethylene can be cited, but the laminated adhesive sheet for decorative molding of the present invention is preferably made of polypropylene. Both the adherend and polyethylene adherend exhibit excellent adhesion.

Fig. 2 is a cross-sectional view illustrating an example of the configuration of a laminated adhesive sheet for decorative molding. As shown in FIG. 2, the laminated adhesive sheet 30 for decorative molding includes a surface side layer 21 and a double-sided adhesive sheet 11 for decorative molding as an adhesive layer. In this specification, when the double-sided adhesive sheet 11 for decorative molding is included in the laminated adhesive sheet 30 for decorative molding, the double-sided adhesive sheet 11 for decorative molding may also be referred to as the adhesive layer 11.

In FIG. 2, the surface-side layer 21 is a single layer, but the surface-side layer 21 may be a layer including multiple layers. That is, in this specification, the layer on the exposed surface side than the adhesive layer 11 is collectively referred to as the surface side layer 21. In addition, in this case, the surface side layer 21 may have an adhesive layer in order to laminate multiple layers, but the adhesive layer contained in the surface side layer 21 is a double layer for decorative molding that is directly attached to the adherend. The surface adhesive sheet 11 (adhesive layer 11) is a different adhesive layer.

Examples of layers constituting the surface side layer include functional layers such as a substrate layer, a decorative layer, a surface protective layer, an adhesive layer, an anti-reflection layer, and an anti-glare layer.

The base material layer is preferably a layer that can be stretched to follow the adherend in the forming step. The material constituting the substrate layer is preferably plastic, for example. As the plastic, for example, ABS resin (copolymer of acrylonitrile, butadiene and styrene), AS resin (copolymer of acrylonitrile and styrene), acrylic resin, polyethylene terephthalate, poly Butylene terephthalate, nylon, polyacetal, polyphenylene ether, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfide, polyether sulfide, poly Acetal, polyether ether ketone, polyphenylene sulfide, polyether imide, polyamide imide, polycarbonate, polyolefin resin (polyethylene, polypropylene, etc.), polystyrene, urethane Acid ester resin, etc. Among these, ABS resin, acrylic resin, polyethylene terephthalate, and polyolefin resin are more preferable. The base material layer may be a colored layer in which carbon (graphite) or the like is blended in these resins.

The decoration layer is preferably a printing layer. The printing layer is formed by, for example, printing on one side of the base layer using ink containing a thermosetting resin or ultraviolet curable resin as a main agent. For printing, a known printing method such as inkjet printing and screen printing can be used.

The surface protective layer is preferably a layer that is arranged on the most exposed surface side among the surface side layers and plays a role of improving scratch resistance or weather resistance. Therefore, the surface protective layer is preferably a layer including a curable resin layer, and more preferably a hard coat layer. Among them, the curable resin is preferably a photocurable resin, and more preferably an ultraviolet curable resin. In this case, the resin composition for forming the surface protective layer preferably contains a photopolymerization initiator in addition to the ultraviolet curable resin, for example.

The surface protection layer may further contain fine particles. As the fine particles, for example, inorganic fine particles can be cited, and metal oxides are preferably exemplified. Moreover, pigments or dyes may be contained as needed. Furthermore, the surface protective layer may optionally contain additives such as pigment dispersant, defoamer, ultraviolet absorber, light stabilizer, antioxidant, antistatic agent, anti-wear agent, and anti-blocking agent.

In order to adhere to the functional layers, the surface side layer may also include an adhesive layer. As an adhesive constituting such an adhesive layer, a known adhesive can be used. Examples of adhesives include natural rubber adhesives, synthetic rubber adhesives, acrylic adhesives, urethane adhesives, silicone adhesives, and the like. The adhesive may be any of a solvent system, a solvent-free system, an emulsion system, and an aqueous system. Among these, from the viewpoints of transparency, weather resistance, durability, cost, etc., an acrylic adhesive is preferred, and a solvent acrylic adhesive is particularly preferred.

The surface side layer may further include a protective film or, when the outermost layer has an adhesive layer, further include an isolation layer. The protective film or isolation layer is provided to temporarily protect the surface protective layer. For example, it is provided to prevent damage to the surface protection layer before use. The protective film is preferably a self-adhesive film containing an ethylene vinyl acetate copolymer, or a polyethylene terephthalate (polyethylene terephthalate, PET) film layered on a urethane-based and/or acrylic-based film. A micro-adhesive film made of a re-peelable adhesive layer. The separator layer preferably has a configuration in which a release layer such as silicone is provided on the surface of the general base layer. Such a separation layer is peeled off during the manufacturing process or use, and can also be removed from the laminated adhesive sheet for decorative molding.

As the structure of the surface side layer, the following layer structure can be mentioned, for example. In addition, in order to adhere each layer, if necessary, an adhesive layer may be provided between each layer. (1) A composition with a decorative layer and a surface protective layer in sequence (2) A composition with a decorative layer and a base layer in sequence (3) A composition with a substrate layer and a decorative layer in sequence (4) A composition with a decorative layer, a base material layer, and a surface protective layer in sequence (5) A configuration in which a protective film is further provided on the outermost surface of the configuration of (1) to (4) above (6) A configuration in which an adhesive layer and a spacer layer are further provided on the outermost surface of the above-mentioned (1) to (4) configuration

(Method for manufacturing laminated adhesive sheet for decorative molding) The manufacturing method of the laminated adhesive sheet for decorative molding includes the step of bonding a double-sided adhesive sheet for decorative molding and the surface side layer. Specifically, in the double-sided adhesive sheet for decorative molding with a release sheet manufactured by the manufacturing method of the double-sided adhesive sheet for decorative molding, the double-sided adhesive sheet for decorative molding exposed by peeling off one release sheet The adhesive surface of the sheet is attached to the surface side layer. As a bonding method, an existing bonding machine can be used. For example, the double-sided adhesive sheet for decorative molding and the surface side layer can be laminated using a combination of roll to roll, sheet to roll, roll to sheet, sheet to sheet, etc. It is preferable to perform bonding while applying pressure with a nip roll or a roller.

(Decorative molding laminate) The present invention relates to a decorative molded laminate formed by attaching a decorative molding laminated adhesive sheet to an adherend. The laminated adhesive sheet for decorative molding included in the decorative molded laminate is the above-mentioned laminated adhesive sheet for decorative molding, and the preferred aspect is also as described above. In addition, in the decorative molding laminate, a decorative molding laminate adhesive sheet is laminated on an adherend, and at least a part of the surface of the adherend is covered. In this specification, the decorative molded laminate may also be simply referred to as a decorative molded body.

Fig. 3 is a cross-sectional view illustrating an example of the structure of a decorative molded laminate. As shown in FIG. 3, the decorative molded laminate 100 has a configuration in which a decorative molded laminated adhesive sheet is laminated on an adherend 50. As shown in FIG. 3, the laminated adhesive sheet for decorative molding has a double-sided adhesive sheet 11 (adhesive layer 11) for decorative molding and a surface side layer 21, and the adhesive layer 11 is directly attached to the adherend 50.

Previously, as the adherend of the decorative molded laminate, polycarbonate resin or ABS resin was used. However, in the present invention, since the adhesive layer contains an olefin elastomer, even if a polyolefin resin is used as the In the case of an adherend of the main component, a decorative molded laminate in which the decorative film is sufficiently closely adhered can also be obtained. Therefore, in the present invention, as the adherend of the decorative molded laminate, a particularly suitable aspect is to use an adherend containing a polyolefin resin as a main component.

The shape of the adherend is not particularly limited, and may be a plate shape or a three-dimensional shape. Moreover, the adherend may have an uneven structure in a part of its surface.

The adherend is preferably a component of a vehicle, a component of an electronic device, or a building material. Examples of vehicle components include automotive components (for example, various materials such as body, bumper, spoiler, mirror, wheels, interior materials and other parts), and two-wheeled vehicle components , Components for railway vehicles. Moreover, as electronic equipment components, electronic equipment, such as a home appliance, or a liquid crystal display device, such as a personal computer, etc. are mentioned. Examples of building materials include furniture and building materials. Furthermore, the adherend may be road materials (such as traffic signs, soundproof walls, etc.), tunnel materials (such as side wall panels, etc.), musical instruments, containers, office supplies, sporting goods, toys, and the like.

(Method of manufacturing decorative molded laminate) The manufacturing method of the decorative molded laminate preferably includes a step of thermally bonding the laminated adhesive sheet for decorative molding to the adherend. As a manufacturing method of the decorative molded laminate, for example, hot press molding, injection molding, insert molding, molding under vacuum or reduced pressure, etc. of the laminated adhesive sheet for decorative molding can be cited. Among them, the manufacturing method of the decorative molded laminate is preferably molding under vacuum or reduced pressure, and the laminated adhesive sheet for decorative molding is an adhesive sheet suitable for decorative molding under vacuum or reduced pressure.

In this specification, forming under vacuum or reduced pressure is referred to as the so-called Three Dimension Overlay Method (TOM) forming. The TOM molding method includes the step of laminating the decorative molding laminated adhesive sheet on the adherend under vacuum or reduced pressure, and the pressure bonding of the decorative molding laminated adhesive sheet to the adherend by pressure difference step. Furthermore, in TOM molding, it is preferable to include a step of heating the surface of the laminated adhesive sheet for decorative molding to 100° C. or higher and 180° C. or lower after the step of pressing the laminated adhesive sheet for decorative molding to the adherend. In this case, it is preferable to use an infrared heater for heating.

In addition, in this specification, molding under vacuum conditions or reduced pressure conditions does not include a method of making a laminated body and a molded body adhere to each other by providing a vacuum hole in the molded body. Specifically, molding under vacuum or reduced pressure can be performed by using the "vacuum forming apparatus" described in Japanese Patent No. 3733564.

In addition, when the injection molding method is used as the manufacturing method of the decorative molded laminate, the decorative molding laminate adhesive sheet is fixed in the mold of the injection molding machine, and injected into the mold to form the polyolefin-based adherend. A resin composition containing a resin as a main component is cured to obtain a decorative molded laminate. Moreover, when insert molding is used as the manufacturing method of the decorative molding laminate, the decorative molding laminate adhesive sheet is heated and softened, and after molding and other treatments, it is inserted into the molding metal mold and injected into the molding metal mold for aggregation. A resin composition containing an olefin-based resin as a main component is cured to obtain a decorative molded laminate. Hot press molding is a molding method in which a laminated adhesive sheet for decorative molding is laminated on an adherend with polyolefin resin as the main component, and then heated and pressurized. A part of the injection molding or insert molding method may also include a hot press step . [Example]

Examples and comparative examples are listed below to more specifically illustrate the characteristics of the present invention. The materials, usage amount, ratio, processing content, processing order, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly understood by the specific examples shown below.

＜Manufacture of adhesive composition＞ Adhesive composition (A-1) 100 parts by mass of olefin-based elastomer (manufactured by Kuraray, Septon 2063), 70 parts by mass of styrene-based tackifier (manufactured by Mitsui Chemicals, FTR8100), and paraffin-based oil (Idemitsu Co., Ltd.) Manufacture, 50 parts by mass of Diana Process Oil (PW-90) and 0.5 parts by mass of silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., X-41-1818) are dissolved in toluene and stirred until uniform to obtain solid content Adhesive composition (A-1) with a concentration of 45% by mass. The stirring is for 4 hours at 23°C. In addition, the solid content refers to an olefin-based elastomer, a silane coupling agent, a thickener, and an oil component.

Adhesive composition (A-2) Except that an olefin-based elastomer (manufactured by Kuraray, Septon 8007L) was used, an adhesive with a solid content concentration of 45% by mass was obtained in the same manner as the preparation method of the adhesive composition (A-1) Composition (A-2). In addition, the olefin-based elastomer (manufactured by Kuraray Co., Ltd., Septon 8007L) is a block copolymer, and is a polymer having a block containing a styrene-based polymer in a part thereof.

Adhesive composition (A-3) Except that the addition amount of styrene-based tackifier was changed to 100 parts by mass and the addition amount of paraffin-based oil was changed to 100 parts by mass, the solid content concentration was obtained in the same manner as in the preparation method of the adhesive composition (A-1) 45 mass% adhesive composition (A-3).

Adhesive composition (A-4) Except that the addition amount of the styrene-based tackifier was changed to 30 parts by mass and the addition amount of the paraffin-based oil was changed to 25 parts by mass, the solid content concentration was obtained in the same manner as the preparation method of the adhesive composition (A-1) 45 mass% adhesive composition (A-4).

Adhesive composition (B-1) In a reaction vessel equipped with a stirrer, a nitrogen introduction tube, a thermometer, and a reflux cooling tube, n-butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) are mixed so that the mass ratio becomes 80:20, and the 2,2 '-Azobis(2,4-dimethylvaleronitrile) is dissolved in the solution as a radical polymerization initiator. By heating the solution to 60°C, the monomer components were randomly copolymerized to obtain a solution of the copolymer (B). With respect to 100 parts by mass of the solid content of the obtained copolymer (B), a xylylene diisocyanate compound (manufactured by Mitsui Chemicals Co., Ltd., Takenate D-110N) as a crosslinking agent is added 0.11 part by mass, ethyl acetate was added so that the solid content concentration became 40% by mass, and an adhesive composition (B-1) was obtained.

Adhesive composition (C-1) As the acid component, the terephthalic acid: isophthalic acid: adipic acid is 30:30:40, and the diol component is 1,4-butanediol and 1,6-hexanediol. It is formulated in a 25:75 manner and heated in the presence of a catalyst (tetrabutyl titanate) to obtain a thermoplastic saturated copolyester resin. The obtained thermoplastic saturated co-polyester resin was dissolved in a solvent (methyl ethyl ketone), and diluted and stirred so as to become a solution with a solid content concentration of 30% by mass. Next, 2 parts by mass of polyisocyanate (manufactured by Japan Polyurethane, "Coronate HX" (hexamethylene) is added to the solution with respect to 100 parts by mass of the thermoplastic saturated copolyester resin. Diisocyanate) with a solid content concentration of 100% by mass) to obtain an adhesive composition (C-1).

＜Making of Adhesive Sheet＞ (Example 1) Using a knife coater, the adhesive composition (A-1) produced as described above was applied to a release sheet (Oji F-Tex (Oji F-Tex) on the side with heavy peeling force) so that the thickness after drying became 50 μm Manufactured by the company: RL-07(2)), and then dried at 100°C for 3 minutes to volatilize the solvent toluene to obtain a double-sided adhesive sheet. By laminating a release sheet (manufactured by Oji F-Tex (Oji F-Tex): RL-07 (L)) on the light-release side on the obtained adhesive sheet, a double-sided adhesive sheet with a release sheet was obtained. Next, the peeling sheet on the light peeling force side of the double-sided adhesive sheet was peeled off, and the surface side layer (manufactured by Mitsubishi Rayon, acryplen HBA001P, pencil hardness 2H, thickness 125 μm) lamination to obtain a laminated adhesive sheet for decorative molding.

(Example 2) Except having changed the adhesive composition (A-1) to the adhesive composition (A-2), it carried out similarly to Example 1, and obtained the laminated adhesive sheet for decorative molding.

(Example 3) Except having changed the adhesive composition (A-1) into the adhesive composition (A-3), it carried out similarly to Example 1, and obtained the laminated adhesive sheet for decorative molding.

(Example 4) Except having changed the adhesive composition (A-1) to the adhesive composition (A-4), it carried out similarly to Example 1, and obtained the laminated adhesive sheet for decoration molding.

(Comparative example 1) Except having changed the adhesive composition (A-1) to the adhesive composition (B-1), it carried out similarly to Example 1, and obtained the laminated adhesive sheet for decorative molding.

(Comparative example 2) Except having changed the adhesive composition (A-1) to the adhesive composition (C-1), it carried out similarly to Example 1, and obtained the laminated adhesive sheet for decorative molding.

(Method of evaluating adhesion) <Production of decorative molded laminate> The decorative molding laminated body was produced using the laminated adhesive sheet for decoration molding obtained in each Example and a comparative example. First, the laminated adhesive sheet for decorative molding from which the release sheet on the heavy peeling force side was removed was set in the TOM molding machine. As the adherend, a polyethylene sheet of 2.0 mm×25 mm×150 mm (manufactured by Sumitomo Chemical Co., Sumitomo Nobrene AZ864) or polypropylene sheet (manufactured by Sumitomo Chemical Co., Sumitomo森 (sumikathene) (registered trademark)-L GA401). The adherend was set in a TOM molding machine (manufactured by Busch Vacuum Co., Ltd., NGF molding machine) so that the adhesive layer of the laminated adhesive sheet for decorative molding faced each other. The decorative molding laminated adhesive sheet was laminated on the molded body at 130° C. using a TOM molding machine to obtain a decorative molded laminated body. ＜Evaluation＞ Using a tensile testing machine, under the conditions of a peeling speed of 300 mm/min, a peeling angle of 180 degrees, a measurement temperature of 23°C, and a relative humidity of 50%, the surface side layer of the molded product produced by the TOM molding machine was self-coated The sticky substance peeled off, and the force (adhesive force) required for peeling at this time was measured, and evaluated according to the following criteria. ◎･･･Adhesive force is 10.0 N/25 mm or more ○･･･The adhesive force is less than 10.0 N/25 mm and 5.0 N/25 mm or more △･･･The adhesive force is less than 5.0 N/25 mm and 3.0 N/25 mm or more ×･･･adhesive force is less than 3.0 N/25 mm

[Table 1] Deployment conditions and evaluation results Example Comparative example 1 2 3 4 1 2 Types of adhesive composition Olefin elastomer A-1 A-2 A-3 A-4 - - Acrylic - - - - B-1 - Polyester series - - - - - C-1 Tightness PP ◎ ○ ○ ○ × × PE ◎ ◎ ○ ◎ △ △

The laminated pressure-sensitive adhesive sheet for decorative molding obtained in the examples showed good adhesion to polyethylene and polypropylene adherends. On the other hand, the laminated adhesive sheet for decorative molding obtained in the comparative example has insufficient adhesion to polyethylene and polypropylene adherends.

1: Double-sided adhesive sheet for decorative molding with release sheet 11: Double-sided adhesive sheet for decorative molding (adhesive layer) 12a, 12b: peeling sheet 21: Surface side layer 30: Laminated adhesive sheet for decorative molding 50: Stickies 100: Decorative forming laminate

Fig. 1 is a cross-sectional view showing an example of the structure of a double-sided adhesive sheet for decorative molding with a release sheet. Fig. 2 is a cross-sectional view showing an example of the structure of a laminated adhesive sheet for decorative molding. 3 is a cross-sectional view showing an example of the structure of a decorative molded laminate.

1: Double-sided adhesive sheet for decorative molding with release sheet

11: Double-sided adhesive sheet for decorative molding (adhesive layer)

12a, 12b: peeling sheet

Claims (9)

A double-sided adhesive sheet for decorative molding, containing an olefin-based elastomer. The double-sided adhesive sheet for decorative molding according to Claim 1, which is used for bonding to an adherend containing a polyolefin resin as a main component. The double-sided adhesive sheet for decorative molding according to claim 1 or 2, wherein the olefin-based elastomer is a block copolymer. The double-sided adhesive sheet for decorative molding according to claim 1 or claim 2, wherein the olefin-based elastomer is a block copolymer, and the block copolymer has a portion containing a styrene-based polymer Block. A laminated adhesive sheet for decorative molding, comprising: the double-sided adhesive sheet for decorative molding according to any one of Claims 1 to 4, and a surface side layer. The laminated adhesive sheet for decorative molding according to claim 5, wherein the laminated adhesive sheet for decorative molding is used for decorative molding under vacuum or reduced pressure. A decorative molding laminate, which is formed by attaching the decorative molding laminated adhesive sheet as described in claim 5 or claim 6 to an adherend. The decorative molded laminate according to claim 7, wherein the adherend contains a polyolefin resin as a main component. The decorative molded laminate according to claim 7 or claim 8, wherein the adherend is a component of a vehicle, a component of an electronic device, or a building material.

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