TWI831936B - Double-sided adhesive sheet for decorative molding, laminated adhesive sheet for decorative molding, and decorative molded laminated body - Google Patents

Abstract

An object of the present invention is to provide 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. The present invention relates to a double-sided adhesive sheet for decorative molding containing an olefin elastomer. Furthermore, the present invention relates to a laminated adhesive sheet for decorative molding, which includes a double-sided adhesive sheet for decorative molding containing an olefin-based elastomer, and a surface side layer.

Description

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

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

Previously, in the case of protecting or modifying (decorating) the surfaces of automobile interior and exterior decorative parts, home appliance parts, building material parts, etc., the molded body was processed by injection molding or vacuum forming, and then the molded body was processed by spraying or the like. The surface of the molded body is coated with paint, dried, and heated to harden. 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 yield of the coating because it requires working steps and production equipment for the molded parts, or requires 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 parts, etc., the use of resin molded articles has been promoted as molded articles. Most of the modification (decoration) of resin molded objects is not suitable for spraying, but various methods have been developed in order to decorate the surface of resin molded objects. Among them, the method of obtaining a decorated molded article by decorating the outermost surface of the molded article with a decorative film has the advantages of high design freedom and excellent productivity compared to the method of coating or printing on the surface with paint or the like. Moreover, the decoration method using decorative films can also be used to decorate molded objects with three-dimensional unevenness. The surface is decorated and therefore used for various purposes.

For example, Patent Document 1 discloses a laminate for decorative molding, which has a base material layer and an adhesive layer, and the adhesive layer includes a silicone-based adhesive layer and an acrylic-based adhesive layer. Furthermore, Patent Document 2 discloses a vacuum forming sheet having an adhesive layer on the lower surface of a surface film. Here, the adhesive layer is prepared by mixing 1.5 to 2.5 equivalents of polyisocyanate into a thermoplastic saturated copolyester resin and hardening the mixture.

[Prior Art Document]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2017-154410

[Patent Document 2] Japanese Patent Application Publication No. 2010-120209

In the decorative formed body, it is of course required that the adherend and the decorative film are fully adherent and not easy to peel off. However, when a polyolefin-based raw material is used for the adherend, if the conventional decorative molding adhesive sheet (decorative molding laminate) is used, the adhesiveness of the decorative film to the adherend may not be fully exerted. problem.

Therefore, in order to solve the problems of the prior art, the present inventors provide a double-sided adhesive sheet for decorative molding and a laminate for decorative molding that exhibit excellent adhesion to an adherend containing a polyolefin-based resin as a main component. Adhesive sheets were studied for this purpose.

As a result of intensive research to solve the above-mentioned problems, the present inventors found that by forming an adhesive layer containing an olefin-based elastomer, excellent adhesion to an adherend containing a polyolefin-based resin as a main component can be obtained Double-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 according to [1], which is used for bonding to an adherend containing a polyolefin-based resin as a main component.

[3] The double-sided adhesive sheet for decorative molding according to [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 a part of the block copolymer has a styrene-based polymer blocks.

[5] A laminated adhesive sheet for decorative molding, including: the double-sided adhesive sheet for decorative molding according to any one of [1] to [4], and a surface side layer.

[6] The laminated adhesive sheet for decorative molding according to [5], wherein the laminated adhesive sheet for decorative molding is used for decorative molding under vacuum conditions or reduced pressure conditions.

[7] A decorative molding laminated body obtained by bonding the decorative molding laminated adhesive sheet described in [5] or [6] to an adherend.

[8] The decorative molded laminate according to [7], wherein the adherend contains a polyolefin-based resin as a main component.

[9] The decorative molded laminated body as described in [7] or [8], wherein the adherend is traffic engineering Tool components, electronic equipment components or building materials.

According to the present invention, it is possible to obtain 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-based resin as a main component.

1: Double-sided adhesive sheet for decorative molding with peel-off sheet

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

12a, 12b: Peel-off sheet

21:Surface side layer

30:Laminated adhesive sheet for decorative molding

50: Adherence

100: Decorative molded laminated body

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 the laminated adhesive sheet for decorative molding.

FIG. 3 is a cross-sectional view showing an example of the structure of a decorative molded laminated body.

Hereinafter, the present invention will be described in detail. The description of the structural elements described below may be based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. In addition, the numerical range represented by "~" in this specification refers to the range including 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 elastomer. Since the adhesive sheet of the present invention has the above-mentioned structure, it exhibits excellent adhesion to an adherend containing a polyolefin-based resin as a main component. Therefore, the double-sided adhesive sheet for decorative molding of the present invention can be preferably used as an adhesive sheet containing polyolefin-based resin. The main component is used for adhering to adherends.

Previously, polycarbonate resin or acrylonitrile butadiene styrene (ABS) resin was used as an adherend for decorative moldings. Therefore, no detailed study has been conducted on an adhesive sheet for decorating an adherend containing a polyolefin-based resin as a main component. Therefore, the present inventors found that when an adherend containing a polyolefin-based resin as a main component is used as an adherend, the conventional decorative film does not have sufficient adhesion to the adherend. It is difficult to obtain a decorative molded article excellent in durability or design. Therefore, the present invention provides a double-sided adhesive sheet for decorative molding that has an optimal structure for exhibiting excellent adhesiveness when using an adherend containing a polyolefin-based resin as a main component.

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

Olefin-based elastomers contain 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 α-olefin. Examples of the olefin-based elastomer include propylene/ethylene copolymer, propylene/ethylene/1-butene copolymer, 1-butene homopolymer, 1-butene/ethylene copolymer, and 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, or 1,3-butadiene copolymer. -Chouji Elastomers containing unsaturated bonds in the polymer chain such as olefin homopolymer (polybutadiene). Furthermore, from the viewpoint of weather resistance, hydrogenated compounds of polyisoprene and polybutadiene can also be used.

The olefin elastomer is preferably a block copolymer. When the olefin-based elastomer is a block copolymer, examples of the block copolymer include: 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 examples of such elastomers include hydrogenated compounds thereof.

When the olefin-based elastomer is a block copolymer, the block copolymer contains a block obtained by polymerizing α-olefin and another block containing a polymer. In this case, examples of the other block containing a polymer include a block containing a styrene-based polymer, a block containing a (meth)acrylate-based polymer, and the like. Among these, the other block containing a polymer is preferably a block containing a styrenic 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 is preferably 30 mass% or more, more preferably 40 mass% or more relative to the total mass of the double-sided adhesive sheet for decorative molding. By setting the content of the olefin-based elastomer within the above range, the double-sided adhesive sheet for decorative molding of the present invention can exhibit superior adhesion compared to an adherend containing a polyolefin-based resin as a main component. Compatibility.

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 within the above range, the double-sided adhesive sheet for decorative molding of the present invention can exhibit superior adhesion to an adherend containing a polyolefin-based resin as a main component.

The double-sided adhesive sheet for decorative molding may contain additives in addition to the olefin elastomer. Examples of additives include silane coupling agents, thickeners, oil components, softeners, anti-aging agents, cross-linking 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 initiator. By containing these additives in the double-sided adhesive sheet for decorative molding, the adhesiveness of the double-sided adhesive sheet can be further improved, thereby improving durability or weather resistance.

Examples of the silane coupling agent include a thiol-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. Among these, it is preferable to use a mercapto-based silane coupling agent in the use of the present invention. Examples of the mercapto silane coupling agent include mercaptotrimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, triethoxy(2-mercaptoethyl)silane, and 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 mass% or more, more preferably 0.1 mass% or more, relative to the total mass of the double-sided adhesive sheet for decorative molding. Moreover, compared to pretending The content of the silane coupling agent is preferably 5.0 mass% or less, more preferably 3.0 mass% or less based on the total mass of the double-sided adhesive sheet for decoration molding.

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

As the oil component, a paraffin-based or naphthenic system oil is preferred, and a paraffin-based system oil can be more preferably used because it does not easily cause deterioration of the rubber.

Examples of the dehydrogenation-type initiator include benzophenone compounds such as methyl benzoate and 4-methylbenzophenone. Relative to the total mass of the double-sided adhesive sheet for decorative molding, the content of the dehydrogenation-type initiator is preferably 0.05 mass% or more, more preferably 0.1 mass% or more. Furthermore, the content of the silane coupling agent is preferably 5.0 mass% or less, more preferably 3.0 mass% or less relative 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 range, the double-sided adhesive sheet for decorative molding can also have active energy ray hardening properties, and therefore the cohesive force can be improved through 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, further 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, the durability can be improved and the adhesion with the adherend can be improved more effectively. Furthermore, by shaping the decoration with When the thickness of the double-sided adhesive sheet is within the above 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 in FIG. 1 is a single-layer double-sided adhesive sheet without a base material.

Examples of the release sheet include a release laminated sheet having a release sheet base material and a release agent layer provided on one side of the release sheet base material, or a polyethylene film or a polypropylene film as a low polarity base material, etc. Polyolefin film. Paper and polymer film are used as the base material for the release sheet in the release laminated sheet. As the release agent constituting the release agent layer, for example, a general-purpose addition-type or condensation-type silicone-based 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 peeling sheet preferably has a pair of peeling sheets with mutually different peeling forces on both surfaces of the double-sided adhesive sheet. That is, it is preferable to have 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 release forces. In the example of FIG. 1 , in order to easily peel off the release sheet, it is preferable to make the release properties of the release sheet 12 a and the release sheet 12 b different. That is, if the releasability from one side is different from the releasability from the other side, it is easy to peel off only the release sheet 12 with high releasability first. In this case, the peelability of the peeling sheet 12 of the peeling sheet 12a and the peeling sheet 12b may be adjusted according to the lamination method or the lamination order.

(Method for manufacturing double-sided adhesive sheet for decorative molding)

The method of manufacturing a double-sided adhesive sheet for decorative molding of the present invention includes the step of curing an adhesive composition containing an olefin-based elastomer. In addition to the olefin elastomer, the adhesive composition may further contain a silane coupling agent, a tackifier, an oil component, a softener, an anti-aging agent, a cross-linking agent, a pigment, a dehydrogenation initiator, etc.

When preparing the adhesive composition, it is preferably produced by dissolving the olefin elastomer in a solvent such as toluene and mixing a silane coupling agent, a tackifier, an oil component, and the like. Alternatively, a method of heating and softening granular rubber containing an olefin-based elastomer, and kneading a silane coupling agent, a tackifier, or an oil component using a kneader may be used.

By applying the adhesive composition prepared as described above using a conventional method, a double-sided adhesive sheet for decorative molding can be obtained. When using an adhesive composition produced by dissolving it in a solvent, it can be formed into a sheet by applying it with a blade coater or the like and then drying the solvent in a drying oven. On the other hand, when an adhesive produced by a kneading method based on heating is used, it can be formed into 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 the second release sheet is preferably laminated after the adhesive sheet is formed on the first release sheet by the above method. In this way, a double-sided adhesive sheet with a release sheet for decorative molding in which release sheets are laminated on both sides of the adhesive sheet can be produced.

(Laminated adhesive sheet for decorative molding)

The present invention relates to a laminated adhesive sheet for decorative molding that is provided with a double-sided adhesive sheet for decorative molding and a surface side layer. Decorative features of laminated adhesive sheets for decorative molding The double-sided adhesive sheet for molding is the double-sided adhesive sheet for decorative molding, and a preferred aspect is as described above. In addition, in this specification, the laminated adhesive sheet for decorative molding may also be called a decorative film.

Since the laminated adhesive sheet for decorative molding of the present invention has the above-described structure, it exhibits excellent adhesion to an adherend containing a polyolefin-based resin as a main component. Therefore, the laminated adhesive sheet for decorative molding of the present invention can be suitably used for laminating to an adherend containing a polyolefin-based 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, the decorative molding laminate covering the surface of the adherend was tested 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 adhesive sheet is peeled off from the adherend, and the adhesive force at this time is measured. The adhesive force at this time is preferably 3.0N/25mm or more, more preferably 5.0N/25mm or more, and further preferably 10.0N/25mm or more. Examples of adherends containing a polyolefin-based resin as a main component include polypropylene adherends and polyethylene adherends. However, the laminated adhesive sheet for decorative molding of the present invention is preferably made of polypropylene. It exhibits excellent adhesion to both the adherend and the adherend made of polyethylene.

FIG. 2 is a cross-sectional view illustrating an example of the structure of the 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 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 also be a layer including multiple layers. That is, in this specification, the layer located on the exposed surface side compared with the adhesive layer 11 is collectively called the surface side layer 21. In addition, in this case, the surface side layer 21 may further have an adhesive layer in order to laminate a plurality of layers, but the adhesive layer contained in the surface side layer 21 is a double decorative molding layer that is directly attached to the adherend. The surface adhesive sheet 11 (adhesive layer 11) has different adhesive layers.

Examples of layers constituting the surface side layer include functional layers such as a base layer, a decorative layer, a surface protective layer, an adhesive layer, an antireflection layer, and an antiglare layer.

The base material layer is preferably a layer that can extend in a manner that follows the adherend during the forming step. The material constituting the base material 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, polyethylene terephthalate, etc. are preferred. Butylene terephthalate, nylon, polyacetal, polyphenylene ether, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polystyrene, polyether styrene, polyethylene Ether ether ketone, polyphenylene sulfide, polyether imide, polyamide imide, polycarbonate, polyolefin resin (polyethylene, polypropylene, etc.), polystyrene, urethane resin, etc. . Among these, ABS resin, acrylic resin, polyethylene terephthalate, and polyolefin resin are more preferred. The base material layer may be a colored layer in which carbon (graphite) or the like is mixed with these resins.

The decorative layer is preferably a printed layer. The printing layer is formed, for example, by printing on one side of the base layer using an ink containing a thermosetting resin or an ultraviolet curing resin as a main ingredient. For printing, well-known printing methods such as inkjet printing and screen printing can be used. Brush method.

The surface protective layer is preferably a layer disposed on the most exposed surface side among the surface side layers and plays a role in 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.

The surface protective layer may further contain microparticles. Examples of the fine particles include inorganic fine particles, and a preferred example is a metal oxide. Furthermore, pigments or dyes may be included if necessary. Moreover, the surface protective layer may contain additives such as pigment dispersants, defoaming agents, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, anti-wear agents, and anti-adhesive agents as necessary.

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

The surface side layer may also include a protective film or, if the outermost layer has an adhesive layer, an isolation layer. A protective film or isolation layer is provided to temporarily protect the surface protective layer. For example, to prevent surface damage before use layer etc. The protective film is preferably a self-adhesive film composed of ethylene vinyl acetate copolymer, or a urethane-based and/or acrylic-based film laminated on a polyethylene terephthalate (PET) film. A micro-adhesive film made of a re-peelable adhesive layer. The isolation layer preferably has a structure in which a release layer such as silicone is provided on the surface of the above-mentioned base material layer. This isolation layer is peeled off during the manufacturing process or during use, and can also be removed from the laminated adhesive sheet for decorative molding.

Examples of the structure of the surface side layer include the following layer structures. In addition, in order to adhere each layer, an adhesive layer may be provided between each layer if necessary.

(1) A decorative layer and a surface protective layer are provided in sequence.

(2) A composition in which a decorative layer and a base material layer are provided in sequence

(3) A composition in which a base material layer and a decorative layer are provided in sequence

(4) A composition consisting of a decorative layer, a base material layer, and a surface protective layer in sequence.

(5) A structure in which a protective film is further provided on the outermost surface of the structures (1) to (4) above.

(6) A composition in which an adhesive layer and an isolation layer are further provided on the outermost surface of the compositions (1) to (4) above.

(Method for manufacturing laminated adhesive sheet for decorative molding)

The manufacturing method of the laminated adhesive sheet for decorative molding includes the step of laminating the 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 method of manufacturing a double-sided adhesive sheet for decorative molding, the double-sided adhesive sheet for decorative molding exposed by peeling off one release sheet The adhesive side of the sheet is attached to the surface side layer. As a laminating method, an existing laminating machine can be used. example For example, the double-sided adhesive sheet for decorative molding and the surface side layer can be bonded using a combination of roll to roll, sheet to roll, roll to sheet, sheet to sheet, etc. In this case , it is preferable to laminate while applying pressure using a nip roller or a roller.

(Decorative molded laminated body)

The present invention relates to a decorative molding laminated body in which a laminated adhesive sheet for decorative molding is bonded to an adherend. The laminated adhesive sheet for decorative molding included in the decorative molded laminated body is the above-mentioned laminated adhesive sheet for decorative molding, and a preferred aspect is as described above. In addition, in the decorative molding laminated body, the laminated adhesive sheet for decorative molding is laminated on the adherend, and at least part of the surface of the adherend is covered. In this specification, the decorative molded laminated body may be simply called a decorative molded body.

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

Conventionally, polycarbonate resin or ABS resin has been used as an adherend for a decorative molded laminated body. However, in the present invention, since the adhesive layer contains an olefin-based elastomer, even if a polyolefin-based resin is used as the adherend, Even in the case of an adherend as the main component, a decorative molded laminate in which the decorative film is fully adhered can be obtained. Therefore, in the present invention, a particularly suitable aspect as an adherend for the decorative molded laminated body is to use an adherend containing a polyolefin-based resin as a main component.

The shape of the adherend is not particularly limited. It can be plate-shaped or three-dimensional. body shape. Moreover, the adherend may also have a concave-convex structure in a part of its surface.

The adherend is preferably a vehicle component, an electronic equipment component or a building material. Examples of vehicle components include automotive components (such as body parts made of various materials, bumpers, spoilers, mirrors, wheels, interior materials and other parts), and components for two-wheeled vehicles. , components for railway vehicles. Examples of electronic equipment components include electronic equipment such as home appliances, liquid crystal display devices such as personal computers, and the like. Examples of building materials include furniture, building materials, and the like. Furthermore, the adherends 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, etc.

(Method for manufacturing decorative molded laminated body)

The method of manufacturing the decorative molding laminated body preferably includes the step of thermally bonding the decorative molding laminated adhesive sheet to an adherend. Examples of methods for producing a decorative molded laminated body include hot press molding, injection molding, insert molding, molding under vacuum conditions or reduced pressure conditions, etc. of the laminated adhesive sheet for decorative molding. Among them, the manufacturing method of the decorative molding laminated body is preferably molding under vacuum conditions or reduced pressure conditions, and the decorative molding laminated adhesive sheet is an adhesive sheet suitable for decorative molding under vacuum conditions or reduced pressure conditions.

In this specification, molding under vacuum conditions or reduced pressure conditions is called so-called three-dimensional overlay method (TOM) molding. The TOM forming method includes the steps of laminating the decorative molding laminated adhesive sheet on the adherend under vacuum conditions or reduced pressure conditions, and the step of press-bonding the decorative molding laminated adhesive sheet to the adherend through air pressure difference. steps. Furthermore, in TOM forming, Preferably, after the step of crimping the laminated adhesive sheet for decorative molding to the adherend, the step of heating the surface of the laminated adhesive sheet for decorative molding to 100° C. or more and 180° C. or less is included. 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 the laminated body and the molded body closely adhere to each other by providing a vacuum hole in the molded body. Specifically, molding under vacuum conditions or reduced pressure conditions 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 molding laminated body, the laminated adhesive sheet for decorative molding is fixed in a metal mold of the injection molding machine, and the polyolefin system constituting the adherend is injected into the metal mold. A resin composition containing resin as a main component is cured to obtain a decorative molded laminated body. Furthermore, when the insert molding method is used as a manufacturing method of a decorative molded laminated body, the laminated adhesive sheet for decorative molding is heated and softened, and after performing processing such as molding, it is inserted into a forming metal mold, and is injected into the forming metal mold to form a polymer. A decorative molded laminated body is obtained by curing a resin composition containing an olefin resin as a main component. Hot press molding is a molding method in which a laminated adhesive sheet for decorative molding is laminated on an adherend mainly composed of polyolefin resin, and then heated and pressed. Part of the injection molding or insert molding method may also include a hot press step. .

[Example]

The features of the present invention will be described in more detail below with reference to Examples and Comparative Examples. Materials, usage amounts, ratios, processing contents, processing procedures, 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, this The scope of the 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 an olefin-based elastomer (Septon 2063 manufactured by Kuraray Co., Ltd.), 70 parts by mass of a styrene-based tackifier (FTR8100 manufactured by Mitsui Chemicals Co., Ltd.), and a 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 Industry Co., Ltd., X-41-1818) were dissolved in toluene and stirred until uniform to obtain a solid component Adhesive composition (A-1) with a concentration of 45% by mass. Stirring was at 23°C for 4 hours. In addition, the solid content refers to olefin elastomer, silane coupling agent, thickener, and oil components.

Adhesive composition (A-2)

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

Adhesive composition (A-3)

The solid content concentration was obtained in the same manner as the production method of the adhesive composition (A-1) except that the added amount of the styrene-based thickener was changed to 100 parts by mass and the added amount of the paraffin-based oil was changed to 100 parts by mass. 45 mass% adhesive composition (A-3).

Adhesive composition (A-4)

The solid content concentration was obtained in the same manner as in the production method of the adhesive composition (A-1) except that the added amount of the styrene-based thickener was changed to 30 parts by mass and the added amount of the paraffin-based oil was changed to 25 parts by mass. 45 mass% adhesive composition (A-4).

Adhesive composition (B-1)

In a reaction vessel equipped with a stirrer, nitrogen introduction pipe, thermometer and reflux cooling pipe, n-butyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were prepared in a mass ratio of 80:20, and 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 are randomly copolymerized to obtain a solution of the copolymer (B). A xylylene diisocyanate compound (Takenate D-110N, manufactured by Mitsui Chemicals Co., Ltd.) as a cross-linking agent was added to 100 parts by mass of the solid content of the copolymer (B) obtained above. 0.11 parts by mass of 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, terephthalic acid: isophthalic acid: adipic acid was prepared in a ratio of 30:30:40. As the diol component, 1,4-butanediol and 1,6-hexanediol were used. The mixture is prepared in a ratio of 25:75 and heated in the presence of a catalyst (tetrabutyl titanate) to obtain a thermoplastic saturated copolyester resin. The obtained thermoplastic saturated copolyester resin was dissolved in a solvent (methyl ethyl ketone), and diluted and stirred so as to obtain a solution with a solid content concentration of 30% by mass. Next, add to this solution Add 2 parts by mass of polyisocyanate (manufactured by Nippon Polyurethane, "Coronate HX" (hexamethylene diisocyanate)) based on 100 parts by mass of the thermoplastic saturated copolymerized polyester resin, and the solid content concentration: 100% by mass), thereby obtaining an adhesive composition (C-1).

<Preparation of adhesive sheet>

(Example 1)

The adhesive composition (A-1) prepared as described above was applied to the release sheet (Oji F-Tex) on the heavy release force side using a knife coater so that the thickness after drying would be 50 μm. Production: RL-07(2)), and then dried at 100°C for 3 minutes to evaporate the toluene solvent to obtain a double-sided adhesive sheet. By laminating a release sheet (manufactured by Oji F-Tex Co., Ltd.: RL-07(L)) on the light release force side on the obtained adhesive sheet, a double-sided adhesive sheet with a release sheet was obtained.

Next, the release sheet on the light release force side of the double-sided adhesive sheet was peeled off and separated from the surface side layer (acryplen HBA001P manufactured by Mitsubishi Rayon Co., Ltd., with a pencil hardness of 2H and a thickness of 125 μm. ) are bonded together to obtain a laminated adhesive sheet for decorative molding.

(Example 2)

A laminated adhesive sheet for decorative molding was obtained in the same manner as in Example 1, except that the adhesive composition (A-1) was changed into the adhesive composition (A-2).

(Example 3)

A laminated adhesive sheet for decorative molding was obtained in the same manner as in Example 1, except that the adhesive composition (A-1) was changed into the adhesive composition (A-3).

(Example 4)

A laminated adhesive sheet for decorative molding was obtained in the same manner as in Example 1, except that the adhesive composition (A-1) was changed into the adhesive composition (A-4).

(Comparative example 1)

A laminated adhesive sheet for decorative molding was obtained in the same manner as in Example 1, except that the adhesive composition (A-1) was changed into the adhesive composition (B-1).

(Comparative example 2)

A laminated adhesive sheet for decorative molding was obtained in the same manner as in Example 1, except that the adhesive composition (A-1) was changed into the adhesive composition (C-1).

(Evaluation method of adhesion)

<Production of decorative molded laminated body>

A decorative molding laminated body was produced using the laminated adhesive sheet for decorative molding obtained in each of the Examples and Comparative Examples. First, the laminated adhesive sheet for decorative molding from which the peeling sheet on the heavy peeling force side was removed was set in the TOM molding machine. As adherends, 2.0 mm × 25 mm × 150 mm polyethylene sheets (Sumitomo Nobrene AZ864 manufactured by Sumitomo Chemical Company) or polypropylene sheets (Sumikarson manufactured by Sumitomo Chemical Company) were used. sumikathene) (registered trademark)-L GA401). The adherend was placed in a TOM molding machine (NGF molding machine manufactured by Busch Vacuum Co., Ltd.) so that the adhesive layer of the laminated adhesive sheet for decorative molding faced each other. A decorative molding laminated adhesive sheet was laminated on the molded body at 130° C. using a TOM molding machine, thereby obtaining a decorative molding laminated body.

<evaluation>

Using a tensile testing machine, the surface side layer of the molded product produced by the TOM molding machine was self-adhesive 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%. When the object is peeled off, the force (adhesive force) required for peeling at this time is measured and evaluated according to the following standards.

◎． ． ． Adhesion force is above 10.0N/25mm

○． ． ． Adhesion force is less than 10.0N/25mm and above 5.0N/25mm

△． ． ． Adhesion force is less than 5.0N/25mm and above 3.0N/25mm

×. ． ． Adhesion force is less than 3.0N/25mm

The laminated adhesive sheet for decorative molding obtained in the Example showed good adhesion to adherends made of polyethylene and polypropylene. On the other hand, the laminated adhesive sheet for decorative molding obtained in the comparative example had insufficient adhesion to adherends made of polyethylene and polypropylene.

1: Double-sided adhesive sheet for decorative molding with peel-off sheet

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

12a, 12b: Peel-off sheet

Claims (7)

A double-sided adhesive sheet for decorative molding, containing an olefin elastomer, a silane coupling agent, a tackifier, an oil component and a dehydrogenation initiator, wherein the olefin elastomer is a block copolymer; the block The copolymer contains a block obtained by polymerizing α-olefin and a block containing a styrene-based polymer; the content of the olefin-based elastomer relative to the total mass of the double-sided adhesive sheet for decorative molding It is 30 mass% or more, wherein the content of the silane coupling agent is 0.05 mass% or more and 5.0 mass% or less relative to the total mass of the double-sided adhesive sheet for decorative molding, and wherein relative to the double-sided adhesive sheet for decorative molding The total mass of the surface-adhesive sheet, the content of the dehydrogenation initiator is 0.05 mass% or more and 5.0 mass% or less. The double-sided adhesive sheet for decorative molding according to Claim 1, which is used for bonding to an adherend containing polyolefin-based resin as a main component. A laminated adhesive sheet for decorative molding, including: the double-sided adhesive sheet for decorative molding according to claim 1 or claim 2, and a surface side layer. The laminated adhesive sheet for decorative molding according to claim 3, wherein the laminated adhesive sheet for decorative molding is used for decorative molding under vacuum conditions or reduced pressure conditions. A decorative molding laminated body formed by bonding the laminated adhesive sheet for decorative molding according to claim 3 or 4 to an adherend. The decorative molded laminated body according to claim 5, wherein the adherend contains a polyolefin-based resin as a main component. The decorative molded laminated body according to Claim 5 or 6, wherein the adherend is a component of a vehicle, a component of an electronic device, or a building material.

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