Peelable adhesive layer and laminate

Abstract

To provide a peelable adhesive layer with good adhesion that does not peel off during normal use, and good release properties that allow it to be peeled off when you want to.SOLUTION: There is provided a peelable adhesive layer. The peelable adhesive layer is a coating film of a coating material for an adhesive layer. The coating material for an adhesive layer is a two-part type coating material consisting of a first agent containing a water-dispersed acrylic resin and a water-dispersed urethane resin, and a second agent containing isocyanate. The water-dispersed urethane resin has a glass transition temperature (Tg) of -80 to 0°C. The water-dispersed acrylic resin has a hydroxy value of 40 to 165 mg KOH / g. The ratio (NCO / OH) of the number of moles of isocyanate groups in the isocyanate to the number of moles of hydroxy groups contained in the first agent is 0.5 to 2.0.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a peelable adhesive layer and a laminate. [Background technology]

[0002] A peelable coating film may be provided on the exterior of an automobile (for example, a clear coating film on the exterior of an automobile) for the purpose of changing the color of the exterior of the automobile or for the purpose of protecting the exterior of the automobile. Such a coating film is peeled off after being used for a certain period of time. During the period of use, high coating film performance as an automobile exterior is required. Paints for peelable coating films are widely sold, for example, those in which synthetic rubber such as styrene-butadiene copolymer is dissolved in organic solvents such as xylene, ethylbenzene, acetone, and methyl ethyl ketone. These paints release volatile organic compounds into the air during the drying process, which raises health and environmental concerns. In recent years, against this background, there has been a demand for water-based paints for peelable coating films (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] US Patent Application Publication No. 2020 / 0216682 Summary of the Invention [Problem to be solved by the invention]

[0004] Such coating films need to maintain appropriate adhesion from the time of application until the time of final peeling so that they do not peel off inadvertently and can be peeled off when desired.

[0005] When the present inventors attempted to apply a conventional water-based one-component paint to the exterior of an automobile, the following problems arose. 1. Adhesion that does not come off during normal use Second: Peelability allows you to peel it off whenever you want.

[0006] The peelability allows the film to be peeled off whenever desired. Even if the adhesion or peelability is appropriate at the beginning of the coating process, heat (e.g., summer temperatures) gradually increases adhesion, and the peelability does not last.

[0007] Therefore, an object of the present invention is to provide a peelable adhesive layer that has good adhesion so that it does not peel off during normal use and good releasability so that it can be peeled off at a desired timing. Another object of the present invention is to provide a laminate that includes such a peelable adhesive layer. [Means for solving the problem]

[0008] The peelable adhesive layer according to the present invention comprises: It is a coating film of paint for adhesive layer, The adhesive layer coating material is a two-component type coating material consisting of a first agent containing a water-dispersible acrylic resin and a water-dispersible urethane resin, and a second agent containing an isocyanate, The water-dispersible urethane resin has a glass transition temperature (Tg) of −80 to 0° C.; The hydroxyl value of the water-dispersible acrylic resin is 40 to 165 mg KOH / g; The ratio (NCO / OH) of the number of moles of isocyanate groups in the isocyanate to the number of moles of hydroxyl groups in the first agent is 0.5 to 2.0. This provides a peelable adhesive layer that has sufficient adhesion to prevent peeling during normal use and excellent releasability to allow peeling at any time.

[0009] The laminate according to the present invention is formed by sequentially adjacently The peelable adhesive layer, This provides a laminate that has good adhesion so that it will not peel off during normal use and good releasability so that it can be peeled off whenever desired.

[0010] In one embodiment of the laminate according to the present invention, the ratio of the mass of the water-dispersed acrylic resin to the total mass of the water-dispersed acrylic resin and the water-dispersed urethane resin is 10 to 90 mass %.

[0011] In one embodiment of the laminate according to the present invention, it is for use in a one-component coating film containing a polymerizable unsaturated monomer having an acid anhydride group, or for use in a two-component coating film containing a urethane resin.

[0012] In one embodiment of the laminate according to the present invention, the peel strength is 3N or more.

[0013] In one embodiment of the laminate according to the present invention, the peel strength after 80° C. / 100 h is 10 N or less.

[0014] In one embodiment of the laminate according to the present invention, the peel strength after an Xe test of 750 MJ is 10 N or less.

[0015] In one embodiment of the laminate according to the present invention, The peelable adhesive layer; A design layer; and the clear layer. Effect of the Invention

[0016] According to the present invention, it is possible to provide a peelable adhesive layer having good adhesion so that it does not peel off during normal use and good releasability so that it can be peeled off when desired. Also, according to the present invention, it is possible to provide a laminate having good adhesion so that it does not peel off during normal use and good releasability so that it can be peeled off when desired. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is a schematic diagram showing an example of a peelable adhesive layer according to the present invention. [Diagram 2] FIG. 2 is a schematic diagram showing an example of the layer structure of the laminate according to the present invention. [Diagram 3] FIG. 3 is a schematic diagram showing another example of the layer structure of the laminate according to the present invention. [Figure 4] FIG. 4 is a schematic diagram showing another example of the layer structure of the laminate according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Hereinafter, embodiments of the present invention will be described. These descriptions are intended to be illustrative of the present invention and are not intended to limit the present invention in any way.

[0019] In the present invention, two or more embodiments can be combined in any manner.

[0020] In the present invention, the paint and the paint composition can be used interchangeably.

[0021] Numerical ranges are intended to include the upper and lower limits of the range unless otherwise specified, for example, -80 to 0°C means a range of -80°C or higher and 0°C or lower.

[0022] The accompanying drawings are schematic diagrams given priority for facilitating understanding of the present invention, and therefore the dimensions and scale of each element in the drawings are not accurate.

[0023] In the present invention, the peel strength, the peel strength after 80° C. / 100 h, and the peel strength after Xe test of 750 MJ are measured by the method described in the Examples.

[0024] In the present invention, each of the resins, solvents, compounds, materials, members, etc. may be used alone or in combination of two or more.

[0025] (peelable adhesive layer) The peelable adhesive layer according to the present invention comprises: It is a coating film of paint for adhesive layer, the adhesive layer coating material is a two-component type coating material consisting of a first agent containing a water-dispersible acrylic resin and a water-dispersible urethane resin, and a second agent containing an isocyanate; The water-dispersible urethane resin has a glass transition temperature (Tg) of −80 to 0° C.; The hydroxyl value of the water-dispersible acrylic resin is 40 to 165 mg KOH / g; In the peelable adhesive layer, the ratio (NCO / OH) of the number of moles of isocyanate groups in the isocyanate to the number of moles of hydroxyl groups contained in the first agent is 0.5 to 2.0.

[0026] FIG. 1 is a schematic diagram showing an example of a peelable adhesive layer according to the present invention.

[0027] The peelable adhesive layer is a coating film of a paint for an adhesive layer, and is usually provided in contact with the exterior of an automobile. After use of the laminate of the present invention, the peelable adhesive layer is peeled off from the exterior of the automobile, thereby peeling the laminate of the present invention from the exterior of the automobile.

[0028] ·Adhesive layer paint The adhesive layer paint that forms the peelable adhesive layer is a two-part type consisting of a first agent and a second agent.

[0029] First agent The first agent contains a water-dispersible acrylic resin and a water-dispersible urethane resin.

[0030] The water-dispersed acrylic resin can be obtained, for example, by solution polymerization of a mixture of polymerizable unsaturated monomers. As the polymerizable unsaturated monomers, (meth)acrylic acid alkyl esters, carboxyl group-containing ethylenically unsaturated monomers, and hydroxyl group-containing ethylenically unsaturated monomers can be used.

[0031] Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate.

[0032] Examples of carboxyl group-containing ethylenically unsaturated monomers include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, maleic anhydride, and fumaric acid.

[0033] Examples of hydroxyl group-containing ethylenically unsaturated monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-methylol acrylamide, allyl alcohol, and ε-caprolactone-modified acrylic monomers.

[0034] The acrylic resin prepared by polymerization may be neutralized with, for example, a basic compound and used in the form of an aqueous solution.

[0035] Examples of basic compounds include organic amines such as monomethylamine, dimethylamine, trimethylamine, triethylamine, diisopropylamine, monoethanolamine, diethanolamine and dimethylethanolamine.

[0036] The water-dispersed acrylic resin has a hydroxyl value of 40 to 165 mg KOH / g. In one embodiment, the water-dispersed acrylic resin has a hydroxyl value (mg KOH / g) of 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 110 or more, 120 or more, 130 or more, 140 or more, 150 or more, or 160 or more. In another embodiment, the water-dispersed acrylic resin has a hydroxyl value (mg KOH / g) of 165 or less, 160 or less, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, or 50 or less. In yet another embodiment, the water-dispersed acrylic resin has a hydroxyl value (mg KOH / g) of 40 to 130.

[0037] The amount of the water-dispersed acrylic resin in the first agent may be appropriately adjusted. In one embodiment, the ratio of the mass of the water-dispersed acrylic resin to the total mass of the water-dispersed acrylic resin and the water-dispersed urethane resin is 10 to 90% by mass. In another embodiment, the ratio of the mass of the water-dispersed acrylic resin to the total mass of the water-dispersed acrylic resin and the water-dispersed urethane resin is 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, or 80% by mass or more. In yet another embodiment, the ratio of the mass of the water-dispersed acrylic resin to the total mass of the water-dispersed acrylic resin and the water-dispersed urethane resin is 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less.

[0038] As the water-dispersed acrylic resin, a commercially available product may be used.

[0039] The water-dispersible urethane resin is preferably a reaction product of a polyol and a polyisocyanate, and may be a reaction product obtained by further reacting a chain extender or a terminal terminator with the reaction product of a polyol and a polyisocyanate.

[0040] Examples of the polyol include polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, and polythioether polyol.

[0041] Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0042] Examples of the polyester polyol include a reaction product of a polycarboxylic acid with a polyester raw material polyol, a ring-opening polymer of ε-caprolactone, and copolymers thereof. Examples of the polycarboxylic acid include adipic acid, sebacic acid, itaconic acid, maleic anhydride, phthalic acid, isophthalic acid, and the like, and examples of the polyester raw material polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tripropylene glycol, butylene glycol, neopentyl glycol, and the like.

[0043] Polycarbonate diol can be prepared, for example, by reacting a polyhydric alcohol (eg, a diol) with dimethyl carbonate.

[0044] Examples of polyhydric alcohols include diols, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, and 1,6-hexanediol.

[0045] Examples of polyisocyanates include ethylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, p-xylylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, and 1,5-naphthylene diisocyanate.

[0046] Examples of chain extenders include ethylene glycol, propylene glycol, 1,4-butanediol, pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, glycerin, and trimethylolpropane.

[0047] Examples of the terminal terminator include monoalcohols such as methanol, butanol, octanol, and alkyl alcohol alkylene oxide adducts; and monoamines such as butylamine and dibutylamine.

[0048] The Tg of the water-dispersed urethane resin is −80 to 0° C. In one embodiment, the Tg of the water-dispersed urethane resin is −80° C. or higher, −70° C. or higher, −60° C. or higher, −50° C. or higher, −40° C. or higher, −30° C. or higher, −20° C. or higher, or −10° C. or higher. In another embodiment, the Tg of the water-dispersed urethane resin is 0° C. or lower, −10° C. or lower, −20° C. or lower, −30° C. or lower, −40° C. or lower, −50° C. or lower, −60° C. or lower, or −70° C. or lower.

[0049] As the water-dispersed urethane resin, a commercially available product may be used.

[0050] The first agent may contain other resins in addition to the water-dispersed acrylic resin and the water-dispersed urethane resin. For example, polyester resin, polyolefin resin, alkyd resin, epoxy resin, SBR, and NBR may be mentioned. In addition, as other components, it may contain pigments, dispersants, defoamers, UV absorbers, hindered amine light stabilizers, antioxidants, viscosity adjusters, surface adjusters, film-forming assistants, rust inhibitors, thickeners, organic solvents, and curing catalysts.

[0051] The laminate according to the present invention is for example used for a one-component coating film containing a polymerizable unsaturated monomer having an acid anhydride group, or for a two-component coating film containing a urethane resin.

[0052] Examples of polymerizable unsaturated monomers having an acid anhydride group include maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, phthalic anhydride, oxydiphthalic anhydride, naphthalenedicarboxylic anhydride, trimellitic anhydride, and pyromellitic anhydride.

[0053] Second agent The second agent contains an isocyanate. Examples of the isocyanate include aliphatic isocyanates, alicyclic isocyanates, alicyclic isocyanates, aromatic isocyanates, and biuret and nurate derivatives thereof.

[0054] Examples of the aliphatic isocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), and trimethylhexamethylene diisocyanate.

[0055] Examples of the aliphatic cyclic isocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, and 1,2-cyclohexane diisocyanate.

[0056] Examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI) and norbornane diisocyanate methyl.

[0057] Examples of aromatic isocyanates include xylylene diisocyanate (XDI), 2,4-tolylene diisocyanate (TDI), and 2,6-tolylene diisocyanate.

[0058] The ratio (NCO / OH) of the number of moles of isocyanate groups in the isocyanate to the number of moles of hydroxyl groups in the first agent (for example, hydroxyl groups in the water-dispersed acrylic resin) is 0.5 to 2.0. In one embodiment, the ratio (NCO / OH) is 0.5 or more, 0.6 or more, 0.8 or more, 1.0 or more, 1.2 or more, 1.4 or more, 1.6 or more, or 1.8 or more. In another embodiment, the ratio (NCO / OH) is 2.0 or less, 1.8 or less, 1.6 or less, 1.4 or less, 1.2 or less, 1.0 or less, 0.8 or less, or 0.6 or less.

[0059] The thickness of the peelable adhesive layer may be appropriately adjusted, and is, for example, 20 to 100 μm.

[0060] Method for preparing coating material for peelable adhesive layer For example, a water-dispersible acrylic resin and a water-dispersible urethane resin are mixed to prepare a first agent. A second agent containing a polyisocyanate is prepared separately. An organic solvent having no hydroxyl group may be mixed into the second agent. The obtained first agent and second agent are mixed to prepare a coating material for a peelable adhesive layer. Usually, the first agent and the second agent are mixed immediately before the coating material for a peelable adhesive layer is applied.

[0061] Formation of peelable adhesive layer The method for forming the peelable adhesive layer is not particularly limited. For example, a paint for a peelable adhesive layer is applied onto an article to be coated, and the coating film is cured to form the peelable adhesive layer.

[0062] The amount of coating material for the peelable adhesive layer to be applied is not particularly limited and may be appropriately set depending on the performance required for the coating film. For example, the coating is applied so that the thickness of the dried coating film is 20 to 100 μm.

[0063] The coating method of the peelable adhesive layer paint is not particularly limited, and examples thereof include air spray coating, airless spray coating, rotary atomization coating, curtain coat coating, etc. These methods may be combined with electrostatic coating. Coating may be performed multiple times.

[0064] After applying the coating material for the peelable adhesive layer, the coating film is cured. The curing conditions can be appropriately set according to the amount applied and the composition, for example, at 60° C. for about 20 minutes.

[0065] (Laminate) The laminate according to the present invention is formed by sequentially adjacently The peelable adhesive layer, and a clear layer or a design layer.

[0066] Fig. 2 is a schematic diagram showing an example of the layer structure of the laminate according to the present invention. The laminate 10 in Fig. 2 is composed of a peelable adhesive layer 1 and a clear layer 2, in that order.

[0067] Fig. 3 is a schematic diagram showing another example of the layer structure of the laminate according to the present invention. The laminate 10 in Fig. 2 is composed of a peelable adhesive layer 1 and a design layer 3 in this order.

[0068] Fig. 4 is a schematic diagram showing another example of the layer structure of the laminate according to the present invention. The laminate 10 in Fig. 2 is composed of a peelable adhesive layer 1, a design layer 3, and a clear layer 2, in that order.

[0069] Clear layer The clear layer is a coating of a coating composition for a clear layer, and serves to protect the layers located on the vehicle body side of the laminate, such as the peelable adhesive layer and any design layer. The clear layer is usually provided as the outermost layer of the laminate.

[0070] The clear layer coating composition can be a known clear coating composition. The clear layer coating composition can be, for example, a clear coating composition described in International Publication No. 2020 / 241342 and Japanese Patent No. 7052119. In addition, automotive repair paints described in JP-A-2022-180115 can also be used.

[0071] The coating composition for the clear layer may be either water-based or solvent-based.

[0072] The thickness of the clear layer may be appropriately adjusted, and is, for example, 20 to 100 μm.

[0073] Design layer The decorative layer is a coating of a coating composition for a decorative layer, and is a layer that imparts decorativeness to the laminate. As the decorative layer, a base layer of a conventionally known topcoat coating for automobiles, or the like can be used.

[0074] As the coating composition for the decorative layer, for example, the coating composition for the decorative layer described in Japanese Patent No. 7052119 can be used. In addition, a coating composition for an automobile repair can also be used.

[0075] The coating composition for the decorative layer may be either water-based or solvent-based.

[0076] The thickness of the design layer may be appropriately adjusted, and is, for example, 10 to 100 μm.

[0077] One embodiment of the laminate according to the present invention includes a peelable adhesive layer, a design layer, and a clear layer, which are adjacent to each other in this order.

[0078] Other layers The laminate may have other layers in addition to the peelable adhesive layer and the clear layer or the design layer.

[0079] In one embodiment of the laminate according to the present invention, the peel strength is 3 N or more. In another embodiment, the peel strength of the laminate is 3-10.

[0080] In one embodiment of the laminate according to the present invention, the peel strength after 80° C. / 100 h is 10 N or less. In another embodiment, the peel strength of the laminate after 80° C. / 100 h is 3 to 10 N.

[0081] In one embodiment of the laminate according to the present invention, the peel strength after an Xe test of 750 MJ is 10 N or less. In another embodiment, the peel strength of the laminate after an Xe test of 750 MJ is 3 to 10 N.

[0082] ·Laminate manufacturing method The laminate is produced, for example, by a method comprising a step (I) of applying a coating material for an adhesive layer to an article to be coated to form a peelable adhesive layer, and a step (II) of applying a coating composition for a decorative layer or a coating composition for a clear layer onto the peelable adhesive layer to form a decorative layer or a clear layer.

[0083] In addition, in the case of the laminate in Figure 4, for example, it is manufactured by a method including a step (I) of applying a paint for an adhesive layer to an article to be coated to form a peelable adhesive layer, a step (II) of applying a paint composition for a design layer onto the peelable adhesive layer to form a design layer, and a step (III) of applying a paint composition for a clear layer onto the design layer to form a clear layer.

[0084] (subject to be coated) The substrate may be flat or three-dimensional. The material of the substrate is not particularly limited. For example, resin or steel plate can be used as the substrate.

[0085] Examples of resins include polyethylene resin, EVA resin, polyolefin resin (polyethylene resin, polypropylene resin, etc.), vinyl chloride resin, styrene resin, polyester resin (including PET resin, PBT resin, etc.), polycarbonate resin, acrylic resin, acrylonitrile butadiene styrene (ABS) resin, acrylonitrile styrene (AS) resin, polyamide resin, acetal resin, phenolic resin, fluororesin, melamine resin, urethane resin, epoxy resin, polyphenylene oxide (PPO), etc.

[0086] Examples of the steel plate include metals such as iron, steel, stainless steel, aluminum, copper, zinc, and tin, and alloys thereof. The steel plate may be subjected to a chemical conversion treatment as necessary, and may further have an electrodeposition coating formed thereon. Examples of the chemical conversion treatment include zinc phosphate chemical conversion treatment, zirconium chemical conversion treatment, and chromium oxide chemical conversion treatment. The electrodeposition coating is formed by electrodeposition coating using, for example, a cationic electrodeposition coating composition or an anionic electrodeposition coating composition.

[0087] Examples of substrates include bodies of automobiles, trucks, motorcycles, buses, etc.; and bodies having an automobile exterior clear coating.

[0088] Examples of clear coatings for automobile exteriors include one-component curing coatings containing a polymerizable unsaturated monomer having an acid anhydride group, and two-component curing coatings containing a urethane resin.

[0089] Process (I) In step (I), a peelable adhesive layer is formed by applying a coating material for a peelable adhesive layer to an object to be coated. The preparation of the coating material for a peelable adhesive layer, application, and formation of the peelable adhesive layer are as described above.

[0090] Process (II) In step (II), a coating composition for a decorative layer or a coating composition for a clear layer is applied onto the peelable adhesive layer to form a decorative layer or a clear layer. The coating composition for a decorative layer may be applied multiple times.

[0091] (Method for preparing coating composition for decorative layer (Y)) The coating composition for the decorative layer may be a known base coating for automobile exteriors or a base coating for automobile repair, and may be either water-based or solvent-based. The coating composition for the decorative layer may be a curing type or a lacquer type. The coating composition for the decorative layer may further contain a pigment. Examples of the pigment include color pigments and luster pigments.

[0092] The coating method of the coating composition for the design layer is not particularly limited, and may be the same as that of the coating for the adhesive layer. The coating amount of the coating composition for the design layer is not particularly limited, and is, for example, an amount such that the dry film thickness of the design layer is 10 to 20 μm. The coating composition for the design layer may be applied multiple times. After the coating composition for the design layer is applied, the coating film is cured. The curing conditions may be appropriately set according to the coating amount and composition, and are, for example, about 20 minutes at 60 ° C.

[0093] The coating composition for the clear layer may be a known clear coating material for automobile exteriors or a clear coating material for automobile repair, and may be either water-based or solvent-based. The coating composition for the clear layer may also contain inorganic particles such as silica.

[0094] The coating method of the clear layer coating composition is not particularly limited, and may be the same as that of the peelable adhesive layer coating. The coating composition for the clear layer may be applied multiple times. The amount of the coating composition for the clear layer is not particularly limited, and may be appropriately set according to the performance required for the coating film, for example, the amount is such that the thickness of the clear coating film after curing is 40 to 60 μm. After the clear layer coating composition is applied, the coating is cured under appropriate curing conditions, for example, at 70° C. for 20 minutes.

[0095] ·Applications of laminates The use of the laminate is not limited and may be appropriately selected. For example, it may be used as a laminate for automobile exteriors for the purpose of changing the color or protecting the automobile exterior. EXAMPLES

[0096] The present invention will be described in more detail below with reference to examples, but these examples are intended to illustrate the present invention and are not intended to limit the present invention in any way. In the examples, "parts" refers to parts by mass.

[0097] Details of the materials used in the examples are as follows: Hardener nax E-CUBE WB Water-based Hardener (manufactured by Nippon Paint) ·Design layer paint Base agent: nax E-CUBE WB 412 Silent Black (manufactured by Nippon Paint) Auxiliary agent: nax E-CUBE WB 911 S-binder (manufactured by Nippon Paint Co., Ltd.) Diluent: nax E-CUBE WB R20 standard diluent (manufactured by Nippon Paint) Clear layer paint Base agent: nax E-CUBE WB (2:1) NN Clear (manufactured by Nippon Paint Co., Ltd.) Hardener: nax E-CUBE WB Water-based Hardener (manufactured by Nippon Paint)

[0098] ·Object to be coated 1 One-component curing clear coating composition: MAC O-1860 Clear (manufactured by Nippon Paint Automotive Coatings)

[0099] (Preparation of object 1) An electrodeposition coating composition (Powernics 150, Nippon Paint Automotive Coatings Co., Ltd. Cation) was electrocoated on a zinc phosphate-treated dull steel plate so that the dry coating thickness was 20 μm, and the plate was heated and cured at 160 ° C for 30 minutes, and then cooled to prepare a steel plate substrate. An aqueous intermediate coating composition (AR-630-X 8110, Nippon Paint Automotive Coatings Co., Ltd.) was applied to the obtained substrate with an air spray gun so that the dry film thickness was 25 μm, and the substrate was preheated in an oven set at 80 ° C for 3 minutes. Next, an aqueous base coating composition (AR-3020-1 202, Nippon Paint Automotive Coatings Co., Ltd.) was applied to the substrate with an intermediate coating layer with an air spray gun so that the dry film thickness was 15 μm, and the substrate was preheated in an oven set at 80 ° C for 3 minutes. Furthermore, a clear coating composition (MAC O-1860 Clear, manufactured by Nippon Paint Automotive Coatings) was applied to the substrate having the intermediate coating layer and the base layer so that the dry film thickness was 35 μm. The substrate was then heated in an oven set at 140° C. for 30 minutes to obtain a substrate 1 having a multi-layer coating film.

[0100] ·Object 2 Two-component curing clear paint composition: Polyurexcel O-2100 Clear (manufactured by Nippon Paint Automotive Coatings)

[0101] (Preparation of clear coating composition) As the base material, a mixture of 100 parts of Polyurexcel O-2100 Clear (manufactured by Nippon Paint Automotive Coatings Co., Ltd.) and 9.7 parts of TMK Thinner (diluent, manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was prepared. As the hardener, 38.3 parts of H-2100 (hardener, manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was prepared and mixed with the mixture of 100 parts of the base material and 9.7 parts of the diluent just before painting to prepare a coating composition for the clear layer.

[0102] (Preparation of object 2) A steel plate with an electrodeposition coating was prepared in the same manner as for the coated object 1. Next, a solvent-based intermediate coating composition (OP-30-P DG 8110, manufactured by Nippon Paint Automotive Coatings) was applied by an air spray gun so that the dry film thickness was 35 μm, and the substrate was heated in an oven set at 140 ° C for 30 minutes. Next, a water-based base coating composition (AR-3020-1 202, manufactured by Nippon Paint Automotive Coatings) was applied by an air spray gun to the substrate with an intermediate coating layer so that the dry film thickness was 15 μm, and the substrate was preheated in an oven set at 80 ° C for 3 minutes. Furthermore, a clear coating composition (Polyurethane Excel O-2100 Clear, manufactured by Nippon Paint Automotive Coatings) was applied to the substrate with an intermediate coating layer and a base layer so that the dry film thickness was 30 μm. Next, the substrate was heated in an oven set at 140 ° C for 30 minutes to obtain a coated object 2 with a multi-layer coating film.

[0103] ·Object to be coated 3 Two-component curing clear paint composition: R-2550-2 (manufactured by Nippon Paint Automotive Coatings)

[0104] (Preparation of clear coating composition) A mixture of 100 parts of R-2550-2 (manufactured by Nippon Paint Co., Ltd.) and 30 parts of T-5025 (diluting agent, manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was prepared as the base resin. 43.4 parts of H-2550 (hardening agent, manufactured by Nippon Paint Automotive Coatings Co., Ltd.) was prepared as the hardening agent, and mixed with the mixture of 100 parts of the base resin and 30 parts of the diluting agent just before painting to prepare the paint for the clear layer.

[0105] (Preparation of object 3) A water-based primer coating composition (WB-1200CD-5, Nippon Paint Automotive Coatings) was applied to the polypropylene material with an air spray gun so that the dry film thickness was 8 μm, and the coating was preheated in an oven set at 80 ° C for 3 minutes. Next, a water-based base coating composition (AR-3020-1 202, Nippon Paint Automotive Coatings) was applied to the substrate with a primer layer with an air spray gun so that the dry film thickness was 15 μm, and the coating was preheated in an oven set at 80 ° C for 3 minutes. Furthermore, a clear coating composition (R-2550-2, Nippon Paint Automotive Coatings) was applied to the substrate with a primer layer and a base layer so that the dry film thickness was 30 μm. Next, the substrate was heated in an oven set at 120 ° C for 35 minutes to obtain a substrate 3 with a multi-layer coating film.

[0106] ·Object to be coated 4 Two-component curing clear paint composition: R-2500-1 (manufactured by Nippon Paint Automotive Coatings)

[0107] (Preparation of clear coating composition) A mixture of 100 parts of R-2550-1 (base agent, Nippon Paint Automotive Coatings) and 30 parts of T-505HCL (dilutant, Nippon Paint Automotive Coatings) was prepared. 44 parts of H-2500 (hardener, Nippon Paint Automotive Coatings) was prepared as a hardener, and mixed with the mixture of 100 parts of base agent and 30 parts of dilutant just before painting to prepare a paint for the clear layer.

[0108] A water-based primer coating composition (WB-1200CD-5, Nippon Paint Automotive Coatings) was applied to the polypropylene material with an air spray gun so that the dry film thickness was 8 μm, and the coating was preheated in an oven set at 80 ° C for 3 minutes. Next, a water-based base coating composition (AR-3020-1 202, Nippon Paint Automotive Coatings) was applied to the substrate with a primer layer with an air spray gun so that the dry film thickness was 15 μm, and the coating was preheated in an oven set at 80 ° C for 3 minutes. Furthermore, a clear coating composition (R-2500-1, Nippon Paint Automotive Coatings) was applied to the substrate with a primer layer and a base layer so that the dry film thickness was 30 μm. Next, the substrate was heated in an oven set at 120 ° C for 35 minutes to obtain a substrate 4 with a multi-layer coating film.

[0109] (Examples 1 to 4) A peelable adhesive layer coating material, decorative layer coating composition 1, and clear layer coating composition 1 were prepared as described below, and laminates were produced.

[0110] Preparation of peelable adhesive layer coatings The following materials were charged in order into a container equipped with a stirrer to obtain a first part of the coating material for the adhesive layer. Urethane resin 67 parts (solids) Acrylic resin 33 parts (solids) Nopal 3303 (urethane associative thickener, manufactured by San Nopco) 2.0 parts BYK-345 (surface conditioner, manufactured by BYK) 0.6 parts Ion-exchanged water 57.8 parts

[0111] As the second agent, nax E-CUBE WB water-based hardener (manufactured by Nippon Paint Co., Ltd.) was used. The obtained first agent and second agent were mixed immediately before painting to prepare a paint for the adhesive layer.

[0112] Coating composition for decorative layer A lacquer-type decorative layer coating composition 1 was prepared by mixing 100 parts of nax E-CUBE WB 412 Silent Black (main agent, manufactured by Nippon Paint Co., Ltd.), 50 parts of nax E-CUBE WB 911 S-binder (auxiliary agent, manufactured by Nippon Paint Co., Ltd.), and 45 parts of nax E-CUBE WB R20 standard diluent (diluent, manufactured by Nippon Paint Co., Ltd.).

[0113] Clear layer coating composition A mixture of 100 parts of nax E-CUBE WB (2:1) NN Clear (manufactured by Nippon Paint Co., Ltd.) and 30 parts of pure water was prepared as the base material. 50 parts of nax E-CUBE WB water-based hardener (hardener, manufactured by Nippon Paint Co., Ltd.) was prepared as the hardener, and mixed with a mixture of 100 parts of the base material and 30 parts of pure water just before painting to prepare clear layer coating composition 1.

[0114] (Preparation of Laminate) Preparation of peelable adhesive layer The paint for the adhesive layer was applied to the object 1 with an air spray gun. Then, the object was heated in an oven set at 60° C. for 20 minutes to prepare a peelable adhesive layer.

[0115] Creating the design layer The decorative layer coating composition 1 was applied to a substrate having a peelable adhesive layer using an air spray gun, and the substrate was dried with an air blower until the coating no longer adhered to the substrate when touched with a finger. This coating and drying process was repeated two more times to form a decorative layer.

[0116] Preparation of clear layer A coating composition 1 for clear layer was applied to a substrate having a peelable adhesive layer and a design layer by an air spray gun. After that, the substrate was left to stand for 30 minutes, and then heated in an oven set at 70°C for 20 minutes to form a clear layer.

[0117] (Examples 5 to 7) A laminate was produced in the same manner as in Example 1, except that the substrate was changed as shown in Table 1.

[0118] (Examples 8 and 9, Comparative Examples 1 to 3) A laminate was produced in the same manner as in Example 1, except that the coating composition for the adhesive layer and the film thickness of the peelable adhesive layer were changed as shown in Table 2.

[0119] Example 10 A laminate was prepared in the same manner as in Example 1, except that the adhesive layer coating composition, the film thickness of the peelable adhesive layer, and the substrate were changed as shown in Table 2.

[0120] (Examples 11 to 13) A laminate was produced in the same manner as in Example 1, except that the coating composition for the adhesive layer and the film thickness of the peelable adhesive layer were changed as shown in Table 3.

[0121] (Examples 14 to 18, Comparative Example 4) A laminate was produced in the same manner as in Example 1, except that the coating composition for the adhesive layer and the film thickness of the peelable adhesive layer were changed as shown in Table 4.

[0122] (Examples 19 to 22, Comparative Examples 5 and 6) A laminate was produced in the same manner as in Example 1, except that the coating composition for the adhesive layer and the film thickness of the peelable adhesive layer were changed as shown in Table 5.

[0123] (Example 23) A laminate was produced in the same manner as in Example 1, except that the paint for the peelable adhesive layer was dried at room temperature until it was dry to the touch, and the film thickness of the peelable adhesive layer was changed.

[0124] Example 24 A laminate was prepared in the same manner as in Example 1, except that the decorative layer coating composition and the clear layer coating composition were changed to the following decorative layer coating composition 2 and clear layer coating composition 2, and the film thickness of the peelable adhesive layer was changed. Preparation of coating composition 2 for decorative layer Decorative layer coating composition 2 was prepared by mixing 100 parts of nax Real 611 Chinching Black NP (main agent, manufactured by Nippon Paint Co., Ltd.) and 33 parts of nax StabiR NEO #20 (diluting agent, manufactured by Nippon Paint Co., Ltd.). Preparation of clear layer coating composition 2 A mixture of 100 parts of nax Multi Eco (3:1) 20LX Clear (main agent, manufactured by Nippon Paint Co., Ltd.), 20 parts of nax Multi #20 Standard Urethane Thinner NEO (diluent, manufactured by Nippon Paint Co., Ltd.), and 33 parts of nax Ultra #20 Hardener (hardener, manufactured by Nippon Paint Co., Ltd.) was mixed immediately before painting to prepare paint composition 2 for the clear layer.

[0125] (Example 25) A laminate was prepared in the same manner as in Example 1, except that the coating composition for the design layer was not used, the coating composition for the clear layer was changed to the following coating composition for the clear layer 3, and the film thickness of the peelable adhesive layer was changed. Preparation of clear layer coating composition 3 A mixture of 100 parts of nax Multi Eco (3:1) Matte Clear (main agent, manufactured by Nippon Paint Co., Ltd.), 50 parts of nax Multi #20 Standard Urethane Thinner NEO (diluent, manufactured by Nippon Paint Co., Ltd.), and 33 parts of nax Ultra #20 Hardener (hardener, manufactured by Nippon Paint Co., Ltd.) was mixed immediately before painting to prepare clear layer coating composition 3.

[0126] (Comparative Examples 7 to 18) A laminate was produced in the same manner as in Example 1, except that the coating material for the adhesive layer was prepared as follows. Preparation of comparative adhesive layer paint The following materials were charged in this order into a container equipped with a stirrer to prepare a comparative adhesive layer coating material. Base resin dispersion (Table 7) 100 parts BYK-345 (surface conditioner, manufactured by BYK) 0.2 parts

[0127] (peel strength measurement) Using a tensile tester (Shimadzu Corporation Autograph AGX-V) equipped with a thermostatic chamber at 20°C, peel strength measurements were carried out between the peelable adhesive layer and the coated object under the following conditions: peel angle 180°, peel speed 300mm / min, sample width 10mm. The peel strength was measured on three samples, the average value was calculated, and the adhesion was evaluated according to the following criteria. Adhesion pass: peel strength is 3N / cm~10N / cm Adhesion failure: Peel strength is less than 3N / cm or greater than 10N / cm

[0128] (Heat resistance test) The produced laminate was heated for 100 hours in an oven at 80° C. After being taken out, it was left to stand at room temperature for more than half a day, and then the peel strength was measured.

[0129] (Xe test) According to the xenon lamp method of JIS K5600-7-7, the laminate was attached to a Super Xenon Weather Meter SX-75 (manufactured by Suga Test Instruments Co., Ltd.) and the illuminance was 100 W / m 2 Accelerated exposure was carried out for 2100 hours at 40°C for 2100 hours.

[0130] [Table 1]

[0131] [Table 2]

[0132] [Table 3]

[0133] [Table 4]

[0134] [Table 5]

[0135] [Table 6]

[0136] [Table 7]

[0137] According to the present invention, it is possible to provide a peelable adhesive layer having good adhesion so that it does not peel off during normal use and good releasability so that it can be peeled off when desired. Also, according to the present invention, it is possible to provide a laminate having good adhesion so that it does not peel off during normal use and good releasability so that it can be peeled off when desired. [Industrial Applicability]

[0138] According to the present invention, it is possible to provide a peelable adhesive layer having good adhesion so that it does not peel off during normal use and good releasability so that it can be peeled off when desired. Also, according to the present invention, it is possible to provide a laminate having good adhesion so that it does not peel off during normal use and good releasability so that it can be peeled off when desired. [Explanation of symbols]

[0139] 1: Peelable adhesive layer 2: Clear layer 3: Design layer 10: Laminate

Claims

1. A peelable adhesive layer, The peelable adhesive layer is a coating film of a paint for an adhesive layer, the adhesive layer coating material is a two-component type coating material consisting of a first agent containing a water-dispersible acrylic resin and a water-dispersible urethane resin, and a second agent containing an isocyanate; The water-dispersible urethane resin has a glass transition temperature (Tg) of −80 to 0° C., The hydroxyl value of the water-dispersed acrylic resin is 40 to 165 mg KOH / g; A peelable adhesive layer, wherein the ratio (NCO / OH) of the number of moles of isocyanate groups contained in the isocyanate to the number of moles of hydroxyl groups contained in the first agent is 0.5 to 2.

0.

2. Adjacent in order, The peelable adhesive layer according to claim 1 , A laminate comprising: a clear layer or a design layer.

3. 3. The laminate according to claim 2, wherein a ratio of the mass of the water-dispersed acrylic resin to a total mass of the water-dispersed acrylic resin and the water-dispersed urethane resin is 10 to 90 mass %.

4. 3. The laminate according to claim 2, which is for use in a one-component coating film containing a polymerizable unsaturated monomer having an acid anhydride group, or for use in a two-component coating film containing a urethane resin.

5. The laminate according to claim 4, having a peel strength of 3N or more.

6. The laminate according to claim 4, having a peel strength of 10 N or less after 80° C. / 100 h.

7. The laminate according to claim 4, which has a peel strength of 10 N or less after a Xe test of 750 MJ.

8. Adjacent in order, The peelable adhesive layer; A design layer; The laminate according to claim 2 , further comprising the clear layer.

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