WO2022224710A1 - クリヤー層を有する積層体の製造方法、これにより得られる積層体、複合塗膜の製造方法、これにより得られる複合塗膜、これを用いた成形体の製造方法並びに成形体、および上記積層体から得られるクリヤー層 - Google Patents

クリヤー層を有する積層体の製造方法、これにより得られる積層体、複合塗膜の製造方法、これにより得られる複合塗膜、これを用いた成形体の製造方法並びに成形体、および上記積層体から得られるクリヤー層 Download PDF

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Publication number
WO2022224710A1
WO2022224710A1 PCT/JP2022/014643 JP2022014643W WO2022224710A1 WO 2022224710 A1 WO2022224710 A1 WO 2022224710A1 JP 2022014643 W JP2022014643 W JP 2022014643W WO 2022224710 A1 WO2022224710 A1 WO 2022224710A1
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WIPO (PCT)
Prior art keywords
clear
solvent
manufacturing
composition
layer
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Ceased
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PCT/JP2022/014643
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English (en)
French (fr)
Japanese (ja)
Inventor
正 香川
剛 入江
貢一 芦塚
功一 湯浅
拓也 清水
輝 日下部
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BASF Japan Ltd
Aisin Corp
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BASF Japan Ltd
Aisin Corp
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Application filed by BASF Japan Ltd, Aisin Corp filed Critical BASF Japan Ltd
Priority to JP2023516371A priority Critical patent/JP7567046B2/ja
Publication of WO2022224710A1 publication Critical patent/WO2022224710A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations

Definitions

  • the present invention provides a method for producing a laminate having a clear layer, a laminate obtained thereby, a method for producing a composite coating film, a composite coating film obtained thereby, a method for producing an insert molded article using the same, a molded article, and a clear layer obtained from the laminate.
  • Metal substrates that make up the body of an automobile generally consist of a base layer for rust prevention and ensuring adhesion to the upper layer, an intermediate and top coating layer for reinforcement and coloring, and a coating layer for protecting and decorating the surface of the coating film. It is covered with a coating film having a laminate structure consisting of a clear layer for the purpose.
  • Each layer of such a laminate can be manufactured by conventional coating techniques such as spray coating with a fluid paint.
  • An example of this is a decorative film applied over an existing coating film.
  • the material used in the method of forming a coating film into a film by extrusion molding or the like and applying it to an object to be coated, the material used must be suitable for extrusion molding, but considering the heating conditions for extrusion molding, etc., it can be applied to film formation. There are restrictions on the types of resins and the like.
  • the decorative film or clear layer obtained by such a method exhibits weather resistance, chemical resistance, and scratch resistance (for example, car wash scratch resistance) when exposed to wind, rain, and high temperatures. Physical property requirements must be met. A film that satisfies all of the above physical properties has not yet been reported, while the materials that satisfy the conditions required in the molding stage are limited.
  • the present invention is a lamination that can provide a clear layer of constant quality, which can suppress the burden on the environment and is simple, in place of the coating film production obtained by conventional painting (coating).
  • An object of the present invention is to provide a method for manufacturing a body and a laminate obtained by this method.
  • the present invention provides a method for producing a composite coating film from the above laminate, a composite coating film obtained thereby, a method for producing a molded article using the composite coating film, a molded article, and a clear obtained from the above laminate. Its purpose is to provide layers.
  • the inventors of the present invention have found that the above problem is Applying a solvent-based clear coating composition onto the base material, Disposing a cover material on the solvent-based clear coating composition while the solvent-based clear coating composition is in an uncured state, The uncured laminate composed of the base material, the solvent-based clear coating composition, and the cover material thus obtained is subjected to aging treatment to cure the uncured solvent-based clear coating composition, Including each step of forming a cured laminate containing a cured clear layer, We have found that this is achieved by a method for producing a laminate, characterized in that the cover material is a material capable of capturing, passing, or capturing and passing the solvent in the solvent-based clear coating composition.
  • the cover material is composed of a resin having a density of 0.09 to 1.4 g/cm 3 , a water absorption rate of 0.3 to 7.0%, a surface roughness Ra of 1 ⁇ m or less, and a pencil hardness of 6B to 4H. preferably.
  • the solvent-based primer coating composition is applied in advance on the base material, Applying a solvent-based clear coating composition onto the solvent-based primer coating composition, Disposing a cover material on the solvent-based clear coating composition while the solvent-based clear coating composition is in an uncured state, An uncured laminate composed of the base material thus obtained, the solvent-type primer coating composition, the solvent-type clear coating composition, and the cover material can be subjected to aging treatment.
  • the above manufacturing method may further include a step of subjecting the uncured laminate to winding treatment to form a wound body, and subjecting the wound body to aging treatment.
  • the cover material can be cellulose, acetylated cellulose, (meth)acrylic resin, polyamide, porous polypropylene and polyethylene, or polyolefin nonwoven fabric.
  • the solvent-based clear coating composition may be a composition containing one or more hydroxyl group-containing (meth)acrylic resins and an isocyanate cross-linking agent, or a composition containing a urethane polymer solution. It may contain stabilizers.
  • Polypropylene compositions containing polypropylene selected from homopolymers, random copolymers or block copolymers of polypropylene or cured products of compositions containing acrylonitrile, butadiene and styrene copolymers can be used, and this polypropylene composition and acrylonitrile Any composition containing a -butadiene-styrene copolymer preferably contains a hindered amine weather stabilizer.
  • a cured product of a composition containing a propylene homopolymer, random copolymer or block copolymer, or acrylonitrile-butadiene-styrene copolymer can be used as the base material, and this hindered amine weather stabilizer can be used. is preferably included.
  • the base material is composed of a resin having a density of 0.09 to 1.4 g/cm 3 , a water absorption rate of 0.3 to 7.0%, a surface roughness Ra of 1 ⁇ m or less, and a pencil hardness of 6B to 4H. good.
  • the base material can be cellulose, acetylated cellulose, (meth)acrylic, polyamide, porous polypropylene and polyethylene, or polyolefin nonwovens.
  • the object of the present invention is achieved by a laminate including a base material, a cured clear layer, and a cover material obtained by any of the above manufacturing methods.
  • Another object of the present invention is to manufacture a composite coating film comprising a base material and a cured clear layer by removing the cover material from the laminate. It is achieved by the method of manufacturing the membrane.
  • the object of the present invention is achieved by the composite coating film obtained by the above manufacturing method.
  • the above object of the present invention is achieved by a method for producing a molded article, which comprises applying the composite coating described above to a substrate to produce a molded article having a clear layer,
  • the molded article is molded by insert-molding the composite coating film onto the substrate, and can have a clear layer as the outermost layer coating.
  • the above substrates are automobiles, motorcycles, bicycles, road materials, ships, railway vehicles, aircraft, buildings, building materials, furniture, home appliances, containers, musical instruments, office supplies, sporting goods, toys, parts thereof, or You can choose from parts.
  • the above object of the present invention is also achieved by a molded article obtained by the above manufacturing method.
  • the object of the present invention is also achieved by a laminate including a base material, a cured clear layer, and a cover material obtained by the above manufacturing method.
  • the object of the present invention is also achieved by a clear layer obtained by removing the base material and the cover material from the above laminate.
  • the solvent in the solvent-based clear coating composition can be removed satisfactorily by directly applying a cover material having predetermined properties to the solvent-based clear coating composition. be done. That is, the covering material serves to trap, pass, or trap and pass the solvent.
  • the manufacturing method of the present invention greatly reduces the burden on the environment, compared to conventional coating (fluid coating) in which spray coating is performed directly on the object to be coated.
  • a method for producing a laminate including a clear layer of uniform quality that is, the quality does not vary depending on the type of clear coating composition
  • the production method of the present invention can provide a laminate comprising the clear layer described above, or such a clear layer, an optional primer layer, and a base layer. Further, the obtained laminate is peeled off from the cover material contained therein, and the clear layer is the outermost layer covering the substrate (covering target) such as an automobile body or a part (part) thereof. By attaching by insert molding or the like, a molded article such as an insert molded article coated with a clear layer having the properties described above can be obtained.
  • FIG. 1 is a diagram for explaining a method of manufacturing a laminate according to one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view for explaining a method of manufacturing a laminate and a molded article using the same according to one embodiment of the present invention.
  • a laminate containing a clear layer that can be used for surface coating of an object to be coated (also referred to as a substrate) is produced.
  • the substrate to which the laminate of the present invention is applied is not particularly limited, it is mainly applied to substrates made of synthetic resins, particularly thermoplastic resins.
  • a representative example of the substrate is synthetic resins in general, including resins that are lightweight yet have excellent strength that have been developed in recent years. Applicable materials include:
  • the base material (base film) of the present invention an optional primer layer (primer film), a clear layer (clear film), and a cover material (cover film) are applied to the object to be coated made of such a synthetic resin.
  • a composite coating film obtained by peeling off the cover material from the laminate obtained by laminating the above can be applied by composite molding such as insert molding.
  • the cover material is preferably maintained as part of the laminate for protection of the clear layer until applied to the object to be coated and is peeled off just prior to application to the object to be coated.
  • the composite coating film When applying the composite coating film to insert molding, (i) the composite coating film is introduced into the mold for insert molding so that the base film side is in contact with the object to be coated (solid work), or (ii) the composite The coating film is placed so that the clear layer side faces the inner surface of the mold, and the composite coating film is deformed into the shape of the mold by the pressure and heat of the melted resin by injection molding.
  • both the material of the base film and the surface of the work made of synthetic resin, which is the material to be coated are melted and fused and heat-sealed, thereby Integrate strongly.
  • the molten resin is fused and heat-sealed with the surface of the composite coating film that has been melt-deformed to be firmly integrated. Furthermore, when a colored base film or an ink layer additionally printed on the base film is used, the clear layer protects this, and a multi-functional layer consisting of multiple layers at once is coated. It will be layered on the object.
  • the order of lamination of the base material, the primer layer and the clear layer is as described. Between and between the primer layer and the clear layer, it is possible to provide further layers, for example printing layers. Similarly, the object to be coated can be subjected to the necessary pretreatment prior to application of the composite coating.
  • the laminate of the present invention comprises a step of applying a solvent-based clear coating composition (also referred to as a clear composition) onto a base member (clear composition applying step), A step of disposing a cover member on the solvent-based clear coating composition in an uncured state (cover member disposing step), and a base material obtained thereby, and a solvent-based A process of curing the solvent-based clear coating composition to form a clear layer by subjecting the laminate in which the solvent-based clear coating composition composed of the clear coating composition and the cover material is uncured to aging treatment (aging curing process).
  • a solvent-based clear coating composition also referred to as a clear composition
  • cover member disposing step A step of disposing a cover member on the solvent-based clear coating composition in an uncured state
  • base material obtained thereby and a solvent-based A process of curing the solvent-based clear coating composition to form a clear layer by subjecting the laminate in which the solvent-based clear coating composition composed of the clear coating composition and the cover material is uncured to aging treatment (aging
  • a step of applying a solvent-based primer coating composition onto the base material (a step of applying a primer composition) can be performed prior to the step of applying the clear composition.
  • a solvent-type primer coating composition (also referred to as a primer composition) is applied in a relatively thin film thickness (e.g., 5 ⁇ m), and after application, before application of the clear composition, it is heated to a high temperature (e.g., 140° C.). Curing can be performed only by the drying step of .
  • the clear composition can be applied after optionally pre-treating the cured primer layer.
  • the "solvent type" in the solvent-based primer coating composition and the solvent-based clear coating composition of the present invention means that each composition contains an organic solvent, which will be described later.
  • the above-described cover material placement step is performed, and a laminate composed of the obtained base material, an optionally provided primer layer, the solvent-based clear coating composition, and the cover material. is subjected to aging treatment and the solvent-based clear coating composition is cured to form a clear layer (aging curing step).
  • the solvent that should be removed from the clear composition before curing is removed satisfactorily by disposing the above-mentioned predetermined cover material directly on the uncured solvent-based clear coating composition.
  • Solvents to be removed are residual solvents used in the preparation of primer and clear compositions or organic solvents that may be added later, especially volatile organic solvents (VOCs).
  • volatile organic solvents (VOC) are about 200 types of compounds defined as "organic compounds that are gaseous when discharged or scattered into the atmosphere" in Article 2, Paragraph 4 of the Air Pollution Control Law. .
  • VOC volatile organic solvents
  • volatile organic solvents (VOC) contained in the clear composition such as cyclohexane, toluene, xylene, ethylbenzene, n-butyl acetate, isobutyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, acetic acid Ethyl, tetrahydrofuran, 1,4-dioxane, acetonitrile, N,N-dimethylformamide, etc., especially n-butyl acetate and xylene can be well captured in the cover material, or can be captured after passing through the cover material, Alternatively, it facilitates the production of desired laminates, coalescing layers and clear layers while minimizing the emission of organic solvents without using spraying means.
  • VOC volatile organic solvents
  • Primer composition application step In the present invention, first, a primer composition is applied to a base material.
  • a primer composition is a material that gives a predetermined adhesive strength to a coating film to form a primer layer. Any known material can be used as the primer composition, and there is no particular limitation, but acrylic, ethylene vinyl acetate, urethane, epoxy resins, modified polypropylene resins and mixtures thereof are used as the main component. .
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • a primer can be omitted.
  • a protective film and an undercoating film are required.
  • the thickness of the coating film of the primer composition is, for example, 1 to 100 ⁇ m, preferably 3 to 65 ⁇ m, particularly 3 to 10 ⁇ m.
  • the primer composition can be applied stably and uniformly, and when the thickness is 100 ⁇ m or less, the necessary flexibility can be ensured when the film is wound up.
  • the solid content (25°C) of the primer composition is generally 5-50% by mass, preferably 10-30% by mass, and the viscosity (25°C) is generally 10-50mPa. s, preferably 20-30 mPa.s. s.
  • the solid content and viscosity are adjusted appropriately according to the coating method of the primer composition.
  • the film thickness of the object becomes sufficient.
  • the primer composition is placed in a drying oven at 40 to 200° C., preferably 70 to 150° C. for 3 to 30 minutes until the solid content of the primer composition reaches about 100%, for example 30 minutes. It is preferably dried over It goes without saying that this step is omitted when producing laminates or composite coatings that do not contain a primer layer.
  • a clear composition is generally a material for forming a clear coat layer as the outermost layer of a coating, and can impart a sense of transparency to the coloring of a colored base material to impart a beautiful appearance. Further, the clear layer itself may also retain a transparent aesthetic and possess physical properties including weatherability, chemical resistance, and scratch resistance.
  • composition means an uncured composition
  • layer such as a primer layer and a clear (coat) layer means a cured layer
  • the thickness of the coating film of the clear composition is, for example, 10-150 ⁇ m, preferably 10-100 ⁇ m, particularly 20-50 ⁇ m. When the thickness is 10 ⁇ m or more, the clear composition can be applied stably and uniformly.
  • the solid content (25°C) of the clear composition is generally 20-90% by mass, preferably 30-60% by mass, and the viscosity (25°C) is generally 10-100 mPa.s. s, preferably from 20 to 70 mPa.s. s.
  • the solid content and viscosity are adjusted appropriately according to the coating method of the clear composition. By setting the solid content to 90% by mass or less and/or the viscosity to 100 mPa ⁇ s or less, the film thickness of the cured product becomes sufficient.
  • the clear composition is preferably dried at 50 to 200°C, preferably 50 to 150°C, until the solid content of the clear composition reaches 98%, preferably about 100%, for example, for 30 minutes. .
  • the application of the primer composition and the clear composition is preferably carried out by coating using a roll coater, flow coater, dipping type coating machine, or a brush, bar coater, applicator, or the like.
  • a roll coater is preferably used in consideration of continuous performance of the preceding and following treatment steps and accurate control of the coating amount. This is because, with this coating method, it is possible to apply a necessary and sufficient coating amount to the base material quickly and to have a constant film thickness.
  • a solid cover material such as a film is laminated on the uncured clear composition, that is, on the side of the clear composition opposite to the above base material (and primer layer). to obtain an uncured laminate.
  • the cover material is left still on the uncured clear composition so as to cover the entire surface without disturbing the surface.
  • a commonly used laminating device such as a laminator machine, can be applied.
  • An uncured laminate containing the base material of the present invention, an optionally provided cured primer layer, an uncured clear composition, and a cover material is obtained as described above.
  • the laminate thus obtained is heated at room temperature (25°C) or above and below the curing temperature of each composition, preferably 25 to 80°C, particularly preferably 40 to 70°C, particularly preferably 40 to 60°C.
  • An aging treatment usually from 1 to 7 days, cures the clear composition and uncured primer composition, if any, to give a cured laminate having a clear layer and optionally a primer layer, respectively. .
  • the organic solvent or gas contained in the clear composition captures, passes through, or captures and passes through the solvent in the solvent-based clear coating composition.
  • capturing means that the organic solvent and gas contained in the clear composition placed in contact with the cover material, and the liquid and gas generated by the reaction of the components in the clear composition are taken into the material and
  • Passing through includes penetrating or adsorbing into the tissue of the material, or adhering to the surface of the covering material or the walls of the pores in the case of porous materials, and "passing through” means that the organic solvent, liquid, or gas Regardless of presence or absence, it refers to passing through the inside of the covering material and bringing it to the outside of the surface of the covering material that does not come into contact with the clear composition/clear layer.
  • the clear composition exists between the base material and the cover material, and is sandwiched between them in a fixed state.
  • the solvent is caught (captured) by the covering and most of it ends up passing through the covering.
  • a highly volatile organic solvent passes through the cover material without necessarily being received by the cover material. This means that gases (such as air) present in the organic solvent or gases (such as CO2 ) and liquids generated during the curing reaction will also pass through the cover material during the aging process, and any bubbles created during this process will also be destroyed. foam.
  • the clear composition particularly the surface of the clear composition, is affected by the cover material provided thereon in direct contact.
  • the cover material has a density of 0.09 to 1.4 g/cm 3 , preferably 1.2 to 1.4 g/cm 3 , a water absorption rate of 0.3 to 7.0%, preferably 0.5 to 1.4 g/cm 3 . 6.5%, surface roughness Ra 1 ⁇ m or less, preferably 0.01 ⁇ m to 1 ⁇ m, more preferably 0.01 ⁇ m to 0.1 ⁇ m, surface pencil hardness 6B to 4H, preferably 2B to 4H, particularly preferably 2H to 4H. Having all the physical properties promotes volatilization of the solvent remaining in the uncured clear composition and improves the appearance and physical properties of the surface of the clear layer of the resulting laminate.
  • the smoothness of the cover material is transferred to the clear layer to form a clear layer that is smooth, highly smooth and, in some cases, excellent in gloss.
  • the clear composition is selected in consideration of the properties such as the physical properties required for the desired clear layer, and the range of each of the above properties of the cover material is selected according to the type of clear composition. As a result, the physical properties of the clear composition are maximized, and the smoothness of the surface of the cover material is transferred to the clear layer. For this transfer it is necessary to have suitable hardness for the clear composition. Examples of suitable combinations of the clear composition and the cover material will be described later.
  • the laminate containing the base material, clear layer, and cover material of the present invention can be applied to a composite coating film on an object to be coated in a state in which the cover material is peeled off from the laminate.
  • a predetermined peelability is also required.
  • the density was measured according to JIS K7112: 1999 Plastics - Non-foamed plastic density and specific gravity measurement methods.
  • the method for measuring the water absorption rate is according to JIS K7209:2000 - Determining the water absorption rate of plastics.
  • Sheet - Measured according to the method for determining water vapor permeability both water absorption and water vapor permeability when the cover material sample was brought into contact with the surface of the clear composition for 24 hours.
  • water absorption rate is defined as “water absorption rate”, but in the present invention, this is read as “organic solvent absorption rate”, and the value is obtained by the same test.
  • the surface roughness Ra was measured according to the arithmetic roughness Ra of JIS B 0601:1994, JIS B 0031:1994.
  • the surface pencil hardness was measured according to JIS K 5600-5-4 "General test methods for paints-Part 5: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method)”.
  • a cover material having a density of 1.2 to 1.4 g/cm 3 , a water absorption of 3.0 to 7.0%, a surface roughness Ra of 0.01 ⁇ m to 0.1 ⁇ m, and a surface pencil hardness of 2H to 4H consist of clear compositions containing aminoplast components such as poly(meth)acrylate and melamine as resin components, clear compositions containing poly(meth)acrylate and poly(block) isocyanate as resin components, and acrylic/urethane-based clear compositions. It is used for resins, etc. (for example, a clear layer containing urethane-modified (meth)acrylate as a main component is obtained).
  • a cover material having a density of 1.1 to 1.2 g/cm 3 , a water absorption of 0.3 to 0.5%, a surface roughness Ra of 0.1 ⁇ m to 1 ⁇ m, and a surface pencil hardness of 6B to 2H (example: acrylic film (Poly(meth)acrylate) is used for clear compositions and the like that contain (mere)acrylate as a resin component.
  • acrylic film (Poly(meth)acrylate) is used for clear compositions and the like that contain (mere)acrylate as a resin component.
  • Physical properties such as chemical resistance and scratch resistance are lower than those of acrylates, but according to the production method of the present invention, the layers obtained by conventional coating of unmodified (mere) acrylates are similar or better. It is effective because it has physical properties and provides a cured layer with improved surface smoothness and gloss, and is particularly useful in fields such as car interior materials, interior panels for buildings, and ornaments. be done.
  • Density 0.09-1.0 g/cm 3 , water absorption ⁇ 0.01%, surface roughness Ra 0.1-1 ⁇ m, surface pencil hardness 6B-H cover material (specific examples: porous polypropylene film and Porous polyethylene film, polyolefin non-woven fabric), depending on the case, can be treated with a clear composition containing poly(meth)acrylate and poly(block)isocyanate as a resin component, acrylic / It is used for a clear composition containing a resin component such as a clear layer containing a urethane-based resin, for example, a urethane-modified (meth)acrylate as a main component.
  • a resin component such as a clear layer containing a urethane-based resin, for example, a urethane-modified (meth)acrylate as a main component.
  • polyamide film is poly(meth)acrylate and a clear composition containing an aminoplast component such as melamine as a resin component. Due to the properties of the material, polyamide has low physical properties such as scratch resistance when compared to the modified (mere) acrylate in (1) above, but according to the production method of the present invention, conventional coating with polyamide Since a layer having physical properties similar to or higher than those of a coating film and improved surface smoothness and glossiness can be obtained, it is suitably used as a coating film for building material parts, home electric appliances, and the like.
  • cover material examples include cellulose, monoacetylcellulose, diacetylcellulose, acetyl(modified)cellulose such as triacetylcellulose (TAC), (meth)acrylic resin or polyamide, acrylic resin, cycloolefin, Porous polyester films, porous polyolefin films, and non-woven fabrics thereof can be mentioned. ) acrylic resin, porous polypropylene and polyethylene, or polyolefin non-woven fabric, particularly preferably acetylated cellulose and polyamide. These may be used singly or as a mixture of a plurality of types, and are selected according to the properties of the clear composition coated with the cover material.
  • TAC triacetylcellulose
  • acrylic resin porous polypropylene and polyethylene
  • polyolefin non-woven fabric particularly preferably acetylated cellulose and polyamide.
  • the uncured clear composition can be fixed by scissors between the cover material and the base material, allowing air and volatile substances such as organic solvents in the clear composition to pass through during aging, thereby transferring the smoothness of the cover material to the surface of the clear layer.
  • triacetyl cellulose alone is extremely preferable as a material suitable for being easily peeled off after curing of the clear layer.
  • the cover material does not contain additives.
  • the cover material contains additives
  • the organic solvent of the clear composition passes through and moves through the cover material while taking in the additives of the cover material.
  • Additives can bleed into the clear composition/clear layer and stain the clear layer surface.
  • the absence of additives in the cover material eliminates this possibility and ensures an excellent surface quality of the clear layer. Furthermore, the manufacturing cost and labor can be reduced.
  • cellulose, monoacetyl cellulose, diacetyl cellulose, acetyl (modified) cellulose such as triacetyl cellulose (TAC), and acrylic resin have excellent smoothness without using additives. can be formed.
  • the cover material is generally produced as a film and has a film thickness in the range of 10-100 ⁇ m, preferably 25-80 ⁇ m, particularly preferably 40-80 ⁇ m.
  • the film thickness is 10 ⁇ m or more, it can adhere to the surface of the clear resin coating composition to be coated thereby to impart smoothness. is released.
  • the film-like cover material (hereinafter also referred to as the cover film) is generally a wound body (roll) in consideration of the convenience of storage and unwinding when bringing it on the clear composition.
  • the film thickness is within the above range, the film can be wound up and unwound satisfactorily.
  • the above-mentioned aging treatment of the clear composition can be performed using equipment such as a heat dryer and a constant temperature drying chamber.
  • equipment such as a heat dryer and a constant temperature drying chamber.
  • cover film forming methods such as melt extrusion molding, solution casting, coextrusion, calendering, lamination, and the like are used.
  • cover material When used to obtain a clear layer with high surface smoothness, it is important that a cover film with excellent surface smoothness can be produced regardless of which film forming method is used for the cover material. This is because the smoothness is transferred to the clear layer by bringing the smooth surface of the cover material into close contact with the surface of the uncured clear composition.
  • the cover film since the cover film is generally formed into a roll shape after being extruded, it is also manufactured by a known machine that also functions as film forming and winding.
  • FIG. 1 is a schematic illustration of a winding process applicable to the method for manufacturing a laminate of the present invention. An example of the winding method of the uncured laminate will be described with reference to the same figure.
  • a roll-shaped base material (base film) 10 is held by rollers 10a, and the unwound base material 10 is transported in the direction of arrow a.
  • the upper surface of the base material 10 is uniformly coated with the clear composition 14 by the roll coater 12 and conveyed in the direction of the drying oven 16 .
  • the clear composition 14 applied on the base material 10 is dried by passing through the drying oven 16 .
  • the drying oven 16 By further using a drying oven (not shown), the primer composition can be applied and dried, and then the above clear composition 14 can be applied.
  • a base material a laminate having a primer layer (hereinafter referred to as a dry film) which is coated with a primer composition once through a roll laminator and dried.
  • a roll-shaped cover material 18 (or a dry film having a primer layer) is supported by a roller 18a and unwound in the direction of arrow b to apply a clear composition on the base material 10 (or a dry film having a primer layer). It is laminated in laminating section 20 by being brought onto article 14 .
  • the laminating section 20 laminates the base material 10 (or a dry film having a primer layer), the clear composition 14, and the cover material 18 between the first laminating roll 20a and the second laminating roll 20b.
  • a laminated body (clear composition uncured laminated body) 22 obtained by lamination is continuously conveyed in the directions of arrows c and d and wound up by rollers 22a, which are means for winding up the laminated body 22. As shown in FIG. In order to apply a predetermined tension to each film and its laminate, a roller 24 is appropriately used as tensioning means.
  • the cover material is laminated by adjusting the pressure of the first lamination roll 20a and the second lamination roll 20b at a lamination pressure of 0 to 7 kg/cm 2 , preferably 1 to 6 kg/cm 2 , at a temperature of 15 to 35°C. Preferably, it can be adjusted to 20-25°C. These values can also be monitored by a control system (not shown) when using the winding device as shown in FIG.
  • the winding speed does not particularly affect the quality of the clear layer.
  • a conveying speed/laminating speed of 20 m/min can be used.
  • the surface of the cover material and the back surface of the base material are in contact with each other. can have an impact.
  • a protective layer protecting film
  • a two-layered base material so that both outer surfaces are mirror surfaces.
  • the winding pressure according to the characteristics of the clear composition that does not impair the surface smoothness of the clear layer even if the protective layer is not provided It is also important to
  • the production of the laminate of the present invention is not limited to the method of producing the wound body described above.
  • a base material having a certain size and shape such as a long or rectangular shape is prepared, the clear composition is applied to the base material, the cover material is allowed to stand on the upper surface of the clear composition, and the clear composition is formed.
  • the laminate of the present invention can also be obtained by bringing the cover material into close contact with the cover material. Also in this case, by selecting the clear composition and the type of cover material, a smooth or highly glossy clear layer can be formed after the cover material is peeled off.
  • the roughness and grains of the back surface of the base material are not transferred to the cover material or the clear layer.
  • the cover material it is possible to increase the thickness of the cover material or to provide the above-described protective layer on the surface.
  • the protective layer in this case must be a layer that does not impair the above-mentioned effects of the cover material. For this reason, layers having properties similar to those of the cover material, in particular acetylated cellulose films, polyester films, polypropylene films, polyethylene films, polyolefin non-woven fabrics, etc., can be used.
  • the clear layer and the cover material are manufactured with a uniform thickness on the base material, but at the end face, the clear layer protrudes from the base material, the cover material, or any one of them.
  • Some unevenness may occur on the end face of the laminate, for example, the adhesive may be not applied to the entire surface of the base material and the cover material and may be dented inside them.
  • the end faces can be cut, for example, to produce a laminated body without unevenness on the end face, for example, a roll-shaped laminated body.
  • the roll-shaped or other shaped laminate obtained as described above is subjected to an aging treatment. Aging is carried out by holding a laminate consisting of a base material, a clear composition, and a cover material as it is, for example, at a temperature of room temperature to 80° C. under atmospheric pressure for about 1 day (24 hours) to 7 days. It reacts reactive compounds in substances. Thereby, a cured product of the clear composition, that is, a clear layer is obtained.
  • the cured clear layer is generally transparent or translucent, preferably transparent, and has a particularly high light transmittance of 90% or more.
  • a surface with excellent gloss of 90 or more, preferably 92 or more can be formed with a No. 4442 microgloss 20° (also called gloss 20°) surface gloss meter (manufactured by Tetsutani Co., Ltd.).
  • a composite coating film can be obtained by peeling off the cover material from the laminated body in which each layer is cured (cover material peeling step). Peeling can be easily done by hand, but can also be done by a film peeling device (for example, a protective film peeling device).
  • a composite coating film having base film/primer layer/clear layer in this order is obtained, and the clear layer is applied directly on the base film.
  • a composite coating film of base film/clear layer can be obtained, and both can be formed into a film-like composite coating film.
  • other layers may be provided between the base film and the primer layer and between the primer layer and the clear layer.
  • other layers see, for example, JP-A-2000-301844, JP-A-1992-366632, JP-A-1992366633, JP-A-2010-234366, and JP-A-2011-093306. .
  • FIG. 2 is a diagram for explaining the laminate of the present invention and the method for producing a molded article using the laminate.
  • FIG. 3 is a cross-sectional view showing a state applied to a substrate 200;
  • the laminate 100 has a primer layer 130 , a clear layer 140 and a cover material 150 in this order on a base film 120 .
  • the laminate 100 may be provided with a protective film (not shown) for storage or aging as described above.
  • the laminate 100 is placed on the surface of the base film 120 side of the substrate 200, such as a work (semi-processed product) such as an automobile body, parts, or parts thereof (preferably made of synthetic resin).
  • a work such as an automobile body, parts, or parts thereof (preferably made of synthetic resin).
  • the base film 120 of the composite coating is melted by the heat of the melted synthetic resin and fused with the substrate 200, preferably to be coated.
  • the surface portion of the synthetic resin is melted and fused with the melted base film, and then integrated through cooling. That is, the substrate is thereby coated with the composite coating film to form an insert molded article.
  • the primer layer is optionally provided, and regardless of the presence or absence of the primer layer, the clear layer constitutes the outermost covering layer of the insert-molded article.
  • the base material By making the base material peelable, not only the cover material but also the base material can be peeled off from the laminate to produce a single clear layer (clear sheet or film).
  • This single layer can be used in various forms such as colorless and colored transparent clear sheets or cured films, lumps, irregular shapes, etc., and can be used as exterior parts of automobiles, fittings, windows, building materials such as partition plates, office products, daily necessities, stationery, Used as toys, ornaments, or their outermost parts, parts or accessories.
  • the base material can be made of the same material as the above-described cover material, in which case both sides of the clear layer can be formed to have high smoothness and good quality. That is, depending on the selection of the base material and the cover material, smoothness can be imparted to only one surface of the single clear layer or to both surfaces.
  • the single clear layer of the present invention has a simple structure of only one layer, and can be manufactured by a simple method using existing equipment. Since expensive manufacturing is not performed, there is also a large economic benefit. Furthermore, since the manufacturing process is carried out by the flow shown in FIG. 1 and aging after the cover material is placed, the amount of clear composition used and solvent volatilization can be easily controlled and processed, and environmental protection can be achieved. Excellent from that point of view. The same applies to the above-mentioned laminates, composite coating films, and methods for producing them, and as a result, composite products such as insert-molded articles obtained by using them are also efficiently produced.
  • Base material base film
  • the base film is appropriately selected in consideration of the material to which the composite coating film is applied.
  • the base film include polypropylene compositions containing polypropylene (PP) selected from polypropylene homopolymers, random copolymers or block copolymers, or compositions containing acrylonitrile-butadiene-styrene copolymers (ABS resin).
  • PP polypropylene
  • ABS resin acrylonitrile-butadiene-styrene copolymers
  • pretreatment such as corona treatment or plasma treatment is also effective.
  • the surface of the base material is modified to improve the wettability (wetting tension), and the base material when applying the primer composition. To prevent repelling of the clear composition on the surface.
  • a composition containing a polypropylene composition and an ABS resin is added with NH-type, NR-type (N-alkyl type), and NOR-type (N-alkoxyl type) hindered amines (HALS). Since it acts as a heat stabilizer, it helps improve the heat resistance and weather resistance of the object to be coated. It is also advantageous in terms of maintaining quality when the manufactured laminate is stored as it is.
  • the base film may be pre-dyed by adding a coloring agent to the resin material in advance, or may have a portion colored on the surface or inside by printing or the like.
  • the base material when the base material is finally peeled off, that is, when the single-layer clear layer described above is obtained, it is preferably 1.2 to 1.4 g/cm 3 , a water absorption of 0.3 to 7.0%, Preferably 0.5 to 6.5%, surface roughness Ra 1 ⁇ m or less, preferably 0.01 ⁇ m to 1 ⁇ m, more preferably 0.01 ⁇ m to 0.1 ⁇ m, surface pencil hardness 6B to 4H, preferably 2B to 4H, especially A base material of 2H to 4H is preferably used. That is, by using the same materials as those mentioned above as preferred examples of the cover material, the solvent remaining in the clear composition can be volatilized during the aging process even on the surface of the base material. It leads to aesthetics and physical properties. Mechanisms and details of solvent capture and passage, and the resulting effects, have already been detailed in relation to the cover material.
  • the base material that can be peeled off from the clear layer and that can improve the surface quality of the base material side of the clear layer include cellulose, acetylated cellulose, (meth)acrylic resin, polyamide, porous polypropylene, and porous high-quality polyethylene or polyolefin non-woven fabric.
  • composition of solvent-based primer coating composition for example, a general primer can be used in which chlorinated polypropylene is used as a main component, reactivity is imparted with an epoxy resin, and the primer is diluted with an organic solvent.
  • materials that contribute to the improvement of the adhesion between the base material and the clear composition that can be used in the present invention are selected from known primers that are generally used for painting vehicle parts (bumpers, etc.). It can be selected and used as appropriate.
  • the clear composition is not particularly limited as long as it is a composition that can be cured and formed into a film by the method of the present invention. It is preferable to use a material from which a clear layer having properties such as scratch resistance and weather resistance can be produced.
  • any conventionally used clear coat composition can be used. Examples include clear compositions containing acrylic resins such as poly(meth)acrylate and aminoplast components such as melamine as resin components, and clear compositions containing poly(meth)acrylate and poly(block)isocyanate as resin components. be able to.
  • the clear layer obtained from the resin component of poly(meth)acrylate and poly(block)isocyanate has particularly excellent scratch resistance, so it is suitable for constructing a coating film for a substrate used outdoors. Highly preferred.
  • the clear composition is an acrylic resin, more specifically, a composition mainly composed of one or more hydroxyl group-containing acrylic resins, particularly hydroxyl group-containing (meth)acrylates, and isocyanate, particularly polyisocyanate. preferably an object.
  • (meth)acrylate means either acrylate or methacrylate
  • poly(meth)acrylate means a polymer containing acrylate or methacrylate
  • polyisocyanate means two per molecule. It means a compound having an isocyanate group as described above.
  • the clear composition of the present invention comprises two types of hydroxyl group-containing acrylic resins: a hydroxyl group-containing (meth)acrylate resin (A) and a hydroxyl group-containing (meth)acrylate resin (B) (also referred to as acrylate (A) and acrylate (B)). It is preferable to contain a resin of In this case, the acrylate (A) has a hydroxyl value of 80 to 220 mgKOH/g, a glass transition temperature of ⁇ 50° C. or more and less than 0° C., and units derived from 4-hydroxybutyl (meth)acrylate in the resin. is a resin containing 25 to 55% by mass.
  • this acrylate (A) can impart sufficient cross-linking density to the coating film, and the clear film (simply referred to as film) as a cured product of the clear composition will have scratch resistance. .
  • the hydroxyl value of acrylate (A) is 80-220 mgKOH/g, preferably 100-200 mgKOH/g, and particularly preferably 120-200 mgKOH/g.
  • the hydroxyl value is 80 mgKOH/g or more, the cross-linking density of the film is sufficiently ensured, the hardness of the film is improved, and the stain resistance is improved.
  • the hydroxyl value is 220 mgKOH/g or less, the compatibility with the curing agent is improved, and the appearance of the film after curing is excellent.
  • Acrylate (A) generally contains 25 to 55% by mass of units derived from 4-hydroxybutyl (meth)acrylate, particularly preferably 30 to 55% by mass.
  • the 4-hydroxybutyl (meth)acrylate in the acrylate (A) is 55% by mass or less, the compatibility with the curing agent is improved and the appearance of the film is stabilized.
  • the glass transition temperature of acrylate (A) is -50°C or more and less than 0°C, preferably -40 to -5°C. When the glass transition temperature is ⁇ 50° C. or higher, sufficient film hardness is obtained, and when it is 0° C. or lower, the mechanical strength of the film is ensured.
  • the DSC method that is, differential scanning calorimetry is used to measure the glass transition temperature.
  • Acrylate (B) is a resin with a hydroxyl value of 80-220 mgKOH/g and a glass transition temperature of 0-50°C. By using this acrylate (B) together, the obtained film has sufficient crosslink density and hardness.
  • the hydroxyl value of acrylate (B) is 80-220 mgKOH/g, preferably 100-200 mgKOH/g, and particularly preferably 120-200 mgKOH/g.
  • the hydroxyl value is 80 mgKOH/g or more, sufficient film hardness and stain resistance can be obtained. Further, when the hydroxyl value is 220 mgKOH/g or less, the compatibility with the curing agent is improved, and the appearance of the resulting film is improved.
  • the glass transition temperature of acrylate (B) is 0 to 50°C, preferably 10 to 50°C. When the glass transition temperature is 0°C or higher, sufficient film hardness is obtained, and when it is 50°C or lower, the mechanical strength of the film is improved.
  • the mass average molecular weight (Mm) of acrylate (A) and acrylate (B) is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 3,000 to 15,000. .
  • Mm mass average molecular weight
  • the film hardness becomes sufficient
  • the mass average molecular weight is 30,000 or less, the compatibility with the curing agent is ensured and the film appearance is good. becomes.
  • the mass average molecular weights of acrylate (A) and acrylate (B) were adjusted by GPC (gel permeation chromatography) using polystyrene as a standard polymer, THF as an eluent, and a sample solution concentration of about 0.1%. It shows the molecular weight obtained by using HLC-8220 GPC manufactured by Tosoh Corporation, with a predetermined column, flow rate: 0.35 ml/min, temperature: 40°C, measurement time: 15 minutes. The same applies to the examples described later.
  • acrylate (A) and acrylate (B) are preferably resins containing 50% by mass or more of units derived from acrylic monomers, more preferably resins containing 70% by mass or more, and 80% by mass.
  • a resin containing the above is particularly preferable.
  • 70% or more, particularly all hydroxyl groups contained in the acrylate (A) are primary hydroxyl groups.
  • units derived from the acrylic monomer described above can be units derived from 4-hydroxybutyl (meth)acrylate, and in addition, radical polymerization having a primary hydroxyl group. It may contain a unit derived from a functional monomer.
  • Examples of radically polymerizable monomers having these hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, allyl alcohol, acrylic 2-hydroxyethyl acid, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, or methacrylic acid
  • Examples include ethylene oxide and/or propylene oxide adducts of 4-hydroxybutyl acid.
  • Acrylate (B) preferably contains a unit derived from a radically polymerizable monomer having a primary hydroxyl group as a unit derived from an acrylic monomer.
  • Both acrylate (A) and acrylate (B) may contain units derived from other radically polymerizable monomers.
  • other radically polymerizable monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, 2-
  • Acrylate (A) and acrylate (B) can be produced by radically polymerizing the above radically polymerizable monomers.
  • each monomer may be blended with a radical polymerization initiator.
  • radical polymerization initiators include 2,2'-azobisisobutyronitrile, 2.2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, 1- Azo compounds such as azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,5,5-trimethylhexanone peroxide, 1,1-bis ( t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)-cyclohexane, 2,2-bis(t-butylperoxy)octane, t-butylhydroperoxy Oquindo, diiso
  • the amount of the radical polymerization initiator to be blended is not particularly limited, but it is preferably 0.01 to 20% by mass with respect to the total amount of the radically polymerizable monomers.
  • organic solvents used in the production of acrylate (A) and acrylate (B) include alicyclic hydrocarbon solvents such as cyclohexane and ethylcyclohexane, aromatic solvents such as toluene, xylene, ethylbenzene and aromatic naphtha.
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, ethyl acetate, n-butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, bis(2-ethylhexyl) adipate, etc.
  • ether solvents such as dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1,3,5-trioxane, acetonitrile, valeronitrile, N,N-dimethylformamide, N,N-diethylformamide, etc.
  • the organic solvent may be a single solvent or a mixed solvent of two or more.
  • the solid content concentration of acrylates (A) and (B) can be arbitrarily selected within a range that does not impair the dispersion stability of the resin, but is generally 10 to 90% by mass, preferably 25 to 85% by mass, more preferably 40 to 80% by mass.
  • the method of adding the radical polymerization initiator is arbitrary when producing acrylate (A) and acrylate (B).
  • Acrylate (A) and acrylate (B) thus obtained can be used either singly or in combination.
  • the content ratio of the hydroxyl group-containing acrylate (A) and the hydroxyl group-containing acrylate (B) in the clear composition of the present invention is 95/5 to 50/95/5 to 50/2 in terms of the solid content mass ratio of the acrylates (A) and (B). 50, preferably 90/10 to 60/40.
  • polyisocyanates (curing agents) that can be used as isocyanates contained in the clear composition of the present invention include isocyanate compounds having at least 2, preferably 3 or more isocyanate groups that react with hydroxyl groups in one molecule.
  • One type may be used alone, or two or more types may be used in combination.
  • Polyisocyanate compounds include, for example, p-phenylene diisocyanate, biphenyl diisocyanate, tolylene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, aromatic diisocyanates such as methylenebis(phenylisocyanate), isophorone diisocyanate, methyl Alicyclic diisocyanates such as cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, lysine methyl ester diisocyanate, bis(isocyanatoethyl) fumarate, 2- Straight-chain aliphatic diisocyanates such as isocyanatoethyl-2,6-diisocyanatohexanoate, and burettes and isocyanurates thereof can be mentioned. Is
  • the clear composition of the present invention preferably contains an aliphatic diisocyanate including the above alicyclic and linear aliphatic diisocyanates, particularly a linear aliphatic diisocyanate, as a curing agent. It is preferably contained in an amount of 50% by mass or more, preferably 85% by mass or more, particularly preferably 100% by mass, based on the total amount of isocyanate used.
  • an aliphatic diisocyanate including the above alicyclic and linear aliphatic diisocyanates, particularly a linear aliphatic diisocyanate, as a curing agent. It is preferably contained in an amount of 50% by mass or more, preferably 85% by mass or more, particularly preferably 100% by mass, based on the total amount of isocyanate used.
  • the content ratio of the isocyanate groups of the isocyanate to the total hydroxyl groups of the acrylate (A) and the acrylate (B) is 0.5 to 1.5, preferably 0.8 to 1.5, in terms of NCO/OH molar ratio. 2.
  • NCO/OH molar ratio is less than or equal to 0.5, sufficient crosslink density is obtained, and acid resistance and film hardness are improved. Further, by setting the NCO/OH molar ratio to 1.5 or less, the weather resistance is improved.
  • the clear composition of the present invention further contains an organic solvent.
  • organic solvents mentioned above as examples used in the production of acrylate (A) and acrylate (B) can be used as the organic solvent, and the same solvents as used in these productions can be used. It is possible to use it as a diluting solvent for the clear composition without removing the residual solvent used for acrylate (A) and acrylate (B). That is, it is possible not to add any organic solvent other than the residual solvent used for acrylate (A) and acrylate (B). Further, the organic solvent to be added may be a single solvent or a mixed solvent of two or more.
  • the clear composition of the present invention is a weather stabilizer system composed of various additives, such as weather stabilizers, particularly ultraviolet absorbers (UV absorbers) and hindered amine weather stabilizers, as necessary.
  • weather stabilizers particularly ultraviolet absorbers (UV absorbers) and hindered amine weather stabilizers, as necessary.
  • antioxidants antioxidants, surfactants, surface modifiers, curing reaction catalysts, antistatic agents, fragrances, dehydrating agents, and rheology modifiers
  • polyethylene wax, polyamide wax, and internally crosslinked resin fine particles, etc. can be used by adding one or more of Known materials can be appropriately used for any of these.
  • a UV absorber and a hindered amine as weather stabilizers.
  • the clear composition of the present invention is used as the outermost coating for the exterior of a vehicle or the like, it is likely to be exposed to various weather changes in the outdoors for a long period of time, especially for private vehicles. In some cases, the gloss and aesthetics of the appearance may affect the function and value of automobiles, including durability. It is possible to maintain the state of the clear film applied to the object in a state close to that at the time of shipment for several tens of years or more, particularly 20 years.
  • triazine-based ultraviolet absorbers and NOR-type hindered amine-based weather stabilizers (HALS) to the clear composition exemplified as preferable for application of the present invention.
  • one of the two types of triazine-based ultraviolet absorbers is a material that absorbs short wavelength (320 nm or less) ultraviolet rays (hereinafter also referred to as a short wavelength UV absorber), and the other is a material that absorbs long wavelength (320 nm or more) ultraviolet rays.
  • Absorbing hereinafter also referred to as long wavelength UV absorber
  • being able to absorb ultraviolet rays in a wide range the quality of the clear film is maintained and the lower layer covered with the clear film is protected from ultraviolet rays.
  • the short wavelength UV absorber is an o-hydroxytris-aryltriazine UV absorber of the following formula (1)
  • the long wavelength UV absorber is an o-hydroxytris-aryltriazine UV absorber of the following formula (2). preferable.
  • Q 1 , Q 2 , Q 3 and Q 4 are independently hydrogen; C 1 -C 18 alkyl; —OH, C 2 -C 18 alkenyloxy, —C(O)OY 1 and —OC(O) C 1 -C 18 alkyl substituted with 1 , 2 or 3 groups selected from the group consisting of Y 2 wherein Y 1 and Y 2 are independently C 1 -C 18 alkyl; C 3 -C 50 alkyl interrupted by oxygen; or C 3 -C 50 hydroxyalkyl interrupted by oxygen; R 14 , R 15 and R 16 are independently of each other hydrogen or C 1 -C 18 alkyl]
  • UV absorbers of formula (1) the following compounds are particularly preferably used.
  • UV absorbers of formula (2) the following compounds are particularly preferably used.
  • the long-wavelength UV absorber and the short-wavelength UV absorber may each be used as one type of compound or as a mixture of multiple types.
  • Commercially available examples of long wavelength UV absorbers include Tinuvin (registered trademark), 460, 477, 479, 970, 1600 (manufactured by BASF Japan Ltd.), ADK STAB (registered trademark) LA-F70 (manufactured by ADEKA Corporation) ).
  • Examples of commercially available short-wave UV absorbers include Tinuvin (registered trademark) 400, 405, 1577 (manufactured by BASF Japan Ltd.) and ADK STAB (registered trademark) LA-46 (manufactured by ADEKA Corporation).
  • UV absorbers protect the composition to which they are added, as well as the objects covered by them (primer layer, base material and substrate, printing ink and pigment).
  • NOR-type hindered amine light stabilizers generally have a molecular weight of greater than 200 g/mol, preferably greater than 500 g/mol, especially greater than 700 g/mol, more preferably greater than 700 g/mol and up to 10,000 g/mol. for example up to 50,000 g/mol. Molecular weights between 700 g/mol and 5,000 g/mol are particularly preferred.
  • NOR-type hindered amine light stabilizers may be added, and commercially available products include TINUVIN (registered trademark) 123, 144, 765, and 770 (manufactured by BASF Japan Ltd.) and ADK STAB (registered trademark). LA-81, 82 or 87 (manufactured by ADEKA Corporation).
  • Such a NOR-type hindered amine light stabilizer has the role of protecting the composition to which it is added from heat, light, and chemicals from the outside world. Therefore, when the NOR-type hindered amine light stabilizer is contained, the clear film of the present invention containing this becomes less susceptible to the influence of the external environment such as acid rain and the internal environment such as the acidic atmosphere associated with resin deterioration. Additionally, such hindered amine light stabilizers can provide thermal stability to the film over long periods of time when the substrate to be coated, such as an automobile, maintains its functionality.
  • ADK STAB registered trademark
  • LA-1000 manufactured by ADEKA Corporation
  • the clear film of the present invention is preferably used as a clear film that constitutes the outermost layer coating of the object to be coated as a top coat, but it is also possible to mix colorants such as dyes and pigments and use it as a colored film.
  • the clear composition of the present invention may be either one-component type or two-component type.
  • it is convenient to use it as a two-liquid type without complicating the process by using a blocked isocyanate, etc., thereby having excellent physical properties and surface quality. of film is obtained.
  • a cover material having predetermined properties onto a clear composition by directly applying a cover material having predetermined properties onto a clear composition, a laminate and a coalescing layer having a clear layer having excellent appearance and mechanical properties, as well as a single layer, can be obtained.
  • a clear layer is obtained as a layer, and the removal of the solvent in the clear composition is performed well through the above-mentioned predetermined cover material, the burden on the environment is suppressed, and the manufacturing process is simple and efficient. This is because the physical properties and surface conditions of the clear layer can be maintained in optimum conditions by using the cover material and clear composition exemplified above as preferred examples.
  • the clear layer obtained by the present invention has a surface formed by the clear composition coming into contact with the cover material having the predetermined properties (both sides of which are formed by the cover material having the predetermined properties and the base material having the same properties as the cover material having the predetermined properties.
  • both sides have extremely excellent smoothness.
  • the substrate covering object to which the laminate or composite coating film of the present invention is applied
  • examples of mainly synthetic resins have been described, but the substrate is not limited to this.
  • it can also be used for metals such as aluminum and stainless steel, CFRP (carbon fiber reinforced plastic), and the like.
  • objects to be coated with the laminate or composite coating film of the present invention include automobiles (body bodies or parts thereof), automobile parts (e.g., bodies, bumpers, spoilers, mirrors, wheels, parts such as interior materials) of various materials), motorcycles, motorcycle parts, bicycles, bicycle parts (e.g., frames, handles, spoilers, mirrors), or road materials (e.g., guardrails, traffic signs, soundproof walls, etc.) ), ships, rail vehicles, aircraft, buildings, building materials, furniture, home appliances, containers, musical instruments, office supplies, sporting goods, toys, and parts or parts thereof.
  • Desmodur N3300 Product name, manufactured by Sumika Covestro Urethane Co., Ltd., liquid HDI nurate type resin (solid content: 100%, NCO content: 23% by mass)
  • Ultraviolet absorber solution 20% by mass xylene solution of Tinuvin 900 and Tinuvin 479 (each trade name, manufactured by BASF Japan)
  • Light stabilizer solution 20% by mass of Tinuvin 292 and Tinuvin 123 (each trade name, manufactured by BASF Japan)
  • Surface conditioner solution BYK-300 (trade name, manufactured by BYK-Chemie) in 10 mass% xylene solution
  • Solvesso 100 trade name, manufactured by Esso, aromatic petroleum naphtha
  • Examples 1 to 3, Comparative Examples 1 to 3 ⁇ Preparation of samples for evaluation of Examples 1 to 3 and Comparative Examples 1 to 3> A black unstretched polypropylene (CPP: cast polypropylene) having a thickness of 100 ⁇ m and having undergone corona treatment was placed on a horizontal table. Using CPP as a base material, a primer was applied to the surface of the corona-treated base material to a thickness of 5 ⁇ m and dried in an oven at 150° C. for 5 minutes. On the dried primer on the base material, the clear composition CC-1 was applied with a table coat to a thickness of 25 ⁇ m to form a clear composition layer.
  • CPP black unstretched polypropylene
  • a cover material was attached to the top surface of the clear composition before drying (on the side opposite to the base material) so as to be in close contact with the clear composition.
  • the resulting four-layered film of the resin layer on the base material was dried by heating in an oven at 40° C. for 4 days. It was confirmed that there were no dents in the resin layer, that no bubbles or air layers were present between the resin layer and the cover film, and that the cover material covered the entire upper surface of the resin layer.
  • a TAC film, FUJITAC FTTG60UL manufactured by Fuji Film Co., Ltd. was used as the cover material.
  • the four-layered film obtained as described above was cut into 10 cm squares, and the entire edges of the resulting square film, that is, the entire circumference, was covered with aluminum tape so that the solvent in the resin layer did not volatilize from the edges. was sealed to
  • the clear composition could not be held between the base material and a film with a four-layer structure could not be obtained.
  • the cover film can be easily peeled off.
  • x The resin layer stuck to the cover film and was difficult to peel off.
  • Table 1 shows the results of each of the above tests.
  • composition 1 Xylene solution of clear composition CC-1 (solid content 49%)
  • Composition 2 Xylene solution of clear composition CC-1 (solid content 80%)
  • Composition 3 butyl acetate solution of clear composition CC-1 (solid content 49%)
  • TAC Triacetyl cellulose (density: 1.22-1.34 g/cm 3 , water absorption 1.7-6.5% (water absorption when in contact with the surface of the clear composition for 24 hours), surface roughness Ra 0.01 ⁇ m to 0.1 ⁇ m, surface pencil hardness 2H)
  • Surface-treated PET Polyethylene terephthalate surface-treated with a silicone release layer (density: 1.34-1.39 g/cm 3 , water absorption 0.10-0.20% (contact with the clear composition surface for 24 hours). water absorption in the case of ), surface roughness Ra 0.1 ⁇ m, surface pencil hardness HB)
  • the resin layer as the clear layer enabled the organic solvent to be removed satisfactorily in a significantly shorter time than in the comparative examples, and that aging and curing were performed well.
  • the cover film from the clear layer after curing was faster than the film using the release agent of the comparative example, although the release agent treatment was not performed. It was conducted.
  • the surface quality of the obtained clear layer was extremely high, and it was observed that the degree of haze was lowered and the smoothness and gloss were greatly improved as compared with the surface obtained by the comparative example. .
  • Example 4 ⁇ Creation of laminate film> Clear composition CC-1 (solvent: 35.1 parts, solid content: 114.9 parts) was used, and the clear composition was applied on a base material (film thickness: 460 ⁇ m) to a film thickness of 60 ⁇ m (film thickness after drying: 30 ⁇ m). ), and the total thickness of the laminate was 520 ⁇ m (dry film thickness: 490 ⁇ m). made. The film thickness of the laminate film after drying was 490 ⁇ m.
  • Example 4 An injection molding machine J220ADS-300H manufactured by The Japan Steel Works, Ltd. was used to prepare a film insert molding sample plate (150 mm x 150 mm square). That is, the sample of Example 4 obtained as described above was cut into 70 mm x 150 mm squares, and after peeling off the cover film, the clear layer side of the laminate film was placed in the center of the inner surface of the mold (#3000). They were aligned and fixed with Sellotape (registered trademark), and polypropylene, which is a resin constituting the substrate, was introduced to the base material side using an injection molding apparatus. By allowing the mold to cool at 80° C. for 25 seconds, the base film and the polypropylene substrate were fused and integrated to obtain a 150 mm square injection molded plate (insert molded product) having a thickness of 3 mm.
  • a film insert molding sample plate 150 mm x 150 mm square
  • Comparative Example 4 ⁇ Production of sample by spray coating for evaluation of Comparative Example 4>
  • the sample of Comparative Example 4 was obtained by cutting a standard coated molding into a 70 mm x 150 mm square. This sample is obtained by forming a clear layer as the outermost layer by conventional spray coating on a substrate used as an exterior part of an automobile.
  • the clear layer of Comparative Example 4 has the highest level of surface quality conventionally applied to luxury cars.
  • the smoothness of the clear layer surface of the samples of Example 4 and Comparative Example 4 was measured using a stylus surface profiler (Dektak 6M stylus profiler, manufactured by Veeco).
  • a stylus surface profiler (Dektak 6M stylus profiler, manufactured by Veeco).
  • Example 4 and Comparative Example 4 have a clear difference in smoothness and gloss even by visual observation, and all 10 observers agree that the samples of Example 4 have smoothness and gloss. was found to be significantly superior to the Comparative Example 4 sample.
  • no non-uniformity was recognized in either the roughness or the gloss of each clear layer surface of each sample of Example 4 and Comparative Example 4, and any position was measured. It is recognized that averaging does not significantly affect the measured values.
  • Example 4 The above data for Example 4 are comparable to the finish polishing (mirror finish) of the coating film of Comparative Example 4 obtained by spray coating.

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PCT/JP2022/014643 2021-04-22 2022-03-25 クリヤー層を有する積層体の製造方法、これにより得られる積層体、複合塗膜の製造方法、これにより得られる複合塗膜、これを用いた成形体の製造方法並びに成形体、および上記積層体から得られるクリヤー層 Ceased WO2022224710A1 (ja)

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WO2025143122A1 (ja) * 2023-12-26 2025-07-03 積水化学工業株式会社 熱硬化性樹脂シート、車両及び車両部品、並びに車両及び車両部品の製造方法

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JP2005169654A (ja) * 2003-12-08 2005-06-30 Dainippon Ink & Chem Inc 熱成形用積層シートの成形方法及びその成形体
JP2005335161A (ja) * 2004-05-26 2005-12-08 Dainippon Ink & Chem Inc 積層シートの製造方法
JP2006062231A (ja) * 2004-08-27 2006-03-09 Dainippon Ink & Chem Inc 成形用積層シートおよびその製造方法
JP2006341388A (ja) * 2005-06-07 2006-12-21 Dainippon Ink & Chem Inc 熱成形用積層シートの成形方法及び成形体
JP2008110651A (ja) * 2006-10-30 2008-05-15 Kaneka Corp 自動車内装材および自動車内装部品
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JP2005169654A (ja) * 2003-12-08 2005-06-30 Dainippon Ink & Chem Inc 熱成形用積層シートの成形方法及びその成形体
JP2005335161A (ja) * 2004-05-26 2005-12-08 Dainippon Ink & Chem Inc 積層シートの製造方法
JP2006062231A (ja) * 2004-08-27 2006-03-09 Dainippon Ink & Chem Inc 成形用積層シートおよびその製造方法
JP2006341388A (ja) * 2005-06-07 2006-12-21 Dainippon Ink & Chem Inc 熱成形用積層シートの成形方法及び成形体
JP2008110651A (ja) * 2006-10-30 2008-05-15 Kaneka Corp 自動車内装材および自動車内装部品
JP2009240960A (ja) * 2008-03-31 2009-10-22 Honda Motor Co Ltd 光輝性塗膜形成方法および塗装物品

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* Cited by examiner, † Cited by third party
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WO2025143122A1 (ja) * 2023-12-26 2025-07-03 積水化学工業株式会社 熱硬化性樹脂シート、車両及び車両部品、並びに車両及び車両部品の製造方法

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