WO2024005020A1 - 転写シート、加飾成形品、及び加飾成形品の製造方法 - Google Patents
転写シート、加飾成形品、及び加飾成形品の製造方法 Download PDFInfo
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- WO2024005020A1 WO2024005020A1 PCT/JP2023/023824 JP2023023824W WO2024005020A1 WO 2024005020 A1 WO2024005020 A1 WO 2024005020A1 JP 2023023824 W JP2023023824 W JP 2023023824W WO 2024005020 A1 WO2024005020 A1 WO 2024005020A1
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- Prior art keywords
- layer
- transfer
- uneven
- resin
- flat
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
- C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14827—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using a transfer foil detachable from the insert
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
- B29C63/02—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
Definitions
- the present disclosure relates to a transfer sheet, a decorated molded product, and a method for manufacturing a decorated molded product.
- Decorative sheets used in such techniques can be broadly classified into laminate-type decorative sheets and transfer-type decorative sheets (ie, transfer sheets).
- a laminate-type decorative sheet is laminated on a supporting base material with the protective layer located on the outermost surface, and by laminating molded resin on the supporting base material side, the supporting base material is included in the resin molded product. Used to be incorporated.
- a protective layer is laminated directly on the supporting base material or via a flat part provided if necessary, and after laminating a molded resin on the side opposite to the supporting base material, By peeling off the base material, the resin molded product is used without any supporting base material remaining.
- a transfer-type decorative sheet other layers such as a design layer or an adhesive layer may be laminated on the protective layer, and if it has a flat part, it is important to place the protective layer on top of the flat part.
- these include the fact that they are laminated, the transfer base material must be peeled off from the protective layer during the molding process, and the surface exposed by peeling off the transfer base material must exhibit excellent physical properties. Therefore, compared to the laminate type, there is a problem that designing the resin composition that forms the protective layer is more difficult.
- an injection molding and simultaneous decoration method has been used to decorate resin molded bodies having complex surface shapes such as three-dimensional curved surfaces.
- the injection molding simultaneous decoration method is to integrate the decorative sheet inserted into the in-mold mold during injection molding with the molten injection resin injected into the cavity to create a resin molded product. This is a method of decorating the surface of Furthermore, due to the difference in the structure of the decorative sheet that is integrated with the resin molded body (the above-mentioned laminate-type and transfer-type decorative sheets), there are usually two methods: injection molding simultaneous lamination decoration method and injection molding simultaneous transfer decoration method. It is broadly divided into.
- the transfer layer side of the transfer sheet is placed toward the inside of the mold, and the transfer sheet is heated from the transfer layer side using a heating plate, and the transfer sheet is molded to follow the shape inside the mold. do.
- molten injection resin is injected into the cavity to integrate the transfer sheet and the injection resin.
- the transfer base material of the transfer sheet is peeled off, thereby obtaining a decorated molded product having a decoration layer to which the transfer layer has been transferred.
- Patent Document 1 and Patent Document 2 disclose a method of manufacturing a molded article whose surface has a partially different matte feeling by using a transfer sheet in which a matte layer is partially provided on a base material.
- the matte layer is provided between the flat portion and the base material. Further, a transfer layer including a protective layer and the like is provided on the opposite side of the flat portion from the matte layer side.
- a transfer sheet is subjected to injection molding, the flat portions are greatly compressed by heat and pressure during molding.
- the mat layer is harder than the flat portion, and therefore deforms less.
- the uneven shape of the matte layer is formed on the transfer layer, and the surface of the resulting decorative molded product is given an uneven design.
- the uneven design on the surface of the decorative molded product is easy to see when observed from a direction perpendicular to the surface of the decorative molded product, but when viewed from a direction horizontal to the surface of the decorative molded product, It may be difficult to see when observing from a direction close to the direction.
- the main purpose of the present disclosure is to provide a transfer sheet that can impart an uneven shape that is easily visible even when observed from various angles to the surface of a decorative molded product. . Furthermore, the present disclosure also aims to provide a method for manufacturing the transfer sheet and a method for manufacturing a decorated molded product using the transfer sheet.
- a transfer sheet having a transfer layer on a release sheet The release sheet includes, in order from the transfer layer side, a release layer and a base material, The release layer is an uneven portion containing a binder resin and a matting agent and having a plurality of convex portions on the transfer layer side; a flat portion where the surface closer to the transfer layer is relatively flat than the uneven portion; It has A transfer sheet, wherein the plurality of convex portions of the uneven portion of the release layer are in contact with the transfer layer.
- the surface of the transfer layer in contact with the uneven portion has an uneven shape due to contact with the uneven portion, Item 2.
- Section 7. Item 7. A decorated molded product, wherein the transfer layer of the transfer sheet according to any one of Items 1 to 6 is laminated on an adherend.
- Section 8. A step of adhering the transfer layer of the transfer sheet according to any one of items 1 to 6 to an adherend, and laminating the transfer sheet on the adherend;
- a method for manufacturing a decorated molded product comprising the step of peeling off the release sheet of the transfer sheet and transferring the transfer layer onto the adherend.
- a transfer sheet that can impart an uneven shape that is easily visible even when observed from various angles to the surface of a decorated molded product. Further, according to the present disclosure, it is also possible to provide a method for manufacturing the transfer sheet and a method for manufacturing a decorated molded product using the transfer sheet.
- FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a transfer sheet of the present disclosure.
- FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a transfer sheet of the present disclosure.
- FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorated molded product with a transfer base material of the present disclosure.
- FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorated molded product with a transfer base material of the present disclosure.
- FIG. 1 is a schematic diagram of a cross-sectional structure of one form of a decorative molded product of the present disclosure.
- the transfer sheet of the present disclosure is a transfer sheet having a transfer layer on a release sheet, and the release sheet includes a release layer and a base material in order from the transfer layer side, and the release layer includes a binder resin and a base material. It has an uneven part that contains a matting agent and has a plurality of protrusions on the transfer layer side, and a flat part whose surface on the transfer layer side is relatively flat than the uneven part, and the uneven part of the release layer It is characterized in that a plurality of convex portions are in contact with the transfer layer.
- the transfer sheet of the present disclosure having the above characteristics can impart an uneven shape that is easily visible even when observed from various angles to the surface of a decorated molded product.
- the transfer sheet, the decorated molded product with a transfer base material, and the decorated molded product of the present disclosure will be described in detail.
- the numerical range indicated by “ ⁇ ” means “more than” and “less than”.
- the expression 2 to 15 mm means 2 mm or more and 15 mm or less.
- the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
- the upper limit value and the upper limit value, the upper limit value and the lower limit value, or the lower limit value and the lower limit value, which are described separately, may be combined to form a numerical range.
- the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.
- the transfer sheet 10 of the present disclosure has a transfer layer 30 on a release sheet 20.
- the release sheet 20 includes a release layer 23 and a base material 22 in this order from the transfer layer 30 side.
- the release layer 23 includes an uneven portion 24 and a flat portion 25.
- the uneven portion 24 has a plurality of protrusions on the transfer layer 30 side. Furthermore, the surface of the flat portion 25 closer to the transfer layer 30 than the uneven portion 24 is relatively flat.
- the uneven portions 24 and the flat portions 25 are formed alternately; It is preferable that a pattern is formed by The pattern shape formed by the uneven portion 24 and the flat portion 25 will be described later (for example, a wood grain conduit pattern).
- the plurality of convex portions of the uneven portion 24 of the release layer 23 are in contact with the transfer layer 30.
- a plurality of convex portions of the uneven portion 24 of the release layer 23 are in contact with the protective layer 32 of the transfer layer 30, respectively.
- the surface of the transfer layer 30 on the release sheet 20 side is in contact with the uneven portion 24 and the flat portion 25 of the release layer 23, and the uneven gaps (recesses) of the uneven portion 24 are connected to the release sheet 20 side of the transfer layer 30.
- the outermost layer (protective layer 32 in FIGS. 1 and 2) is buried therein.
- the concave portions of the uneven portions 24 are not impregnated with the resin composition forming the flat portions 25. That is, in forming the uneven portion 24 and the flat portion 25, the resin composition forming the flat portion 25 is applied to a position different from the position where the uneven portion 24 is formed.
- a portion of the recessed portion of the uneven portion 24 contains a resin composition that forms the flat portion 25.
- the resin composition forming the flat portion 25 is applied from above the uneven portion 24, and is partially impregnated into the recesses of the uneven portion 24.
- the surface of the transfer layer 30 in contact with the uneven portion 24 has an uneven shape due to contact with the uneven portion 24.
- the tips of the plurality of convex portions included in the uneven shape of the transfer layer 30 are located closer to the base material 22 than the surface of the transfer layer 30 that is in contact with the flat portion 25. Therefore, when the release sheet 20 is peeled off from the transfer layer 30, the uneven convex portions on the surface of the transfer layer 30 protrude beyond the flat portions (see FIG. 5). This is particularly preferable because the uneven shape becomes even more visible when observed from various angles.
- the transfer layer 30 includes, in order from the release sheet 20 side, a protective layer 32, a primer layer 34, a printing layer 36, and an adhesive layer 38.
- the transfer layer 30 preferably has a protective layer 32, and the primer layer 34, printing layer 36, and adhesive layer 38 are layers provided as necessary.
- the base material functions as a transfer base material for transferring the transfer layer to an adherend.
- a decorated molded product with a transfer base material see, for example, FIGS. 3 and 4
- a decorated molded product is obtained by peeling off a release sheet including a base material and a release layer from the decorated molded product with a transfer base material.
- the form of the base material may be either sheet-like or film-like.
- Base materials include polyolefin resins such as polyethylene and polypropylene, vinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene/vinyl acetate copolymers, ethylene/vinyl alcohol copolymers, polyethylene terephthalate, and polyethylene.
- Typical examples include polyester resins such as naphthalate and polybutylene terephthalate, acrylic resins such as methyl poly(meth)acrylate and ethyl poly(meth)acrylate, styrene resins such as polystyrene, and nylon 6 or nylon 66.
- plastic films made of resin such as polyamide resin. Among these plastic films, biaxially stretched polyester films are preferred because of their excellent heat resistance and dimensional stability.
- the thickness of the base material is preferably 12 to 150 ⁇ m, more preferably 25 to 100 ⁇ m. Further, the surface of the base material may be subjected to physical treatment such as corona discharge treatment or oxidation treatment, or coating of a paint called an anchor agent or primer in advance in order to improve the adhesion with the release layer.
- an antistatic layer may be provided on the side of the base material opposite to the release layer side.
- the antistatic layer may be in contact with the base material, or an antiblocking layer, a primer layer, etc. may be provided between the antistatic layer and the base material.
- the release layer includes an uneven portion and a flat portion.
- the uneven portion has a plurality of protrusions on the transfer layer side.
- the surface of the uneven portion on the base material side is flat.
- the surface of the flat portion is relatively flat on the transfer layer side than the uneven portion. Further, the surface of the flat portion on the base material side is flat.
- the uneven portion and the flat portion of the release layer will be explained respectively.
- the uneven portion is provided only on a portion of one surface of the base material.
- By partially forming the uneven portion it is possible to provide the surface of the transfer layer (the interface between the transfer layer and the release layer) with an uneven shape corresponding to the uneven shape of the uneven portion.
- the transfer sheet of the present disclosure it is possible to produce, for example, a decorated molded product provided with a pattern design with a difference in gloss within the surface of the protective layer.
- the uneven portion 24 of the release layer 23 may be in contact with the surface of the base material, or there may be other layers such as a primer layer, an easy-to-adhesion layer, etc. between the base material and the uneven portion 24 (e.g., a layer between the base material and the release layer).
- the uneven portion 24 may be in contact with the surface of the other layer.
- the flat portion 25 of the release layer 23, which will be described later, may be in contact with the surface of the base material, or other layers such as a primer layer, an easy-to-adhesion layer, etc. (for example, , a layer that increases the adhesion between the base material and the release layer 23), and the flat portion 25 may be in contact with the surface of the other layer.
- the uneven portion 24 of the release layer 23 is in contact with the surface of the base material.
- the flat portion 25 of the release layer 23 is in contact with the surface of the base material.
- the surfaces of the uneven portion 24 and the flat portion 25 of the release layer 23 on the base material side are formed so as to be in contact with the surface of the same layer.
- the uneven portion 24 and the flat portion 25 are formed so as to be in contact with the surface of the base material or the surface of the other layer described above (the layer between the base material and the release layer 23). is preferable, and more preferably formed so as to be in contact with the surface of the base material.
- the plurality of convex portions of the uneven portion of the release layer are in contact with the transfer layer.
- a plurality of convex portions of the uneven portion 24 of the release layer 23 are in contact with the protective layer 32 of the transfer layer 30, respectively.
- the surface of the transfer layer 30 on the release sheet 20 side is in contact with the uneven portion 24 and the flat portion 25 of the release layer 23, and the uneven gaps (recesses) of the uneven portion 24 are connected to the release sheet 20 side of the transfer layer 30.
- the surface layer (protective layer 32 in FIGS. 1 and 2) is buried therein.
- the uneven portion includes a binder resin and a matting agent. It is preferable that the binder resin contains a thermoplastic resin.
- a flat portion which will be described later, is usually formed after the uneven portion is cured, resulting in poor adhesion between the uneven portion and the flat portion. For this reason, when the transfer sheet of the present disclosure is transferred to an adherend, separation occurs between the uneven portions and the flat portions, and the release layer tends to remain on the decorative molded product.
- the shape of the uneven portion is disturbed due to curing shrinkage, and when a decorative molded product is produced, the design of the matte portion tends to be poor.
- the uneven part when forming a flat part on the uneven part without completely curing the thermosetting resin when forming the uneven part, the uneven part may swell due to the solvent contained in the coating liquid for forming the flat part depending on the degree of curing. There is a possibility. As a result, when a decorative molded product is produced, the design of the matte portion may deteriorate.
- by forming the uneven portion using a thermoplastic resin as a main component of the binder resin it is possible to improve the adhesion between the flat portion and the uneven portion.
- the transfer sheet of the present disclosure it is possible to suppress the difference in peel strength between the flat portion and the transfer layer (protective layer), and it is possible to improve the peelability. .
- the binder resin consists essentially of a thermoplastic resin.
- the term "main component" when the main component of the binder resin is a thermoplastic resin means that the proportion of the thermoplastic resin in the binder resin is 50% or more, preferably 60% or more, and more preferably 80% or more. % or more, more preferably 90% or more, even more preferably 95% or more, and "substantially” means that the proportion of the thermoplastic resin in the binder resin is 95% or more, preferably 98% or more. % or more, more preferably 100%.
- the uneven portion is preferably formed mainly of a binder resin and a matting agent, and is preferably substantially composed of the binder resin and a matting agent.
- "main component” means that the proportion of the binder resin and matting agent in the uneven portion is 50% or more, preferably 60% or more, more preferably 80% or more, still more preferably 90% or more, and still more preferably 95% or more. % or more, and “substantially” means that the proportion of the binder resin and matting agent in the uneven portion is 95% or more, preferably 98% or more, and more preferably 100%. means.
- the average height of the uneven portion is preferably about 0.1 ⁇ m or more, more preferably about 0.5 ⁇ m or more, and still more preferably about 1.0 ⁇ m or more, and , preferably about 8 ⁇ m or less, more preferably about 6 ⁇ m or less, even more preferably about 4 ⁇ m or less, and preferred ranges include about 0.1 to 8 ⁇ m, about 0.5 to 6 ⁇ m, and the like.
- the method for measuring the average height is as described in the section ⁇ Structural analysis of peeling layer> described below, and specifically, according to the method described in Examples.
- the average peak height of the uneven portion is preferably about 1.5 ⁇ m or more, more preferably about 2.0 ⁇ m or more, and even more preferably about 2.5 ⁇ m or more.
- the thickness is preferably about 10 ⁇ m or less, more preferably about 8 ⁇ m or less, even more preferably about 6 ⁇ m or less, and preferred ranges include about 1.5 to 10 ⁇ m, about 2 to 8 ⁇ m, and the like.
- the average peak height of the uneven portion is the height of the top 10% of the tallest protrusions among the heights of the protrusions included in the uneven portion (the reference is the position of the surface of the base material on the transfer layer side).
- the height is the average value of the top five heights.
- the method for measuring the average peak height is as described in the section ⁇ Structural analysis of peeling layer> described later, and specifically, according to the method described in Examples.
- the variation (%) in the height of the uneven portion is preferably about 32 to 80%, more preferably about 35 to 75%. %, more preferably about 40 to 65%.
- the method for measuring the variation (%) in the peak height is as described in the section ⁇ Structural analysis of peeling layer> described below, and specifically, according to the method described in Examples.
- ⁇ Structural analysis of release layer> Regarding the structural analysis of the uneven portion of the release layer, if the uneven portion is printed on the base material and a sheet before the flat portion is printed is available, the sheet is targeted for analysis.
- a commercially available shape analysis laser microscope (for example, VK-X1000 manufactured by Keyence Corporation) is used. A total of three locations are measured, with an arbitrary 100 um width of the uneven portion as the measurement area. At that time, the surface of the base material on which the release layer is formed is defined as the zero height point.
- the area ratio of the uneven portion within the surface of the base material is selected depending on the pattern shape formed by the uneven portion and the flat portion, and is preferably 1% or more, more preferably 5% or more, and 10% or more. % or more, more preferably 12% or more, even more preferably 15% or more. Further, the area ratio is preferably 99% or less, more preferably 95% or less, even more preferably 90% or less, even more preferably 88% or less, and 85% or less. It is even more preferable that there be.
- thermoplastic resins examples include polyolefin resins such as polypropylene and polyethylene, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, vinyl chloride resins, and cellulose resins. etc. are used.
- ABS resins acrylonitrile-butadiene-styrene resins
- acrylic resins vinyl chloride resins
- cellulose resins etc.
- the resins listed above can be used alone or in combination.
- acrylic resins and cellulose resins are preferred from the viewpoint of dispersibility of the matting agent and adhesion to flat areas.
- acrylic resins and cellulose resins can be suitably used because they have stability against ionizing radiation.
- the acrylic resin is not particularly limited, but includes, for example, a homopolymer of (meth)acrylic ester, a copolymer of two or more different (meth)acrylic ester monomers, or a (meth)acrylic ester and other polymers. Examples include copolymers with monomers.
- (Meth)acrylic resins include, more specifically, poly(meth)methyl acrylate, poly(meth)ethyl acrylate, poly(meth)propyl acrylate, poly(meth)butyl acrylate, and (meth)acrylic acid.
- Methyl-butyl (meth)acrylate copolymer ethyl (meth)acrylate-butyl (meth)acrylate copolymer, ethylene-methyl (meth)acrylate copolymer, styrene-methyl (meth)acrylate copolymer
- examples include (meth)acrylic acid esters such as polymers.
- examples of cellulose resins include nitrocellulose resins.
- the weight average molecular weight of the thermoplastic resin is preferably 10,000 or more and 200,000 or less, more preferably 30,000 or more and 150,000 or less.
- the coating liquid for forming the uneven portion can be easily adjusted, and the shape stability of the uneven portion can be improved.
- the "weight average molecular weight” here means the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
- the matting agent contained in the uneven portion has an average particle size of 0.5 ⁇ m or more.
- the average particle size of the matting agent is preferably 1.0 ⁇ m or more, more preferably 2.0 ⁇ m or more, and 3.0 ⁇ m or more. More preferably.
- the average particle diameter of the matting agent is 20 ⁇ m, considering the visibility of the printed layer in the area where the uneven shape is given by the uneven parts and the ease of forming the uneven parts. It is preferably at most 15 ⁇ m, more preferably at most 15 ⁇ m, even more preferably at most 10 ⁇ m.
- the ratio of the average particle diameter of the matting agent to the average height of the uneven portion is preferably 1 or more, more preferably 1.2 or more, and even more preferably 1.4 or more.
- the ratio satisfies the above numerical value, a sufficient matte effect can be imparted to the decorative molded product.
- the ratio is preferably 10 or less. It is more preferably 8 or less, and even more preferably 6 or less.
- the average particle size is determined by observing a cross section in the thickness direction of the layer with a scanning electron microscope (SEM) under the conditions of an accelerating voltage of 3.0 kV and a magnification of 50,000 times, and randomly selecting 100 particles. This is the average value (arithmetic mean diameter) of particle diameters measured for non-agglomerated particles.
- SEM scanning electron microscope
- the matting agent may be inorganic particles or organic particles.
- inorganic particles include silica, alumina, clay, talc, diatomaceous earth, zeolite, calcium carbonate, barium sulfate, zinc oxide, titanium oxide, and glass beads.
- organic particles include various synthetic resin particles, such as melamine resin, benzoguanamine resin, benzoguanamine/melamine/formalin condensate, acrylic resin, urethane resin, and styrene resin. They can also be used in combination.
- the shape of the particles may be spherical or irregular.
- silica particles are preferable because they provide a good matte feel to the surface of the decorated molded product and have the advantage of being low in production cost.
- the oil absorption amount of the matting agent is preferably 150 ml/100 g or more, more preferably 200 ml/100 g or more, and still more preferably 250 ml/100 g or more, and the upper limit is, for example, 450 ml/100 g or more. 100 g or less, and preferred ranges include 150 to 450 ml/100 g, and 200 to 350 ml/100 g. If the oil absorption amount of the matting agent contained in the uneven portion is 150 ml/100 g or more, for example, when a resin composition for forming a flat portion is formed over the uneven portion (see Fig. 2), the resin composition will not absorb the uneven portion. It is easily absorbed into the parts (particularly in minute recesses), and can suitably suppress flattening of the uneven shape of the uneven parts.
- the oil absorption amount of the matting agent is a value measured in accordance with the provisions of JIS K 5101-13-2 Part 13: Oil Absorption - Section 2: Boiled Linseed Oil Act.
- the matting agent is preferably contained in an amount of 50 parts by mass or more and 180 parts by mass or less (solid content) per 100 parts by mass (solid content) of the binder resin.
- an appropriate fine uneven shape can be formed on the surface of the uneven portion and the surface of the flat portion on the uneven portion.
- the flexibility of the layer is low, so cracks may occur in the uneven part during the manufacturing process of the decorative molded product, causing the shape to become disordered. There is a risk that the design of the matte portion of the material may deteriorate.
- the uneven portion has flexibility even with the above-mentioned amount of matting agent, and it is thought that the shape of the uneven portion was maintained during the manufacturing process of the decorative molded product.
- the content of the matting agent is more preferably 75 parts by mass or more, and even more preferably 90 parts by mass or more, based on 100 parts by mass (solid content) of the binder resin.
- the content of the matting agent is more preferably 160 parts by mass or less, and even more preferably 140 parts by mass or less.
- the uneven portion preferably contains an additive that enhances the releasability, such as silicone or fluorine.
- the content of the additive is preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 5 parts by mass or less, based on 100 parts by mass (solid content) of the binder resin. , more preferably 3 parts by mass or less, and preferred ranges include about 0.3 to 5 parts by mass, and about 0.5 to 3 parts by mass.
- the resin composition that forms the flat part is formed over the uneven part as described above, the resin composition that forms the flat part is present in the recesses of the uneven part, so the contact between the uneven part and the transfer layer is This has the advantage of lower adhesion and higher releasability. Therefore, in this case, the advantage of including an additive that improves releasability in the uneven portion is reduced.
- the formation pattern of the uneven portion be appropriately selected depending on the pattern of the printed layer, which will be described later.
- the pattern include wood grain (wood grain conduit), stone grain, cloth grain, sand grain, circle, square, polygon, geometric pattern, and letters.
- a coating liquid for forming the uneven portion is prepared by adding additives as necessary to a thermoplastic resin as a binder resin and a matting agent, and adding an appropriate solvent.
- This coating liquid is applied onto a base material by a known means such as gravure printing or screen printing, and is dried to partially form uneven portions.
- the flat portion is partially provided on the substrate. That is, on the base material, there are regions where flat portions are provided and regions where uneven portions are provided. Furthermore, the concave portions of the uneven portion may be impregnated with a resin composition that forms the flat portion. For example, uneven parts are partially formed on one surface of the base material, and then a resin composition that forms flat parts is applied to the entire surface of the base material (including the top of the uneven parts), dried, When cured, a flat part is formed in the part of the base material where the uneven part is not formed, and the resin composition further penetrates into the concave part of the concave and convex part, and the resin composition forms part of the concave part to form the flat part. The composition will fill.
- the surface of the flat portion on the transfer layer side is relatively flatter than that of the uneven portion.
- the average peak height of the flat portion is preferably about 4 ⁇ m or less, more preferably about 3 ⁇ m or less, and even more preferably about 2 ⁇ m or less.
- the method for measuring the average height can be confirmed by the method described in the section ⁇ Structural Analysis of Peeling Layer> described above, and specifically by the method described in Examples.
- the pattern of the uneven portions can be maintained.
- the convex portions of the uneven portion are in contact with the surface of the transfer layer, but the flat portions are also in contact with the surface of the transfer layer.
- the resin component of the flat portion is not particularly limited as long as it has a low adhesion to the surface of the transfer layer (for example, a protective layer) and can easily peel off the transfer layer from the base material.
- the composition of the resin component forming the flat portion is preferably different from the composition of the resin component forming the uneven portion.
- the resin component forming the flat portion include a cured product of a thermosetting resin composition and a cured product of an ionizing radiation-curable resin composition. Specifically, fluorine resins, silicone resins, acrylic resins, polyester resins, polycarbonate resins, polyolefin resins, polystyrene resins, polyurethane resins, vinyl chloride-vinyl acetate copolymer resins, etc.
- a cured product of an ionizing radiation curable resin composition is preferred, and a cured product of an electron beam curable resin composition is more preferred, as it has excellent strength and can be instantly cured to give an accurate and precise shape. .
- An ionizing radiation-curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation-curable functional group.
- the ionizing radiation-curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and preferably includes functional groups having an ethylenic double bond such as (meth)acryloyl group, vinyl group, and allyl group. It will be done.
- ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quantum that can polymerize or crosslink molecules, and ultraviolet rays (UV) or electron beams (EB) are usually used, but other It also includes electromagnetic waves such as X-rays and ⁇ -rays, and charged particle beams such as ⁇ -rays and ion beams.
- UV ultraviolet rays
- EB electron beams
- cured products of electron beam curable resin compositions particularly preferred are cured products of electron beam curable resin compositions.
- the ionizing radiation-curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation-curable resins.
- (meth)acrylate monomers having a radically polymerizable unsaturated group in the molecule are preferred, and polyfunctional (meth)acrylate monomers are particularly preferred.
- the polyfunctional (meth)acrylate monomer include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group. From the viewpoint of heat resistance and moldability, the number of functional groups is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, even more preferably 2 or more and 4 or less, particularly preferably 2 or more and 3 or less. These polyfunctional (meth)acrylate monomers may be used alone or in combination.
- composition in which one or more of these polyfunctional (meth)acrylate monomers and one or more of the below-mentioned polymerizable oligomers are mixed.
- crosslink density, inter-crosslink molecular weight, etc. of the cured product can be adjusted, and various physical properties of the cured product can be adjusted.
- Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group.
- Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, and the like.
- the number of functional groups in these polymerizable oligomers is preferably 2 or more and 8 or less from the viewpoint of heat resistance and moldability, and the upper limit is more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3 or less.
- the resin component be an acrylic (meth)acrylate compound or a urethane (meth)acrylate compound.
- (meth)acrylate means "acrylate or methacrylate.”
- the resin component may be either an acrylic (meth)acrylate compound, a urethane (meth)acrylate compound, or a mixture thereof.
- the acrylic (meth)acrylate compound and the urethane (meth)acrylate compound may be monomers, oligomers, or a mixture of monomers and oligomers.
- the weight average molecular weight of the monomer and oligomer used for the flat portion is preferably 250 or more and 30,000 or less, more preferably 250 or more and 20,000 or less, and 250 or more and 15,000 or less, from the viewpoint of heat resistance and moldability. More preferred.
- the weight average molecular weight is an average molecular weight measured by GPC analysis and converted to standard polystyrene.
- the flat portion is preferably formed mainly of a cured product of a thermosetting resin composition or a cured product of an ionizing radiation-curable resin composition, and is substantially formed of a cured product of a thermosetting resin composition. It is preferable to consist of a cured product or a cured product of an ionizing radiation-curable resin composition.
- the "main component” means that the proportion of the cured product of the thermosetting resin composition or the cured product of the ionizing radiation-curable resin composition in the flat portion is 50% or more, preferably 60% or more, more preferably It means 80% or more, more preferably 90% or more, even more preferably 95% or more, and "substantially” means that the cured product of the thermosetting resin composition in the flat part or ionizing radiation It means that the ratio of the cured product of the curable resin composition is 95% or more, preferably 98% or more, and more preferably 100%.
- additives such as a curing agent and a polymerization initiator may be added to the resin composition forming the flat portion.
- the uneven portion and the flat portion may contain a common binder resin.
- the composition of the resin component forming the flat portion is preferably different from the composition of the resin component forming the uneven portion.
- the type of binder resin thermoplastic resin is as described for the uneven portion.
- the flat portion may contain a mold release agent to improve mold release properties from the protective layer.
- the release agent include silicone and waxes such as synthetic wax and natural wax.
- synthetic waxes include polyolefin waxes such as polyethylene wax and polypropylene wax.
- a crosslinkable and curable mold release component such as reactive silicone as the mold release agent.
- the mass ratio of the mold release agent to the total solid content of the flat portion is preferably 0.3 to 10% by mass, more preferably 0.5 to 5% by mass.
- the flat portion preferably has a thickness that does not differ too much from the average thickness of the adjacent uneven layer.
- the difference between the thickness of the flat portion and the average thickness of the uneven layer is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the thickness of the flat portion is preferably 5 to 650%, more preferably 10 to 450%, and even more preferably 15 to 200% of the average height of the uneven portion.
- the flat portion may further contain a matting agent.
- a matting agent the same one used for the uneven portion can be used.
- the amount of the matting agent added is preferably smaller than the amount added in the uneven portion.
- the amount of the matting agent added is 0.1 parts by mass or more and 10 parts by mass or less (solid content), more preferably 1.0 parts by mass or more, based on 100 parts by mass (solid content) of the resin component of the flat part.
- the content is preferably 5 parts by mass or less.
- the average particle size of the matting agent contained in the flat portion is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more.
- the average particle diameter of the matting agent contained in the flat portion is preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less, considering the visibility of the printed layer when it is made into a decorative molded product.
- the greater the difference in gloss between the uneven and flat areas the better the visibility of the uneven areas, so the average particle size of the matting agent contained in the flat areas should be at least 0.2 ⁇ m smaller than the average particle size contained in the uneven areas. is preferable, and more preferably smaller than 0.5 ⁇ m.
- the ratio of the average particle diameter of the matting agent to the thickness of the flat portion is preferably 1 or more, more preferably 1.2 or more, and even more preferably 1.4 or more. When the ratio satisfies the above numerical value, a sufficient matte effect can be imparted to the decorative molded product. On the other hand, if the flat portion is thin compared to the average particle size of the matting agent, the matting agent may fall off from the uneven portions, so in consideration of the retention of the matting agent, the ratio is preferably 10 or less. It is more preferably 8 or less, and even more preferably 6 or less.
- a matting agent contained in the uneven part and the flat part is used. It is preferable that the average particle size, the amount added, and the ratio of the average particle size of the matting agent to the layer thickness are different from each other, and it is more preferable that the uneven portions exhibit a matte design compared to the flat portions.
- the flat portion can be formed by a known printing method such as a gravure printing method, an offset printing method, a letterpress printing method, or a silk screen printing method.
- the protective layer is provided on the release sheet side of the transfer layer.
- the region formed on the uneven portion has a shape corresponding to the uneven shape of the uneven portion.
- the region formed on the flat portion of the protective layer has a shape corresponding to the surface shape of the flat portion.
- the protective layer preferably contains a cured product of a curable resin composition.
- the cured product of the curable resin composition include a cured product of a thermosetting resin composition, a cured product of an ionizing radiation curable resin composition, and a cured product of a mixture thereof. From the viewpoint of scratch resistance, a cured product of an ionizing radiation-curable resin composition is preferred. Moreover, among the cured products of the ionizing radiation curable resin composition, the cured products of the electron beam curable resin composition are preferred from the viewpoint that crosslinking and curing can be easily completed at the time of forming the protective layer.
- the thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating.
- the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin.
- a curing agent is added to these curable resins as necessary.
- the ionizing radiation-curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation-curable resins.
- polymerizable monomer As the polymerizable monomer, (meth)acrylate monomers having a radically polymerizable unsaturated group in the molecule are preferred, and polyfunctional (meth)acrylate monomers are particularly preferred.
- polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group, Acrylate monomers having acryloyl groups are preferred. These polymerizable oligomers may be used alone or in combination.
- the number of functional groups in the polymerizable monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, even more preferably 2 or more and 4 or less, particularly preferably 2 or more and 3 or less.
- Examples of the polymerizable oligomer include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the functional group.
- Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, and the like.
- polycarbonate (meth)acrylate oligomers are preferred.
- the polycarbonate (meth)acrylate oligomer is not particularly limited as long as it has a carbonate bond in the main chain and a (meth)acrylate group at the terminal or side chain, and may be a urethane (meth)acrylate oligomer having a polycarbonate skeleton. It may also be a certain polycarbonate-based urethane (meth)acrylate oligomer.
- the number of functional groups in these polymerizable oligomers is preferably 2 or more and 8 or less from the viewpoint of heat resistance and moldability, and the upper limit is more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3 or less.
- a monofunctional (meth)acrylate in the ionizing radiation curable resin, can be appropriately used in combination with the above-mentioned polyfunctional (meth)acrylate etc. for the purpose of lowering the viscosity.
- These monofunctional (meth)acrylates may be used alone or in combination.
- the weight average molecular weight of the monomer and oligomer used in the protective layer is preferably 250 or more and 30,000 or less, more preferably 250 or more and 20,000 or less, and 250 or more and 15,000 or less. More preferred.
- the protective layer does not substantially contain particles such as organic particles and inorganic particles. By not containing particles in the protective layer, the pattern of the underlying printed layer can be easily recognized. Substantially no particles in the protective layer means that the total solid content of the protective layer is 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less. , more preferably 0% by mass.
- the protective layer may further contain a thermoplastic resin as a resin component other than the cured product of the curable resin composition.
- a thermoplastic resin as a resin component other than the cured product of the curable resin composition.
- the thermoplastic resin general-purpose resins such as acrylic resin, polyester resin, and urethane resin can be used.
- the content of the thermoplastic resin is preferably 0.1 to 20% by mass of the total solids of the protective layer, more preferably 0.5 to 10% by mass, and 1 to 5% by mass. is even more preferable.
- the thickness of the protective layer is preferably 0.5 to 30 ⁇ m, more preferably 1 to 20 ⁇ m, and even more preferably 1 to 10 ⁇ m from the viewpoint of the balance between surface hardness and moldability.
- the protective layer can be formed by a known printing method such as a gravure printing method, an offset printing method, a letterpress printing method, or a silk screen printing method.
- thermosetting resin composition and/or the ionizing radiation-curable resin composition may be completely cured at the time of forming the protective layer, but from the viewpoint of moldability, the thermosetting resin composition and/or the ionizing radiation-curable resin composition may be completely cured at the time of forming the protective layer.
- the resin composition and/or the ionizing radiation-curable resin composition is kept in an uncured or semi-cured state, and after being transferred to the adherend, the thermosetting resin composition and/or the ionizing radiation-curable resin composition is cured. may be allowed to proceed and be completely cured.
- the printing layer is a layer for imparting a desired design to the decorative molded product.
- the pattern of the printing layer is arbitrary, and examples thereof include wood grain, stone grain, cloth grain, sand grain, circle, square, polygon, geometric pattern, letters, solid printing, and the like.
- the printing layer preferably contains a binder resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin, and a pigment and/or dye.
- a binder resin such as a polyvinyl resin, a polyester resin, an acrylic resin, a polyvinyl acetal resin, or a cellulose resin, and a pigment and/or dye.
- the thickness of the printed layer is preferably 0.5 to 40 ⁇ m, more preferably 1 to 30 ⁇ m from the viewpoint of design.
- the printing layer can be formed by a known printing method such as a gravure printing method, an offset printing method, a letterpress printing method, or a silk screen printing method.
- the adhesive layer has the role of improving the adhesion between the transfer layer and an adherend such as a resin molded body. Note that if the adhesiveness between the protective layer and the adherend is good, the adhesive layer may not be provided.
- the adhesive layer it is preferable to use a resin having adhesive properties suitable for the material of the adherend.
- the material of the adherend is an acrylic resin
- the material of the adherend is polyphenylene oxide/polystyrene resin, polycarbonate resin, or styrene resin
- the material of the adherend is polypropylene resin, it is preferable to use chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, or coumaron indene resin.
- the adhesive layer may contain additives such as ultraviolet absorbers and infrared absorbers.
- the thickness of the adhesive layer is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
- the adhesive layer can be formed by a known printing method such as a gravure printing method, an offset printing method, a letterpress printing method, or a silk screen printing method.
- the primer layer is a layer provided as necessary to improve the adhesion between the protective layer and the printing layer.
- the primer layer mainly contains a resin component.
- the resin component of the primer layer preferably contains a cured product of a curable resin composition in consideration of imparting heat resistance when placed in a high temperature environment such as in-mold molding.
- the curable resin composition include thermosetting resin compositions and ionizing radiation curable resin compositions.
- the thermosetting resin composition and the ionizing radiation-curable resin composition of the primer layer the same ones as those exemplified as the thermosetting resin composition and the ionizing radiation-curable resin composition of the protective layer can be used.
- the primer layer preferably contains a cured product of a thermosetting resin composition.
- the thermosetting resin composition include two-component curable urethane resins containing various polyol compounds such as polyether polyols, polyester polyols, and acrylic polyols, and curing agents such as isocyanate compounds.
- the thickness of the primer layer is preferably 0.1 to 6 ⁇ m, more preferably 0.5 to 5 ⁇ m.
- the primer layer may have a one-layer structure, but it can also have a structure in which two or more layers are laminated, taking into consideration the adhesion between the layers.
- the primer layer can be formed by a known printing method such as a gravure printing method, an offset printing method, a letterpress printing method, or a silk screen printing method.
- FIGS. 1 to 5 A decorated molded product manufactured using the transfer sheet of the present disclosure will be explained using FIGS. 1 to 5.
- 3 is a schematic cross-sectional view of the decorative molded product 41 with a transfer base material shown in FIG. 1
- FIG. 4 is a schematic cross-sectional view of the decorative molded product 41 with a transfer base material shown in FIG. be.
- FIG. 5 is a cross-sectional schematic diagram of a decorated molded product obtained by peeling off the release sheet 20 from the decorated molded product 41 with a transfer base material shown in FIG.
- the decorative molded product 40 includes an adherend 42 and a transfer layer 30 covering the adherend.
- the transfer layer 30 includes an adhesive layer 38, a printing layer 36, a primer layer 34, and a protective layer 32 in this order from the adherend side.
- the protective layer 32 is located at the outermost layer of the decorative molded product 40.
- the adherend is a resin molded body made of resin.
- the shape of the adherend may be a flat plate or a three-dimensional shape having a curved surface or the like. Further, the adherend may be colored.
- the resin molded body can be formed from a thermoplastic resin or a thermosetting resin.
- a thermoplastic resin include polystyrene resins, polyolefin resins, ABS resins (including heat-resistant ABS resins), AS resins, PC/ABS resins, PC/AS resins, AN resins, polyphenylene oxide resins, Examples include polycarbonate resin, polyacetal resin, acrylic resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polysulfone resin, and polyphenylene sulfide resin.
- the protective layer in the decorative molded product of the present disclosure has an uneven shape that is substantially complementary to the surface shape of the release layer of the release sheet. Further, it is preferable that the flat portion of the protective layer has an uneven shape that is substantially complementary to the flat portion of the release layer of the release sheet. In the decorative molded product of the present disclosure, for example, it is preferable that the uneven convex portions on the surface of the protective layer protrude more than the flat portions. Such a surface structure of the decorative molded product has an uneven shape that is easily visible even when observed from various angles.
- the decorative molded product of the present disclosure includes the steps of (1) adhering the transfer layer of the transfer sheet to an adherend and laminating the transfer sheet on the adherend, and (2) peeling off the release sheet of the transfer sheet. and transferring the transfer layer onto the adherend.
- the transfer sheet of the present disclosure is particularly suitably applied to the production of decorated molded products by in-mold molding (injection molding and simultaneous transfer decoration method). According to the present disclosure, a pattern with different gloss can be transferred to the surface of a resin molded body having a complicated surface shape such as a three-dimensional curved surface.
- One embodiment of the method for manufacturing a decorated molded product by in-mold molding includes the following steps. (S1) arranging the transfer layer side of the transfer sheet toward the inside of the in-mold mold; (S2) a step of injecting a resin for the adherend into the in-mold mold; (S3) integrating the transfer sheet and the resin to form a laminate in which the transfer sheet is laminated on the surface of the resin molded body (adherent); (S4) A step of peeling off the release sheet of the transfer sheet after taking out the laminate from the mold or at the same time as taking out the resin molded body from the mold.
- Example 1 A biaxially stretched polyethylene terephthalate film with a thickness of 75 ⁇ m was prepared as a base material for the release sheet.
- a coating liquid 1 for uneven portions for forming uneven portions of the release layer and a coating liquid for flat portions for forming flat portions of the release layer were prepared.
- the composition of each coating liquid is as described below.
- coating liquid 1 for uneven portions was applied in a pattern (wood grain conduit pattern) on one side of the base material by gravure printing and dried.
- the coating liquid for flat areas is applied to the areas where the coating liquid 1 for uneven areas is not applied, and by irradiating with an electron beam under the conditions of 165 KeV and 7 Mrad (70 kGy), the uneven areas and the flat areas are separated.
- a release sheet was obtained by forming adjacent release layers alternately.
- a coating liquid for a protective layer was applied onto the release layer of the release sheet, and an electron beam was irradiated under the conditions of 165 KeV and 5 Mrad (50 kGy) to form a protective layer with a thickness of 3 ⁇ m.
- coating liquid 1 for primer layer was applied onto the protective layer and dried to form a primer layer having a thickness of 2 ⁇ m.
- a brown ink (acrylic resin composition) was applied onto the primer layer using a gravure printing method and dried to form a 6 ⁇ m thick printed layer with a wood grain pattern.
- Examples 2 to 5 Transfer sheets of Examples 2 to 5 were obtained in the same manner as in Example 1, except that the thickness of the flat portion was set to the thickness shown in Table 1 (see FIG. 1).
- Example 6 A biaxially stretched polyethylene terephthalate film with a thickness of 75 ⁇ m was prepared as a base material for the release sheet.
- a coating liquid 2 for uneven portions for forming uneven portions of the release layer and a coating liquid for flat portions for forming flat portions of the release layer were prepared.
- the composition of each coating liquid is as described below.
- coating liquid 2 for uneven portions was applied in a pattern (wood grain conduit pattern) on one side of the base material by gravure printing and dried.
- the coating liquid for flat areas is applied to the areas where the coating liquid 2 for uneven areas is not applied, and the uneven areas and flat areas are irradiated with an electron beam under the conditions of 165 KeV and 7 Mrad (70 kGy).
- a release sheet was obtained by forming adjacent release layers alternately.
- a protective layer, a primer layer, a printing layer, and an adhesive layer were sequentially formed in the same manner as in Example 1 to obtain a transfer sheet of Example 6 ( Figure 1 reference).
- Example 7 A biaxially stretched polyethylene terephthalate film with a thickness of 75 ⁇ m was prepared as a base material for the release sheet.
- a coating liquid 3 for uneven portions for forming uneven portions of the release layer and a coating liquid for flat portions for forming flat portions of the release layer were prepared.
- the composition of each coating liquid is as described below.
- the uneven portion coating liquid 3 was applied in a pattern (wood grain conduit pattern) on one side of the base material by gravure printing and dried to form an uneven portion.
- a coating solution for flat areas is applied to the entire surface of the substrate including the uneven areas, and an electron beam is irradiated under the conditions of 165 KeV and 7 Mrad (70 kGy) to separate the uneven areas and the flat areas.
- a release sheet was obtained by forming adjacent release layers alternately.
- a protective layer, a primer layer, a printing layer, and an adhesive layer were sequentially formed in the same manner as in Example 1 to obtain a transfer sheet of Example 7 ( Figure 2 reference).
- Example 8-9 Transfer sheets of Examples 8 and 9 were obtained in the same manner as in Example 7, except that the thickness of the flat portion was set to the thickness shown in Table 1 (see FIG. 2).
- Example 10 to 11 and Comparative Example 1 A biaxially stretched polyethylene terephthalate film with a thickness of 75 ⁇ m was prepared as a base material for the release sheet.
- a coating liquid 4 for forming uneven portions for forming uneven portions of the release layer and a coating liquid for forming flat portions for forming flat portions of the release layer were prepared.
- the composition of each coating liquid is as described below.
- the coating liquid 4 for uneven portions was applied in a pattern (wood grain conduit pattern) on one side of the base material by gravure printing and dried to form uneven portions.
- a coating solution for flat areas is applied to the entire surface of the substrate including the uneven areas, and an electron beam is irradiated under the conditions of 165 KeV and 7 Mrad (70 kGy) to separate the uneven areas and the flat areas.
- a protective layer, a primer layer, a printing layer, and an adhesive layer were sequentially formed on the release layer of the obtained release sheet in the same manner as in Example 7, and the results were obtained in Examples 10 to 11 and Comparative Example 1, respectively.
- a transfer sheet was obtained (see Figure 2).
- Example 12 A biaxially stretched polyethylene terephthalate film with a thickness of 75 ⁇ m was prepared as a base material for the release sheet.
- a coating liquid 5 for uneven portions for forming uneven portions of the release layer and a coating liquid for flat portions for forming flat portions of the release layer were prepared.
- the composition of each coating liquid is as described below.
- the uneven portion coating liquid 5 was applied in a pattern (wood grain conduit pattern) on one side of the base material by gravure printing and dried to form an uneven portion.
- a coating solution for flat areas is applied to the entire surface of the substrate including the uneven areas, and an electron beam is irradiated under the conditions of 165 KeV and 7 Mrad (70 kGy) to separate the uneven areas and the flat areas.
- a release sheet was obtained by forming adjacent release layers alternately.
- a protective layer, a primer layer, a printing layer, and an adhesive layer were sequentially formed on the release layer of the obtained release sheet in the same manner as in Example 7 to obtain transfer sheets of Examples 10 to 11, respectively. (See Figure 2).
- a biaxially stretched polyethylene terephthalate film with a thickness of 75 ⁇ m was prepared as a base material for the release sheet.
- a coating liquid 6 for uneven portions that forms uneven portions of the release layer and a coating liquid 6 for flat portions that forms flat portions of the release layer were prepared.
- the composition of each coating liquid is as described below.
- the coating liquid 6 for uneven portions was applied in a pattern (wood grain conduit pattern) on one side of the base material by gravure printing, and dried to form uneven portions.
- a coating solution for flat areas is applied to the entire surface of the substrate including the uneven areas, and an electron beam is irradiated under the conditions of 165 KeV and 7 Mrad (70 kGy) to separate the uneven areas and the flat areas.
- a release sheet was obtained by forming adjacent release layers alternately.
- a protective layer, a primer layer, a printing layer, and an adhesive layer were sequentially formed in the same manner as in Example 7 to obtain a transfer sheet of Comparative Example 2. (see Figure 2).
- Coating liquid for uneven areas Coating liquids 1 to 6 for uneven areas were prepared, respectively, with the following formulations.
- Coating liquid for uneven parts 1 Nitrocellulose resin (thermoplastic resin, weight average molecular weight: 50,000) 100 parts by mass Matting agent (amorphous silica, average particle size 3 ⁇ m, oil absorption 250 ml/100 g) 130 parts by mass Silicone 2 parts by mass Solvent (ethyl acetate) appropriate amount
- Coating liquid 2 for uneven parts Nitrocellulose resin (thermoplastic resin, weight average molecular weight: 50,000) 100 parts by mass Matting agent (spherical silica, average particle size 3 ⁇ m, oil absorption 30 ml/100g) 130 parts by mass Silicone 2 parts by mass Solvent (ethyl acetate) Appropriate amount unevenness Partial coating liquid 3: Nitrocellulose resin (thermoplastic resin, weight average molecular weight: 50,000) 100 parts by mass Matting agent (amorphous silica, average particle size 3 ⁇ m, oil ab
- Coating liquid for flat areas A coating solution for flat areas was prepared with the following formulation. Coating liquid for flat areas: Bifunctional polycarbonate acrylate (weight average molecular weight: 5,000) 84 parts by mass Pentaerythritol triacrylate (PETA) 14 parts by mass Matting agent (amorphous silica, average particle size 3 ⁇ m, oil absorption 350 ml/100 g) 5 parts by mass Reactive silicone 2 parts by mass of solvent (mixture of methyl ethyl ketone and isopropyl alcohol) Appropriate amount
- a protective layer coating solution having the following formulation was prepared. 95 parts by mass of tetrafunctional urethane acrylate (weight average molecular weight: 10,000) 5 parts by mass of trifunctional acrylate monomer (weight average molecular weight: 300) Solvent (mixture of methyl ethyl ketone and isopropyl alcohol) Appropriate amount
- Coating liquid for primer layer A primer layer coating liquid having the following formulation was prepared. ⁇ Coating liquid for primer layer> Acrylic polyol (hydroxyl value: 80 mgKOH/g, Tg: 90°C) 100 parts by mass XDI (m-xylylene diisocyanate) 10 parts by mass Solvent (methyl ethyl ketone) Appropriate amount
- the sheet on which the uneven portion was printed on the base material and before the flat portion was printed was targeted for analysis.
- a shape analysis laser microscope (VK-X1000 manufactured by Keyence Corporation) was used. A total of three locations were measured, with an arbitrary width of 100 um on the uneven portion as the measurement area. At that time, the surface of the base material on which the release layer was formed was set as the zero height point.
- cross-sectional observation was performed using a scanning electron microscope (FlexSEM1000II manufactured by Hitachi High-Tech Corporation) on a sample obtained by cross-sectionally polishing the transfer sheet, and the height of the uneven portion in a 50 ⁇ m wide area was 6. Similar measurement results were obtained by measuring twice.
- the cross-sectional structure analysis method based on cross-sectional observation requires more time.
- the decorative molded products produced in Examples and Comparative Examples were visually observed from an accuracy of 60 degrees ⁇ 10 degrees, and the visibility was evaluated as follows based on the presence or absence of gloss difference between areas with uneven parts and flat areas. It was evaluated based on the following criteria. 20 subjects performed the evaluation, and the average score was calculated. (Visibility evaluation criteria) 2 points: There is a clear difference in gloss. 1 point: There is a difference in gloss, but the clarity of the difference in gloss is lower than the rating of "2 points.” 0 points: There is no noticeable difference in gloss.
- Average score of evaluation criteria is 1.8 or more
- B+ Average score of evaluation criteria is 1.4 or more and less than 1.8
- the transfer sheets of Examples 1 to 12 are transfer sheets having a transfer layer on a release sheet, and the release sheet includes a release layer and a base material in order from the transfer layer side, and the release layer includes: It contains a binder resin and a matting agent, and has an uneven part having a plurality of protrusions on the transfer layer side, and a flat part where the surface on the transfer layer side is relatively flat than the uneven part, and the release layer A plurality of convex portions of the uneven portion are in contact with the transfer layer.
- the transfer sheets of Examples 1 to 12 were able to impart an uneven shape to the surface of the decorated molded product that was easily visible even when observed from various angles.
- Transfer sheet 20 Release sheet 22 Base material 23 Release layer 24 Uneven portion 25 Flat portion 30 Transfer layer 32 Protective layer 34 Primer layer 36 Printing layer 38 Adhesive layer 40 Decorative molded product 41 Decorative molded product with transfer base material 42 Adherent
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- Laminated Bodies (AREA)
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- Lining Or Joining Of Plastics Or The Like (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
項1. 離型シート上に転写層を有する転写シートであって、
前記離型シートは、前記転写層側から順に、剥離層と、基材とを備え、
前記剥離層は、
バインダー樹脂及びマット剤を含み、前記転写層側に複数の凸部を有する凹凸部分と、
前記凹凸部分よりも前記転写層側の表面が相対的に平坦である平坦部分と、
を有しており、
前記剥離層の前記凹凸部分の前記複数の凸部が、前記転写層に接している、転写シート。
項2. 前記転写層の前記凹凸部分と接している表面は、前記凹凸部分と接することで凹凸形状を有しており、
前記転写層の前記凹凸形状に含まれる複数の凸部の先端は、前記転写層が前記平坦部分と接している表面よりも、前記基材側に位置している、項1に記載の転写シート。
項3. 前記凹凸部分に含まれる前記マット剤の吸油量が、150ml/100g以上である、項1または2に記載の転写シート。
項4. 前記凹凸部分の前記複数の凸部の平均ピーク高さが、3.3μm以上である、項1~3のいずれか1項に記載の転写シート。
項5. 前記平坦部分の厚みは、前記凹凸部分の平均高さの5%以上650%以下である、項1~4のいずれか1項に記載の転写シート。
項6. 前記平坦部分は、前記マット剤を含む、項1~5のいずれか1項に記載の転写シート。
項7. 項1~6のいずれか1項に記載の転写シートの前記転写層が、被着体に積層されてなる、加飾成形品。
項8. 項1~6のいずれか1項に記載の転写シートの前記転写層を被着体と接着し、前記被着体上に前記転写シートを積層する工程と、
前記転写シートの前記離型シートを剥離して、前記被着体上に前記転写層を転写する工程と、を含む、加飾成形品の製造方法。
図1及び図2の模式図に示すように、本開示の転写シート10は、離型シート20上に転写層30を有する。離型シートは20、転写層30側から順に、剥離層23と、基材22とを備える。剥離層23は、凹凸部分24と平坦部分25とを備えている。凹凸部分24は、転写層30側に複数の凸部を有する。また、平坦部分25は、凹凸部分24よりも転写層30側の表面が相対的に平坦である。本開示の転写シート10を離型シート20側から平面視した場合、凹凸部分24と平坦部分25とは交互に形成されていることが好ましく、凹凸部分24と平坦部分25とは交互に形成されてパターンを形成していることが好ましい。凹凸部分24と平坦部分25とが形成するパターン形状については、後述のとおりである(例えば木目導管パターンなどである)。
本開示において、基材は、転写層を被着体に転写するための転写用基材として機能する。本開示の転写シート(例えば図1,2参照)を被着体に転写することで、転写用基材付き加飾成形品(例えば図3,4参照)が得られる。さらに、転写用基材付き加飾成形品から、基材と剥離層を含む離型シートを剥離することにより、加飾成形品が得られる。
剥離層は、凹凸部分と平坦部分とを備えている。凹凸部分は、転写層側に複数の凸部を有する。凹凸部分の基材側の表面は平坦である。また、平坦部分は、凹凸部分よりも転写層側の表面が相対的に平坦である。また、平坦部分の基材側の表面は平坦である。以下、剥離層の凹凸部分と平坦部分について、それぞれ説明する。
凹凸部分は、基材の一方の面上の一部のみに設けられる。凹凸部分を部分的に形成することにより、転写層の表面(転写層と剥離層との界面)に凹凸部分の凹凸形状に対応した、凹凸形状を付与することができる。本開示の転写シートを用いることにより、例えば、保護層面内で艶差があるパターンの意匠が付与された加飾成形品を製造することができる。
剥離層の凹凸部分の構造分析については、基材上に凹凸部分が印刷され、且つ、平坦部分を印刷する前のシートが入手可能な場合は、当該シートを分析対象とする。市販の形状解析レーザー顕微鏡(例えばキーエンス社製のVK-X1000)を使用する。凹凸部分の任意の100um幅を測定エリアとして、合計3カ所を測定する。その際、剥離層が形成されている基材の表面を高さゼロ地点とする。一方、前記のシートが入手できない場合には、別の構造分析法として、転写シートを断面研磨したサンプルに対して、市販の走査電子顕微鏡(例えば日立ハイテク社製のFlexSEM1000II)を用いて断面観察を行い、50μm幅のエリアの凹凸部分の高さ6回測定する。なお、断面観察による構造分析法には、より多くの時間を要する。
平坦部分は、基材上に部分的に設けられる。すなわち、基材上には、平坦部分が設けられている領域と、凹凸部分が設けられている領域とが存在している。さらに、凹凸部分の凹部には、平坦部分を形成する樹脂組成物が含浸されていてもよい。例えば基材の一方側の表面に凹凸部分を部分的に形成し、さらに、基材の全面(凹凸部分の上も含めて)に対して、平坦部分を形成する樹脂組成物を塗布、乾燥、硬化させると、基材の凹凸部分が形成されていない部分には平坦部分が形成され、さらに、凹凸部分の凹部に当該樹脂組成物が浸透し、当該凹部の一部を平坦部分を形成する樹脂組成物が埋めることになる。
<保護層>
保護層は、転写層の離型シート側に設けられる。保護層の離型シート側の表面形状は、凹凸部分上に形成された領域は、凹凸部分の凹凸形状に対応した形状となる。一方、保護層が平坦部分と接触している場合、保護層の平坦部分上に形成された領域は、平坦部分の表面形状に対応した形状となる。
印刷層は、加飾成形品に所望の意匠性を付与するための層である。印刷層のパターンは任意であり、例えば、木目、石目、布目、砂目、円、四角形、多角形、幾何学模様、文字、ベタ印刷等が挙げられる。
接着層は、樹脂成形体等である被着体と、転写層との接着性を良好にする役割を有する。なお、保護層と被着体との接着性が良好な場合は、接着層を設けなくてもよい。
プライマー層は、保護層と印刷層との密着性を向上するために、必要に応じて設けられる層である。
本開示の転写シートを用いて製造される加飾成形品を、図1~5を用いて説明する。図3は、図1に示された転写用基材付き加飾成形品41の断面略図であり、図4は、図2に示された転写用基材付き加飾成形品41の断面略図である。また、図5は、図3の転写用基材付き加飾成形品41から離型シート20を剥離して得られる加飾成形品の断面概略図である。加飾成形品40は、被着体42と、被着体を被覆する転写層30とを有する。図5において、転写層30は、被着体側から順に、接着層38、印刷層36、プライマー層34及び保護層32を備える。保護層32が加飾成形品40の最表層に位置する。
被着体は、樹脂からなる樹脂成型体である。被着体の形状は、平板状であってもよいし、曲面等を有する三次元形状であってもよい。また、被着体は有色であってもよい。
本開示の加飾成形品における保護層は、離型シートの剥離層の表面形状と略相補的な凹凸形状を有する。また、保護層の平坦部分は、離型シートの剥離層の平坦部分と略相補的な凹凸形状を有することが好ましい。本開示の加飾成形品においては、例えば、保護層の表面の凹凸形状の凸部は、平坦部分よりも突出していることが好ましい。加飾成形品のこのような表面構造は、様々な角度から観察しても視認しやすい凹凸形状となる。
本開示の加飾成形品は、(1)転写シートの転写層を被着体と接着し、被着体上に転写シートを積層する工程と、(2)転写シートの離型シートを剥離して、被着体上に転写層を転写する工程と、を含む。
(S1)転写シートの転写層側をインモールド成形用金型の内側に向けて配置する工程と、
(S2)上記インモールド成形用金型内に被着体用の樹脂を射出注入する工程と、
(S3)転写シートと、上記樹脂とを一体化させて、樹脂成形体(被着体)の表面上に転写シートを積層させた積層体を形成する工程と、
(S4)積層体を金型から取り出した後、または、樹脂成形体を金型から取り出すと同時に、転写シートの離型シートを剥離する工程。
<転写シートの製造>
(実施例1)
離型シートの基材として、厚み75μmの二軸延伸ポリエチレンテレフタレートフィルムを用意した。また、剥離層の凹凸部分を形成する凹凸部分用塗布液1と、剥離層の平坦部分を形成する平坦部分用塗布液を用意した。各塗布液の組成については後述の通りである。次に、グラビア印刷により、基材の一方面に、凹凸部分用塗布液1をパターン状(木目導管パターン)に塗布、乾燥させた。次に、平坦部分用塗布液を前記凹凸部分用塗布液1が塗布されていない箇所に塗布し、165KeV、7Mrad(70kGy)の条件で電子線を照射することで、凹凸部分と平坦部分とが隣接するようにして交互に形成された剥離層を形成し、離型シートを得た。凹凸部分の平均ピーク高さ(μm)、平均高さ(μm)、ピーク高さのばらつき(%)(変動変数=標準偏差/平均)及び平坦部分の厚み(μm)は、それぞれ、表1に記載のとおりである。次に、離型シートの剥離層上に、保護層用塗布液を塗布し、165KeV、5Mrad(50kGy)の条件で電子線を照射して、厚み3μmの保護層を形成した。次いで、保護層上に、プライマー層用塗布液1を塗布、乾燥し、厚み2μmのプライマー層を形成した。次いで、プライマー層上に、茶褐色インキ(アクリル系樹脂組成物)をグラビア印刷法で塗布し、乾燥し、厚み6μmの木目模様の印刷層を形成した。次いで、印刷層上に、熱可塑性樹脂(アクリル系樹脂)を溶剤で希釈した接着剤層用塗布液を塗布、乾燥し、厚み2μmのヒートシール性を有する接着層を形成した。上記の工程により、実施例1の転写シートを得た(図1参照)。
平坦部分の厚みを表1に記載の厚みに設定したこと以外は、実施例1と同様にして、それぞれ、実施例2~5の転写シートを得た(図1参照)。
離型シートの基材として、厚み75μmの二軸延伸ポリエチレンテレフタレートフィルムを用意した。また、剥離層の凹凸部分を形成する凹凸部分用塗布液2と、剥離層の平坦部分を形成する平坦部分用塗布液を用意した。各塗布液の組成については後述の通りである。次に、グラビア印刷により、基材の一方面に、凹凸部分用塗布液2をパターン状(木目導管パターン)に塗布、乾燥させた。次に、平坦部分用塗布液を前記凹凸部分用塗布液2が塗布されていない箇所に塗布し、165KeV、7Mrad(70kGy)の条件で電子線を照射することで、凹凸部分と平坦部分とが隣接するようにして交互に形成された剥離層を形成し、離型シートを得た。凹凸部分の平均ピーク高さ(μm)、平均高さ(μm)、ピーク高さのばらつき(%)(変動変数=標準偏差/平均)及び平坦部分の厚み(μm)は、それぞれ、表1に記載のとおりである。得られた離型シートの剥離層上に、実施例1と同様にして、保護層、プライマー層、印刷層、及び接着層を順に形成して、実施例6の転写シートを得た(図1参照)。
離型シートの基材として、厚み75μmの二軸延伸ポリエチレンテレフタレートフィルムを用意した。また、剥離層の凹凸部分を形成する凹凸部分用塗布液3と、剥離層の平坦部分を形成する平坦部分用塗布液を用意した。各塗布液の組成については後述の通りである。次に、グラビア印刷により、基材の一方面に、凹凸部分用塗布液3をパターン状(木目導管パターン)に塗布、乾燥させることで、凹凸部分を形成した。次に、凹凸部分の上も含めて基材上の全面に、平坦部分用塗布液を塗布し、165KeV、7Mrad(70kGy)の条件で電子線を照射することで、凹凸部分と平坦部分とが隣接するようにして交互に形成された剥離層を形成し、離型シートを得た。凹凸部分の平均ピーク高さ(μm)、平均高さ(μm)、ピーク高さのばらつき(%)(変動変数=標準偏差/平均)及び平坦部分の厚み(μm)は、それぞれ、表1に記載のとおりである。得られた離型シートの剥離層上に、実施例1と同様にして、保護層、プライマー層、印刷層、及び接着層を順に形成して、実施例7の転写シートを得た(図2参照)。
平坦部分の厚みを表1に記載の厚みに設定したこと以外は、実施例7と同様にして、それぞれ、実施例8~9の転写シートを得た(図2参照)。
離型シートの基材として、厚み75μmの二軸延伸ポリエチレンテレフタレートフィルムを用意した。また、剥離層の凹凸部分を形成する凹凸部分用塗布液4と、剥離層の平坦部分を形成する平坦部分用塗布液を用意した。各塗布液の組成については後述の通りである。次に、グラビア印刷により、基材の一方面に、凹凸部分用塗布液4をパターン状(木目導管パターン)に塗布、乾燥させることで、凹凸部分を形成した。次に、凹凸部分の上も含めて基材上の全面に、平坦部分用塗布液を塗布し、165KeV、7Mrad(70kGy)の条件で電子線を照射することで、凹凸部分と平坦部分とが隣接するようにして交互に形成された剥離層を形成し、離型シートを得た。凹凸部分の平均ピーク高さ(μm)、平均高さ(μm)、ピーク高さのばらつき(%)(変動変数=標準偏差/平均)及び平坦部分の厚み(μm)は、それぞれ、表1に記載のとおりである。得られた離型シートの剥離層上に、実施例7と同様にして、保護層、プライマー層、印刷層、及び接着層を順に形成して、それぞれ、実施例10~11及び比較例1の転写シートを得た(図2参照)。
離型シートの基材として、厚み75μmの二軸延伸ポリエチレンテレフタレートフィルムを用意した。また、剥離層の凹凸部分を形成する凹凸部分用塗布液5と、剥離層の平坦部分を形成する平坦部分用塗布液を用意した。各塗布液の組成については後述の通りである。次に、グラビア印刷により、基材の一方面に、凹凸部分用塗布液5をパターン状(木目導管パターン)に塗布、乾燥させることで、凹凸部分を形成した。次に、凹凸部分の上も含めて基材上の全面に、平坦部分用塗布液を塗布し、165KeV、7Mrad(70kGy)の条件で電子線を照射することで、凹凸部分と平坦部分とが隣接するようにして交互に形成された剥離層を形成し、離型シートを得た。凹凸部分の平均ピーク高さ(μm)、平均高さ(μm)、ピーク高さのばらつき(%)(変動変数=標準偏差/平均)及び平坦部分の厚み(μm)は、それぞれ、表1に記載のとおりである。得られた離型シートの剥離層上に、実施例7と同様にして、保護層、プライマー層、印刷層、及び接着層を順に形成して、それぞれ、実施例10~11の転写シートを得た(図2参照)。
離型シートの基材として、厚み75μmの二軸延伸ポリエチレンテレフタレートフィルムを用意した。また、剥離層の凹凸部分を形成する凹凸部分用塗布液6と、剥離層の平坦部分を形成する平坦部分用塗布液を用意した。各塗布液の組成については後述の通りである。次に、グラビア印刷により、基材の一方面に、凹凸部分用塗布液6をパターン状(木目導管パターン)に塗布、乾燥させることで、凹凸部分を形成した。次に、凹凸部分の上も含めて基材上の全面に、平坦部分用塗布液を塗布し、165KeV、7Mrad(70kGy)の条件で電子線を照射することで、凹凸部分と平坦部分とが隣接するようにして交互に形成された剥離層を形成し、離型シートを得た。凹凸部分の平均ピーク高さ(μm)、平均高さ(μm)、ピーク高さのばらつき(%)(変動変数=標準偏差/平均)及び平坦部分の厚み(μm)は、それぞれ、表1に記載のとおりである。得られた離型シートの剥離層上に、実施例7と同様にして、保護層、プライマー層、印刷層、及び接着層を順に形成して、それぞれ、比較例2の転写シートを得た(図2参照)。
それぞれ、下記処方の凹凸部分用塗布液1~6を調製した。
凹凸部分用塗布液1:
ニトロセルロース樹脂(熱可塑性樹脂、重量平均分子量:50,000) 100質量部
マット剤(不定形シリカ、平均粒径3μm、吸油量250ml/100g) 130質量部
シリコーン 2質量部
溶剤(酢酸エチル)適量
凹凸部分用塗布液2:
ニトロセルロース樹脂(熱可塑性樹脂、重量平均分子量:50,000) 100質量部
マット剤(球状シリカ、平均粒径3μm、吸油量30ml/100g) 130質量部
シリコーン 2質量部
溶剤(酢酸エチル)適量
凹凸部分用塗布液3:
ニトロセルロース樹脂(熱可塑性樹脂、重量平均分子量:50,000) 100質量部
マット剤(不定形シリカ、平均粒径3μm、吸油量250ml/100g) 130質量部
溶剤(酢酸エチル)適量
凹凸部分用塗布液4:
ニトロセルロース樹脂(熱可塑性樹脂、重量平均分子量:50,000) 100質量部
マット剤(不定形シリカ、平均粒径3μm、吸油量200ml/100g) 130質量部
溶剤(酢酸エチル)適量
凹凸部分用塗布液5:
ニトロセルロース樹脂(熱可塑性樹脂、重量平均分子量:50,000) 100質量部
マット剤(不定形シリカ、平均粒径3μm、吸油量150ml/100g) 130質量部
溶剤(酢酸エチル)適量
凹凸部分用塗布液6:
ニトロセルロース樹脂(熱可塑性樹脂、重量平均分子量:50,000) 100質量部
マット剤(球状及び不定形シリカの混合物、平均粒径3μm、吸油量100ml/100g) 130質量部
溶剤(酢酸エチル)適量
下記処方の平坦部分用塗布液を調製した。
平坦部分用塗布液:
2官能ポリカーボネートアクリレート(重量平均分子量:5,000) 84質量部
ペンタエリスリトールトリアクリレート(PETA) 14質量部
マット剤(不定形シリカ、平均粒径3μm、吸油量350ml/100g) 5質量部
反応性シリコーン 2質量部
溶剤(メチルエチルケトンとイソプロピルアルコール混合物) 適量
下記処方の保護層用塗布液を調製した。
4官能ウレタンアクリレート(重量平均分子量:10,000)95質量部
3官能アクリレートモノマー(重量平均分子量:300)5質量部
溶剤(メチルエチルケトンとイソプロピルアルコール混合物) 適量
下記処方のプライマー層用塗布液を作製した。
<プライマー層用塗布液>
アクリルポリオール(水酸基価:80mgKOH/g、Tg:90℃)100質量部
XDI(m-キシリレンジイソシアナート)10質量部
溶剤(メチルエチルケトン)適量
実施例及び比較例で得られた各転写シートについて、それぞれ、以下の方法により転写シートの剥離層の構造分析を行った。剥離層について測定された凹凸部分の平均ピーク高さ(μm)、平均高さ(μm)、ピーク高さのばらつき(%)(変動変数=標準偏差/平均)、及び平坦部分の厚み(μm)を表1に示す。
実施例及び比較例で得られた各転写シートを用い、以下の手順で加飾成形品を製造した。上下一組のインモールド成形用金型の一方の側に、実施例1~12及び比較例1~2の転写シートをそれぞれ配置した。このとき、接着層が金型の内側(射出樹脂と接する側)を向くように配置した。次いで、金型を締め、金型内に射出樹脂(PC/ABS樹脂)を注入し、転写シートと射出樹脂を含む射出樹脂層とを一体化させた積層体(10cm×16cm×厚さ2mmの板状体)を得た。次いで、金型を開けた後、積層体から転写シートの離型シート(基材~平坦部分)を剥がし、実施例1~12、比較例1~2の加飾成形品を得た。
実施例及び比較例で得られた加飾成形品の表面を以下の方法で観察し、表面凹凸形状の凸部が平坦部よりも高い位置にあるか否かの確認(高い位置にあればOK、無ければNG)と、様々な角度からの表面凹凸形状の視認性(意匠性)を評価した。結果を表1に示す。
(視認性の評価基準)
2点:艶差が明瞭であるもの
1点:艶差があるものの、「2点」の評価より艶差の明瞭性が劣るもの
0点:艶差が感じられないもの
B+:評価基準の平均点が1.4以上1.8未満
B:評価基準の平均点が1.0以上1.4未満
C:評価基準の平均点が1.0未満
20離型シート
22基材
23剥離層
24凹凸部分
25平坦部分
30転写層
32保護層
34プライマー層
36印刷層
38接着層
40加飾成形品
41転写用基材付き加飾成形品
42被着体
Claims (8)
- 離型シート上に転写層を有する転写シートであって、
前記離型シートは、前記転写層側から順に、剥離層と、基材とを備え、
前記剥離層は、
バインダー樹脂及びマット剤を含み、前記転写層側に複数の凸部を有する凹凸部分と、
前記凹凸部分よりも前記転写層側の表面が相対的に平坦である平坦部分と、
を有しており、
前記剥離層の前記凹凸部分の前記複数の凸部が、前記転写層に接している、転写シート。 - 前記転写層の前記凹凸部分と接している表面は、前記凹凸部分と接することで凹凸形状を有しており、
前記転写層の前記凹凸形状に含まれる複数の凸部の先端は、前記転写層が前記平坦部分と接している表面よりも、前記基材側に位置している、請求項1に記載の転写シート。 - 前記凹凸部分に含まれる前記マット剤の吸油量が、150ml/100g以上である、請求項1または2に記載の転写シート。
- 前記凹凸部分の前記複数の凸部の平均ピーク高さが、3.3μm以上である、請求項1または2に記載の転写シート。
- 前記平坦部分の厚みは、前記凹凸部分の平均高さの5%以上650%以下である、請求項1または2に記載の転写シート。
- 前記平坦部分は、前記マット剤を含む、請求項1または2に記載の転写シート。
- 請求項1または2に記載の転写シートの前記転写層が、被着体に積層されてなる、加飾成形品。
- 請求項1または2に記載の転写シートの前記転写層を被着体と接着し、前記被着体上に前記転写シートを積層する工程と、
前記転写シートの前記離型シートを剥離して、前記被着体上に前記転写層を転写する工程と、を含む、加飾成形品の製造方法。
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| CN202380050425.0A CN119365340A (zh) | 2022-06-27 | 2023-06-27 | 转印片、装饰成型品和装饰成型品的制造方法 |
| JP2024530885A JP7605378B2 (ja) | 2022-06-27 | 2023-06-27 | 転写シート、加飾成形品、及び加飾成形品の製造方法 |
| EP23831460.3A EP4549147A1 (en) | 2022-06-27 | 2023-06-27 | Transfer sheet, decorative molded article, and method for producing decorative molded article |
| JP2024215444A JP2025038032A (ja) | 2022-06-27 | 2024-12-10 | 転写シート、加飾成形品、及び加飾成形品の製造方法 |
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| JP (3) | JP2024003748A (ja) |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05139095A (ja) * | 1991-11-19 | 1993-06-08 | Dainippon Printing Co Ltd | 艶消し転写箔及び化粧材 |
| JP2010149383A (ja) * | 2008-12-25 | 2010-07-08 | Nissha Printing Co Ltd | 部分マット転写シートの製造方法 |
| US20120003442A1 (en) * | 2010-07-01 | 2012-01-05 | Sipix Chemical Inc. | Decoration film |
| JP4885281B2 (ja) | 2010-01-19 | 2012-02-29 | 日本写真印刷株式会社 | 地汚れ防止部分マットハードコート転写シート |
| WO2015174044A1 (ja) * | 2014-05-13 | 2015-11-19 | 凸版印刷株式会社 | 転写フィルム、及びこれを用いた転写成形品 |
| JP2017159649A (ja) * | 2016-03-04 | 2017-09-14 | 大日本印刷株式会社 | 加飾成形品、加飾成形品の製造方法及び転写シート |
| JP2018126984A (ja) * | 2017-02-10 | 2018-08-16 | 大日本印刷株式会社 | 多面付け部分凹凸転写シートの中間基材及びこれを用いた離型シート、並びに、多面付け部分凹凸転写シート及びこれを用いた加飾成形品の製造方法 |
| JP2019006086A (ja) * | 2017-06-28 | 2019-01-17 | 大日本印刷株式会社 | 加飾成形品、加飾成形品の製造方法、転写シート及び表示装置 |
| JP6866963B2 (ja) | 2019-03-29 | 2021-04-28 | 大日本印刷株式会社 | 転写シート及び加飾成形品の製造方法 |
-
2023
- 2023-02-28 JP JP2023029390A patent/JP2024003748A/ja active Pending
- 2023-06-27 WO PCT/JP2023/023824 patent/WO2024005020A1/ja not_active Ceased
- 2023-06-27 CN CN202380050425.0A patent/CN119365340A/zh active Pending
- 2023-06-27 JP JP2024530885A patent/JP7605378B2/ja active Active
- 2023-06-27 EP EP23831460.3A patent/EP4549147A1/en active Pending
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2024
- 2024-12-10 JP JP2024215444A patent/JP2025038032A/ja active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05139095A (ja) * | 1991-11-19 | 1993-06-08 | Dainippon Printing Co Ltd | 艶消し転写箔及び化粧材 |
| JP2010149383A (ja) * | 2008-12-25 | 2010-07-08 | Nissha Printing Co Ltd | 部分マット転写シートの製造方法 |
| JP4885281B2 (ja) | 2010-01-19 | 2012-02-29 | 日本写真印刷株式会社 | 地汚れ防止部分マットハードコート転写シート |
| US20120003442A1 (en) * | 2010-07-01 | 2012-01-05 | Sipix Chemical Inc. | Decoration film |
| WO2015174044A1 (ja) * | 2014-05-13 | 2015-11-19 | 凸版印刷株式会社 | 転写フィルム、及びこれを用いた転写成形品 |
| JP2017159649A (ja) * | 2016-03-04 | 2017-09-14 | 大日本印刷株式会社 | 加飾成形品、加飾成形品の製造方法及び転写シート |
| JP2018126984A (ja) * | 2017-02-10 | 2018-08-16 | 大日本印刷株式会社 | 多面付け部分凹凸転写シートの中間基材及びこれを用いた離型シート、並びに、多面付け部分凹凸転写シート及びこれを用いた加飾成形品の製造方法 |
| JP2019006086A (ja) * | 2017-06-28 | 2019-01-17 | 大日本印刷株式会社 | 加飾成形品、加飾成形品の製造方法、転写シート及び表示装置 |
| JP6866963B2 (ja) | 2019-03-29 | 2021-04-28 | 大日本印刷株式会社 | 転写シート及び加飾成形品の製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2024005020A1 (ja) | 2024-01-04 |
| EP4549147A1 (en) | 2025-05-07 |
| JP2025038032A (ja) | 2025-03-18 |
| JP2024003748A (ja) | 2024-01-15 |
| JP7605378B2 (ja) | 2024-12-24 |
| CN119365340A (zh) | 2025-01-24 |
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