JP2019051683A - Three-dimensional molding and method for manufacturing three-dimensional molding - Google Patents

Abstract

To provide a three-dimensional molding in which a resin film is uniformly laminated on the surface of an adherend having a recess.SOLUTION: There is provided a three-dimensional molding 70 in which an adhesive sheet 11, a vapor-deposited layer 22 and a resin film 21 are coated on at least the surface of a recess 72 of an adherend having the recess 72 in this order, where the three-dimensional molding 70 contains a plastic resin or a carbon fiber-reinforced plastic, the adhesive sheet 11 contains an acrylic polymer and has a film thickness of 20-200 μm, and the resin film 21 is one or more selected from an acrylic resin, a polyolefin resin, an urethane resin, a polyamide resin, a polycarbonate resin and an ABS resin.SELECTED DRAWING: Figure 7

Description

  The present invention relates to a three-dimensional molded article and a method for producing a three-dimensional molded article.

Acrylic adhesives are used for laminating and bonding substrates such as touch panels, mobile phones, displays, and laminated glass.
Patent Document 1 describes an adhesive sheet for a protective film that is suitable for a panel protective film of a portable information terminal such as a mobile phone or a touch panel, particularly for a glass panel, and can be adhered according to the shape of the panel. Patent Document 1 discloses a protective film pressure-sensitive adhesive sheet in which a hard coat layer, a transparent substrate film, an adhesive layer, a polyester film, a pressure-sensitive adhesive layer, and a release sheet are sequentially laminated.
Patent Document 2 describes a pressure-sensitive adhesive containing a main polymer having a crosslinkable functional group, a low molecular weight polymer having a hydrogen bonding functional group, and an isocyanate crosslinker as an acrylic pressure-sensitive adhesive used for a touch panel. Has been.

JP 2012-35431 A JP 2013-1769 A

  By the way, there are a wide variety of shapes and types of adherends and laminates to be bonded by an adhesive. For example, when a resin film is coated on an adherend having a complicated shape via an adhesive layer, the resin film can be adhered following the shape of the adherend, and it is required to adhere evenly and uniformly.

The pressure-sensitive adhesive sheet for protective film described in Patent Document 1 has a complicated layer structure, is expensive, and has a problem that it is difficult to adhere along a high step due to the elastic force of the resin film.
Patent Document 2 describes that, as an effect, the electrical characteristics of the transparent conductive film are small, the heat-and-moisture stability and the step following property are good, and whitening and foaming hardly occur. This is expected to be difficult to adhere to.

  This invention is made | formed in view of the said situation, Comprising: At least the surface of a recessed part of the three-dimensional molded product which has a recessed part provides the three-dimensional molded article which coat | covered the resin film uniformly, and the manufacturing method of this three-dimensional molded article Is an issue.

That is, the present invention employs the following configuration.
[1] A three-dimensional molded article in which an adhesive sheet, a vapor deposition layer, and a resin film are coated in this order on at least the concave surface of the adherend having a concave part, and the three-dimensional molded article is made of plastic resin or carbon fiber reinforced plastic. The adhesive sheet contains an acrylic polymer and has a film thickness of 20 μm to 200 μm, and the resin film is made of an acrylic resin, a polyolefin resin, a urethane resin, a polyamide resin, a polycarbonate resin, or an ABS resin. A three-dimensional molded product, which is one or more selected from the group.
[2] The three-dimensional molded product according to [1], wherein the vapor deposition layer is an aluminum vapor deposition layer.
[3] The three-dimensional molded product according to [1] or [2], wherein the adhesive sheet, the vapor-deposited layer, and the resin film have portions that are coated on the side surface and the upper surface of the three-dimensional molded product and are not coated on the lower surface. .
[4] A method for producing a three-dimensional molded article in which an adhesive sheet, a vapor deposition layer, and a resin film are coated in this order on at least the surface of a concave portion of an adherend having a concave portion, comprising an acrylic polymer and a polymerization initiator. And laminating the adhesive sheet on the vapor deposition layer surface side of the resin film in which the vapor deposition layer is formed, and a step of producing a resin laminate in which the resin film and the adhesive sheet are laminated. And a step of manufacturing a vapor deposition layer-containing resin laminate having an adhesive sheet, a vapor deposition layer, and a resin film in this order, and pressing the vapor deposition layer-containing resin laminate on the adherend to form a surface shape of the adherend. And a step of coating the adherend with the vapor-deposited layer-containing resin laminate while stretching the vapor-deposited layer-containing resin laminate, and a method for producing a three-dimensional molded product.
[5] The method for producing a three-dimensional molded product according to [4], wherein the resin film is made of an unstretched resin.
[6] The method for producing a three-dimensional molded product according to [4] or [5], wherein the resin film is made of a resin that does not break under double-stretching conditions.

  ADVANTAGE OF THE INVENTION According to this invention, the solid molded product which coat | covered the resin base material layer uniformly on the surface of the solid molded product which has a recessed part can be provided.

It is a figure which shows an example of sectional drawing of the laminated body used for this embodiment. It is a figure which shows an example of sectional drawing of the resin laminated body used for this embodiment. It is a schematic sectional drawing of an example of the vacuum forming apparatus used for this embodiment. It is a schematic sectional drawing of an example of the vacuum forming apparatus used for this embodiment. It is a schematic sectional drawing of an example of the vacuum forming apparatus used for this embodiment. It is a schematic sectional drawing of an example of the vacuum forming apparatus used for this embodiment. It is a schematic sectional drawing of an example of the three-dimensional molded product of this embodiment.

<Three-dimensional molded product>
The three-dimensional molded product of this embodiment is a three-dimensional molded product in which an adhesive sheet, a vapor deposition layer, and a resin film are coated in this order on the surface of at least the concave portion of the adherend having the concave portion. In the present embodiment, the three-dimensional molded product includes a plastic resin or a carbon fiber reinforced plastic.
The adhesive sheet contains an acrylic polymer and has a film thickness of 20 μm or more and 200 μm or less.
Furthermore, the resin film is at least one selected from the group consisting of acrylic resin, polyolefin resin, urethane resin, polyamide resin, polycarbonate resin, and ABS resin.

The three-dimensional molded product in this embodiment has a recessed part. Specifically, a three-dimensional molded product having an angle of 80 degrees or more with respect to the extending direction of the surface of the main body portion of the three-dimensional molded product is exemplified.
“An angle of 80 degrees or more” means an angle formed by two line segments in contact with the surface in the cross section of the molded body, and the angle outside the molded body is 80 degrees or more. Examples of the step having an angle of 90 degrees or more that the adherend may have include an angle of 120 degrees, 150 degrees, and 170 degrees.
In FIG. 7, the schematic sectional drawing of an example of the three-dimensional molded product 70 of this embodiment is shown. The three-dimensional molded product 70 has a steep angle at a portion indicated by reference numeral 71, and has a curved concave portion at a portion indicated by reference numeral 72. The part shown with the code | symbol 71 has a steep angle of 80 degree | times or more with respect to the extending | stretching direction of the surface of the main-body part of a three-dimensional molded object. The three-dimensional molded product 70 shown in FIG. 7 is merely an example, and is not particularly limited as long as it is a three-dimensional molded product having a recess in the present embodiment.

Even if the three-dimensional molded product of this embodiment has a recessed part and a steep angle, the vapor deposition layer and the resin base material layer are coat | covered in this order uniformly in the whole surface of the three-dimensional molded product.
In the present embodiment, the three-dimensional molded product includes a plastic resin or a carbon fiber reinforced plastic.

 In the three-dimensional molded product of the present embodiment, it is preferable that the vapor deposition layer and the resin film have portions that are covered on the side surface and the upper surface of the three-dimensional molded product and are not covered on the lower surface. The three-dimensional molded product of the present embodiment can cover the surface of the three-dimensional molded product with the adhesive layer, the vapor deposition layer, and the resin base material layer in this order using a vacuum molding device described later. By appropriately changing the composition of the vapor deposition layer, excellent design can be imparted to a three-dimensional molded product having a complicated shape.

 Examples of the three-dimensional molded product in the present embodiment include various three-dimensional molded products that require design properties, such as vehicle-mounted components and toys.

 Hereinafter, the three-dimensional molded article of the present invention will be described while explaining the method for producing the three-dimensional molded article of the present invention.

<Method for producing three-dimensional molded product>
The manufacturing method of the three-dimensional molded product of this embodiment manufactures the resin laminated body which laminated | stacked the adhesive sheet containing an acrylic polymer and a polymerization initiator on the surface of a resin film, and the said resin film and the said adhesive sheet laminated | stacked. And a resin laminate for producing a deposited layer-containing resin laminate having the adhesive sheet, the deposited layer, and the resin film in this order by laminating the adhesive sheet on the deposited layer surface side of the resin film having the deposited layer formed thereon. A step of manufacturing, the deposition layer-containing resin laminate is pressed against the adherend, and the adherend is contained in the deposition layer while stretching the deposition layer-containing resin laminate according to the surface shape of the adherend. And a step of covering with a resin laminate.

≪Process for manufacturing resin laminates≫
The step of producing a resin laminate is a step of laminating an adhesive sheet containing an acrylic polymer and a polymerization initiator on the surface of the resin film, and producing a resin laminate in which the resin film and the adhesive sheet are laminated. It is.
In this step, a sheet-like adhesive layer is manufactured. In the method for producing a molded body of the present embodiment, by using a sheet-like adhesive layer, it can be coated with a resin film following the surface shape of the adherend.

  In this step, it is preferable to first produce an adhesive raw material composition containing an acrylic polymer and a polymerization initiator. The adhesive raw material composition preferably contains an organic solvent because it can be applied with higher accuracy when dissolved in an organic solvent. An adhesive sheet is obtained by drying the solvent from the adhesive raw material composition. That is, the composition of the adhesive raw material composition may be a composition obtained by adding a solvent to the composition of the adhesive resin composition constituting the adhesive sheet. The adhesive sheet functions as an adhesive layer at room temperature (before thermosetting).

The adhesive sheet in this invention can be manufactured by apply | coating the adhesive raw material composition in the state containing the solvent to the separator film, drying, and also protecting with a separator film.
In this embodiment, before the step of producing a resin laminate, an acrylic raw material and a polymerization initiator are mixed to produce an adhesive raw material composition, and the adhesive raw material composition is applied onto a separator. In addition, it is preferable to further include a step of manufacturing another adhesive sheet sandwich body by stacking and sandwiching another separator.

 The adhesive raw material composition is preferably applied using a die or a pipe doctor. In drying the solvent, it is preferable to dry by heating, blowing, decompressing, or a combination thereof. Regarding the drying time of the solvent, considering productivity, it is preferably 10 minutes or less, and more preferably 2 to 5 minutes. Further, since it is necessary to sufficiently dry the organic solvent, it is preferable to dry the organic solvent at a temperature equal to or higher than the boiling point of the organic solvent, and it is preferable to dry the thermal polymerization initiator at a half-life temperature of 1 minute or less.

  Hereinafter, each material which comprises an adhesive bond layer is demonstrated.

-Acrylic polymer The monomer constituting the acrylic polymer is an acrylic monomer having an ester group (-COO-), an acrylic monomer having a carboxyl group (-COOH), an amide group (-CONR ₂ , R is a hydrogen atom or Non-acrylic monomers such as acrylic monomers having a substituent such as an alkyl group, acrylic monomers having a nitrile group (—CN), olefins, styrene, vinyl esters, vinyl ethers, and vinyl silane. The acrylic polymer is preferably a copolymer composed of two or more monomers. The number average molecular weight of the acrylic polymer before photopolymerization is preferably about 5 to 1,000,000, for example. As for a viscosity, about 1000-10000 mPa * s is mentioned, for example.

  As an acrylic monomer having an ester group (—COO—), an alkyl (meth) acrylate, a (meth) acrylate having a hydroxy group (hydroxyl group), a (meth) acrylate having an alkoxy group or a polyether group, an amino group, or a substituent Examples thereof include (meth) acrylate having an amino group. In this specification, (meth) acrylate is a general term for acrylate and methacrylate.

Examples of the acrylic monomer having a carboxy group (—COOH) include acrylic acid, methacrylic acid, (meth) acrylate having a carboxyl group (—COOH), and the like.
Examples of the acrylic monomer having an amide group (-CONR ₂ , R is a hydrogen atom or a substituent such as an alkyl group) include acrylamide and methacrylamide.
Examples of the acrylic monomer having a nitrile group (—CN) include acrylonitrile and methacrylonitrile.

In the acrylic polymer, it is preferable that 50% by weight or more of the constituent monomer is composed of an acrylic monomer. In particular, 50% by weight or more of the constituent monomers are represented by the general formula CH ₂ = CR ¹ -COOR ² (wherein R ¹ represents hydrogen or a methyl group, and R ² represents an alkyl group having 1 to 14 carbon atoms). It is preferable that it consists of 1 type (s) or 2 or more types of alkyl (meth) acrylate. Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) ) Acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate. In particular, it is preferable to use an alkyl (meth) acrylate having 4 to 12 carbon atoms of the alkyl group R ² as an essential component (for example, 50 to 100 mol%).

  Examples of the (meth) acrylate containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. , 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctane (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate The above is mentioned.

-Acrylic monomers or acrylic oligomers Among the acrylic monomers or acrylic oligomers, the acrylic monomers contain the same monomers as those constituting the acrylic polymer, such as alkyl (meth) acrylates and hydroxyl groups ( 1 type, or 2 or more types, such as a meth) acrylate and acrylamide, are mentioned. The number of polymerizable functional groups such as a (meth) acryloyl group in one molecule may be one or two or more.

  In particular, when a (meth) acrylate monomer having a hydroxyl group is contained as at least a part of the acrylic monomer or acrylic oligomer, the polar hydroxyl group is easily dispersed throughout the adhesive sheet. This is preferable because moisture hardly aggregates even in a high humidity (higher temperature) environment and the white turbidity of the adhesive sheet is suppressed. In the (meth) acrylate having a hydroxyl group, the number of hydroxyl groups in one molecule may be one or two or more.

Moreover, curable urethane acrylate can be used as at least a part of the acrylic monomer or acrylic oligomer. Urethane acrylate is a compound having a urethane bond (—NH—COO—) and a (meth) acryloyloxy group (X ₂ = CX—COO— as X═H or CH ₃ ) in the same molecule. The curable urethane acrylate is a compound having curability due to the (meth) acryloyloxy group which is a polymerizable functional group in the urethane acrylate. The number of urethane bonds in one molecule may be one or two or more. The number of (meth) acryloyloxy groups in one molecule may be one or two or more.

  Examples of the urethane acrylate include a compound obtained by reacting a (meth) acrylate compound having a hydroxyl group with an isocyanate compound, a urethane prepolymer obtained by reacting a polyol compound and a polyisocyanate compound, and having a hydroxyl group (meta ) Compounds obtained by reacting acrylate compounds. Examples of the polyol compound include polyester polyol and polyether polyol.

 The acrylic monomer or acrylic oligomer is preferably a liquid (fluid) that becomes part of the polymer by curing with a polymerization initiator and has a lower viscosity than the polymer. It is also possible to use acrylic monomers and acrylic oligomers in combination. Examples of the acrylic oligomer include acrylate oligomers such as urethane acrylate oligomers. The number of polymerizable functional groups that the acrylic monomer or acrylic oligomer has is, for example, 1 to 10, or 2 to 5. In this embodiment, it is preferable to use a polyfunctional acrylate monomer.

  The adhesive resin composition preferably contains 5 to 50 parts by weight of an acrylic monomer or an acrylic oligomer with respect to 100 parts by weight of the acrylic polymer. If the amount of the acrylic monomer or acrylic oligomer added is too large, the adhesive force of the adhesive resin layer may be excessively reduced when polymerized.

-Polymerization initiator As a polymerization initiator, a thermal polymerization initiator is preferable, and the radical initiator which decomposes | disassembles with heat and starts the superposition | polymerization (radical polymerization) of a monomer and hardening of resin is mentioned. As the radical initiator, from the viewpoint of facilitating the handling of the adhesive sheet, (organic) peroxide type, azo type and the like are preferable.

  In the present embodiment, the polymerization start temperature of the thermal polymerization initiator is preferably lower by 10 ° C. or more and 50 ° C. or less than the heating temperature in the coating step described later. When the polymerization start temperature satisfies the above conditions, the polymerization reaction of the polymer component contained in the adhesive sheet can be simultaneously performed by the heat treatment in the coating step.

  Specific examples of (organic) peroxide-based thermal polymerization initiators include benzoyl peroxide, acetyl peroxide, decanoyl peroxide, lauroyl peroxide, and other diacyl peroxides, dicumyl peroxide, and di-t-butyl peroxide. Examples thereof include alkylperoxy esters such as dialkyl peroxide, t-butylperoxybenzoate, and t-butylperoxy-2-ethylhexanoate, and hydroperoxides such as cumene hydroperoxide and t-butylhydroperoxide. Preferred organic peroxides include t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, di- Lauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, disuccinic acid peroxide, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5 , 5 Trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-butylperoxylaurate, t-hexylperoxybenzoate, t-butylperoxyacetate, t-butylperoxybenzoate, n- Examples include butyl 4,4-bis (t-butylperoxy) valerate, dicumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, and p-menthane hydroperoxide.

  As the azo-based thermal polymerization initiator, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethyl) Valeronitrile), 2,2'-azobis (4-cyanovaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (methylisobutyrate) 1,1′-azobis (1-cyclohexanecarbonitrile) and the like.

  It is preferable that the addition amount of the thermal polymerization initiator is 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the acrylic polymer.

  A polymerization retarder can be added to the adhesive sheet. Use of a polymerization retarder facilitates control of the degree of polymerization. Moreover, it is preferable from a viewpoint of improving the followable | trackability with respect to a deformation | transformation of a base material.

The adhesive resin composition can further contain optional components other than those described above.
For example, a crosslinking agent (curing agent) such as an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or a metal chelate compound is preferably used for crosslinking an acrylic polymer or a polymer formed by polymerization of an acrylic monomer or an acrylic oligomer. It is done. In this case, if necessary, a polymer or monomer having a functional group that reacts with the crosslinking agent is used as at least a part of the acrylic polymer, the acrylic monomer, or the acrylic oligomer. The functional group that reacts with the crosslinking agent is, for example, a hydroxyl group or a carboxyl group in the case of an isocyanate crosslinking agent. The addition amount of the crosslinking agent is preferably, for example, 1.5 equivalents or less with respect to the functional group of the polymer.
The curing of the acrylic polymer by the crosslinking agent (curing agent) may be advanced by aging at the stage of producing an adhesive sheet before being bonded to the adherend.

  Examples of other optional components include an antioxidant, a filler, and a plasticizer. The adhesive raw material composition used for the production of the adhesive resin layer may contain a solvent such as water or an organic solvent, or may be a solvent-free syrup-like composition. When there is a corrosive material such as an oxide conductive film such as ITO or a base metal on the base material, and the adhesive resin layer comes into contact with this, the adhesive resin composition is made of corrosive acid or the like. For example, it is preferable to use a polymer having a low acid value.

  In this embodiment, it is preferable that the adhesive sheet obtained by the process of manufacturing the adhesive sheet sandwiched body is in a state of being sandwiched between two separators. In the step of producing a resin laminate to be described later, it is preferable that one separator of the adhesive sheet sandwiching body is peeled and laminated on the resin film, and then the other separator is peeled off.

≪Process for coating with resin film≫
FIG. 1 shows a cross-sectional view of an example of the laminated body 10. The laminated body 10 preferably includes two separators 12 and 13 and an adhesive sheet 11 laminated therebetween. The adhesive resin composition constituting the adhesive sheet 11 is as described above. Both surfaces 11a and 11b of the adhesive sheet 11 have adhesiveness at normal temperature (becomes adhesive surfaces).

  The adhesive sheet 11 is made of an adhesive resin composition throughout the thickness direction. If it consists of the adhesive resin composition which satisfy | fills a requirement, the adhesive sheet 11 may be comprised from 2 or more layers which consist of the same kind or different kind of adhesive resin composition. When the adhesive sheet 11 consists of a single-layer adhesive resin layer, it is preferable because the layer configuration can be simplified and the cost can be reduced. The adhesive resin composition includes an acrylic adhesive resin (polymer). The optical properties of the adhesive resin composition are not limited, but may be transparent, translucent or opaque.

  Separator 12,13 has peelability in the surface 12a, 13a of the side which contact | connects the adhesive sheet 11 (it becomes a peeling surface). Examples of the configuration of the separators 12 and 13 include a configuration in which a release agent layer is provided on one or both sides of the resin film, and a configuration in which a release agent is included in the resin of the resin film. Instead of the resin film, paper, synthetic paper, metal foil, various sheets, and the like can be used. It is preferable that the separators 12 and 13 have transparency because the adhesive sheet 11 can be optically inspected with the laminate 10 from which the separators 12 and 13 are not peeled off.

  The laminated body 10 shown in FIG. 1 can bond a to-be-adhered body and a resin film by the adhesive surfaces 11a and 11b exposed by peeling the separators 12 and 13 from the adhesive sheet 11.

In FIG. 2, an example of the resin laminated body 20 which laminated | stacked the resin film 21 on the adhesive sheet 11 is shown.
When forming the resin laminate 20 as shown in FIG. 2, the order in which the separators 12 and 13 are peeled is not particularly limited. For example, a resin film may be bonded to one adhesive surface exposed by peeling one separator.

The adhesive sheet 11 preferably has a haze value of 3.0 or less, more preferably 2.5 or less, and particularly preferably 1.0 or less. The total light transmittance of the adhesive sheet 11 is preferably 80% or more, more preferably 82% or more, and particularly preferably 85% or more.
When the haze value of the adhesive sheet 11 is in the above range, for example, when a transparent resin film is coated, it is possible to ensure transparency in the molded body.

The thickness of the adhesive sheet 11 is preferably 20 μm or more, more preferably 25 μm or more, and particularly preferably 30 μm or more. The adhesive sheet 11 is preferably 200 μm or less, more preferably 190 μm or less, and particularly preferably 185 μm or less.
The upper limit value and the lower limit value can be arbitrarily combined.

The adhesive sheet 11 preferably has an adhesive strength after heating of 30 N / 25 mm or more, more preferably 35 N / 25 mm or more, and particularly preferably 40 N / 25 mm or more. The adhesive strength is a value measured by a measurement method (peeling measurement method A) defined in JIS C6471.
In this embodiment, the adhesive strength of the adhesive sheet is improved by heating in the coating step described later.

  In the present embodiment, the resin film forming material is preferably at least one selected from the group consisting of acrylic resins, polyolefin resins, urethane resins, polyamide resins, polycarbonate resins, and ABS resins. Of these, acrylic resins, polycarbonate resins, and ABS resins are particularly preferable.

≪Process for producing vapor-deposited layer-containing resin laminate≫
In this embodiment, the process of forming a printing layer or a vapor deposition layer on a resin film is provided before the process of manufacturing a resin laminated body for the purpose of the design improvement, intensity | strength improvement, etc. By printing the design on the resin film by a conventional method, the design can be imparted to the adherend when the adherend is coated with the resin film. In addition, by depositing a metal component such as aluminum on the resin film, a metallic luster can be imparted to the adherend when the adherend is coated with the resin film.

≪Coating process≫
The step of coating heats the vapor deposition layer-containing resin laminate, presses the vapor deposition layer-containing resin laminate on the adherend planarly in a reduced pressure environment, and then opposes the resin film against the adherend. This is a step of pressurizing the environment on the side.
In this step, it is preferable to use a vacuum forming apparatus. FIG. 3 shows an example of a vacuum forming apparatus 30 that can be suitably used in the present embodiment.
The vacuum molding apparatus that can be suitably used in the present embodiment includes molding chambers at the top and bottom, and performs vacuum molding of the vapor-deposited layer-containing resin laminate between the two molding chambers. A vacuum circuit and an air circuit are respectively piped in the upper and lower molding chambers.

 The upper molding chamber 31 and the lower molding chamber 32 can be closed together and separated. That is, the upper molding chamber 31 is provided with a driving device 34a, which can be raised and lowered. A table 36 is disposed inside the lower molding chamber 32, and the table 36 can be raised and lowered by a driving device 34b. As each drive device 34, an air cylinder, a hydraulic cylinder, a servo motor, etc. can be used, for example. On the table 36, an adherend 33 to be covered with the vapor deposition layer-containing resin laminate 20 is placed. The vapor deposition layer-containing resin laminate 20 is fixed between the upper molding chamber 31 and the lower molding chamber 32 by a clamp 35. Further, the vacuum forming apparatus 30 includes a gas supply chamber 37 and a gas suction chamber 38.

 A heater 39 is incorporated in the upper molding chamber 31, and the vapor deposition layer-containing resin laminate 20 is heated by the heater 39 between the molding chambers closed together. An example of the heater 39 is a near infrared heater.

The usage method of this vacuum forming apparatus 30 is as follows.
As shown in FIG. 3, the adherend 33 is placed and set on the table 36 in the lower molding chamber 32. The vapor deposition layer-containing resin laminate 20 is fixedly set on the upper surface of the lower molding chamber 32 with a clamp 35. At this time, the upper molding chamber and the lower molding chamber are both at atmospheric pressure.

 As shown in FIG. 4, the upper molding chamber 31 is lowered, the upper molding chamber and the lower molding chamber are closed and matched, and the molding chamber is closed. The upper molding chamber and the lower molding chamber are both brought into a vacuum suction state or a reduced pressure state (represented by black dots in the figure) from the atmospheric pressure state by a vacuum tank (not shown).

 As shown in FIG. 4, the upper molding chamber and the lower molding chamber are both in a vacuum suction state or a reduced pressure state. The heater 39 is turned on (represented by solid black in the figure), and the vapor deposition layer-containing resin laminate 20 is heated. When the vapor-deposited layer-containing resin laminate 20 is heated, it tends to sag due to its own weight (see a two-dot chain line).

 By heating the vapor deposition layer-containing resin laminate 20 with the heater 39, softening of the resin film and curing of the adhesive sheet proceed simultaneously. When the resin film is softened by heating, the resin film extends according to the surface shape of the adherend when pressed, and the resin film can be covered according to the surface shape of the adherend.

 As shown in FIG. 5, the table 36 in the lower molding chamber 32 is then raised. At this time, the upper molding chamber and the lower molding chamber are in a substantially vacuum state.

 As shown in FIG. 5, the vacuum in the upper molding chamber 31 is released and the atmosphere is put in, so that the vapor deposition layer-containing resin laminate 20 is covered with the adherend 33 via an adhesive sheet as indicated by an arrow. .

 As shown in FIG. 6, when the coating is completed, the heater 39 is turned off, the vacuum in the lower molding chamber is released to return to the atmospheric pressure state, the upper molding chamber is raised, the coated adherend 60 is taken out, and the coating is performed. The process ends.

 In this step, the upper molding chamber is pressurized by the valve connected to the gas supply chamber 37 and the valve connected to the gas suction chamber 38, the lower molding chamber is controlled to a reduced pressure environment, and the vapor deposition layer-containing resin laminate 20 is placed in a horizontal state. By maintaining, the resin film can be stretched following the surface shape of the adherend, and the adherend can be uniformly coated with the resin film.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these examples.

<Example 1: Production of three-dimensional molded product>
≪Adhesive manufacturing process≫
SK Dyne (registered trademark) 2094 (Soken Chemical Co., Ltd.) is used as the polymer solution containing the acrylic polymer, E-AX (Soken Chemical Co., Ltd.) is used as the cross-linking agent, and the cross-linking agent is used with respect to 100 parts by weight of the acrylic polymer. It mix | blended in the ratio of 0.1 weight part. In the obtained mixture, 15 parts by weight of urethane acrylate UV-3310 as a reactive fluid resin component and t-butylperoxy-2-ethylhexanoate (NOF CORPORATION) as a thermal polymerization initiator were used. Product name: Perbutyl (registered trademark) O) 0.1 part by weight was added to prepare an adhesive raw material composition.

≪Resin laminate manufacturing process≫
Using the applicator on the upper surface of the separator (manufactured by Fujimori Kogyo Co., Ltd .; product name: 125E-0010DG2.5AS, thickness 125 μm), the thickness of the adhesive sheet (adhesive layer) after drying is 50 μm. Then, in the drying process, the solvent was dried at 90 ° C. for 2 minutes to prepare a laminate in which the adhesive sheets were laminated.
Next, a separator (manufactured by Fujimori Kogyo Co., Ltd .; product name: 38E-0010BDAS, thickness 38 μm) was bonded to the upper surface of the obtained adhesive sheet of the laminate to prepare a resin laminate.
Thereafter, by aging for one week, the reaction between the acrylic polymer and the crosslinking agent (epoxy) is terminated, and the crosslinked acrylic polymer, the reactive fluid resin component, and the thermal polymerization initiator. The resin laminated body of Example 1 in which three types exist was formed.

<Example 2: Production of three-dimensional molded product>
About the resin laminated body of Example 2, the resin laminated body was manufactured by the method similar to Example 1 except having changed the composition as described in Table 1 below.

<Comparative Example 1: Production of three-dimensional molded product>
The resin laminate of Comparative Example 1 was produced by the same method as Example 1 except that the thickness of the adhesive sheet after drying was 220 μm.

In Table 1, the numerical value in [] is the blending amount (part by mass).
In Table 1, "SK Dyne 2094" and "SK Dyne 2147" are trade names of acrylic polymers, SK Dyne (registered trademark) 2094 (Soken Chemical Co., Ltd., acid value: 33, number average molecular weight 70,000, solid Fraction concentration 25%), SK Dyne (registered trademark) 2147 (Soken Chemical Co., Ltd., acid value: 33).

  “E-AX” indicates a trade name of Epoxy Curing Agent (Soken Chemical Co., Ltd.). “TD-75” indicates a trade name of an isocyanate curing agent (Soken Chemical Co., Ltd.). “4HBA” represents 4-hydroxybutyl acrylate, an acrylic monomer of Osaka Organic Chemical Industry Co., Ltd.

  “UV-3310” represents a trade name of urethane acrylate (Nippon Synthetic Chemical Industry Co., Ltd.). The physical properties of UV-3310 are: viscosity at 60 ° C .: 40000 to 70000 mPa · s, weight average molecular weight Mw: 5000, number of oligomer functional groups: 2, glass transition temperature Tg: 22 ° C.

 Perbutyl (registered trademark) O is a thermal polymerization initiator containing t-butylperoxy-2-ethylhexanoate as an active ingredient. Perbutyl O has a one-minute half-life of 134 ° C., and Perhexa V has a one-minute half-life of 172 ° C. “Irg651” is a photopolymerization initiator containing 2,2-dimethoxy-2-phenylacetophenone (also known as benzyldimethyl ketal) as an active ingredient.

≪Coating process≫
An adherend 33 is placed on a table 36 that moves up and down in a vacuum forming apparatus 30 (trade name NGF-0510-R, manufactured by Fuse Vacuum Co., Ltd.) having an upper forming chamber 31 and a lower forming chamber 32. installed. The resin laminate 20 was set on the clamp 35 of the molding apparatus. Next, while the pressure in each of the upper and lower molding chambers 31 and 32 is reduced to 1.0 kPa, the resin laminate 20 is heated using a near-infrared heater until the temperature of the resin laminate 20 reaches 150 ° C. The material was raised, the adherend 33 and the resin laminate 20 were pressure-bonded, and then 150 kPa of compressed air was introduced only into the upper molding chamber 31 and held for 30 seconds. After the holding, the upper and lower molding chambers 31 and 32 were opened to atmospheric pressure to obtain a coated molded body 60.

  As the three-dimensional molded product used in this example, a cylindrical three-dimensional molded product having a recess having a length of 7 cm, a width of 7 cm, and a height of 7 cm was used. A schematic cross-sectional view of the three-dimensional molded product 70 used is shown in FIG. The three-dimensional molded product 70 has a recess in the portion indicated by reference numeral 72 and the like. Further, the portion indicated by reference numeral 71 has a bending angle of 90 ° or more.

<Evaluation>
-Adhesiveness Adhesiveness was evaluated according to the following evaluation criteria.
○: No peeling was observed at the end of the three-dimensional molded product 70.
X: Peeling was observed at the end of the three-dimensional molded product 70.

-Recess of the concave part The concave part 72 of the three-dimensional molded product 70 was observed.
(Double-circle): The resin laminated body was not received from the three-dimensional molded product, and was sticking neatly.
○: The resin laminate was not received from the three-dimensional molded product.
X: The resin laminate was obtained from a three-dimensional molded product.

-Adhesion of a vertical part The floating and foaming of the vertical part of the three-dimensional molded product 70 were observed.
○: The resin laminate was not received from the three-dimensional molded product.
X: The resin laminate was obtained from a three-dimensional molded product.

The adhesive strength was measured by a measurement method (peeling measurement method A) defined in JIS C6471.

  As described in the above results, in Example 1 to which the present invention was applied, the resin base material layer could be bonded to the three-dimensional molded product having the recess without any depression in the recess. In addition, the resin base material layer could be bonded without any more vertical portions.

10: Laminate, 11: Adhesive sheet, 12, 13: Separator, 20: Deposition layer-containing resin laminate, 21: Resin base layer, 22: Deposition layer, 30: Vacuum molding chamber, 31: Upper molding chamber, 32 : Lower molding chamber, 33: Solid molded product, 34: Drive device, 35: Clamp, 36: Table, 37: Gas supply chamber, 38: Gas suction chamber, 60: Solid coated with resin base material layer and vapor deposition layer Molded product, 70: Solid molded product

Claims (6)

On the surface of at least the concave portion of the adherend having a concave portion, a three-dimensional molded article in which an adhesive sheet, a vapor deposition layer, and a resin film are coated in this order,
The three-dimensional molded product includes a plastic resin or a carbon fiber reinforced plastic,
The adhesive sheet includes an acrylic polymer, and has a film thickness of 20 μm to 200 μm,
The three-dimensional molded product, wherein the resin film is at least one selected from the group consisting of an acrylic resin, a polyolefin resin, a urethane resin, a polyamide resin, a polycarbonate resin, and an ABS resin.   The three-dimensional molded product according to claim 1, wherein the vapor deposition layer is an aluminum vapor deposition layer.  The three-dimensional molded product according to claim 1, wherein the adhesive sheet, the vapor deposition layer, and the resin film have a portion that is covered on a side surface and an upper surface of the three-dimensional molded product and is not covered on a lower surface. A method for producing a three-dimensional molded article in which an adhesive sheet, a vapor deposition layer, and a resin film are coated in this order on at least the surface of a concave portion of an adherend having a concave portion,
Laminating an adhesive sheet containing an acrylic polymer and a polymerization initiator on the surface of the resin film, and producing a resin laminate in which the resin film and the adhesive sheet are laminated,
Laminating the adhesive sheet on the vapor deposition layer surface side of the resin film on which the vapor deposition layer is formed, and manufacturing a vapor deposition layer-containing resin laminate having the adhesive sheet, the vapor deposition layer, and the resin film in this order;
The vapor-deposited layer-containing resin laminate is pressed against the adherend, and the adherend is covered with the vapor-deposited layer-containing resin laminate while the vapor-deposited layer-containing resin laminate is stretched following the surface shape of the adherend. A process for producing a three-dimensional molded product.  The method for producing a three-dimensional molded product according to claim 4, wherein the resin film is made of an unstretched resin. The method for producing a three-dimensional molded product according to claim 4 or 5, wherein the resin film is made of a resin that does not break under double-stretching conditions.

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