JP2019051681A - Method for producing molded body - Google Patents

Abstract

To provide a method for producing a molded body capable of uniformly coating a resin film onto an adherend.SOLUTION: A method for producing a molded body includes: a step of laminating an adhesive sheet containing an acrylic polymer and a polymerization initiator onto a surface of a resin film to produce a resin laminate where the resin film and the adhesive sheet are laminated; and a step of pressing the resin laminate onto an adherend, and coating the adherend with the resin film while stretching the resin film so as to follow the surface shape of the adherend, where the shape when the resin laminate is viewed in plan view is larger than the shape when the adherend is viewed in plan view, and the coating step includes heating the resin laminate, pressing the resin laminate under pressure-reduced environment while making the resin laminate planarly overlapping the adherend, and then pressurizing environment on an opposite side to the adherend of the resin film.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a molded body.

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: It aims at providing the manufacturing method of a molded object which can coat | cover a resin film uniformly to a to-be-adhered body.

That is, the present invention employs the following configuration.
[1] A step of laminating an adhesive sheet containing an acrylic polymer and a polymerization initiator on the surface of a resin film to produce a resin laminate in which the resin film and the adhesive sheet are laminated, and the resin laminate Covering the adherend with the resin film while stretching the resin film following the surface shape of the adherend, and viewing the resin laminate in plan view The shape at the time is larger than the shape when the adherend is viewed in plan, and in the covering step, the resin laminate is heated and the resin laminate is planarly planarized in a reduced pressure environment. And then pressing the environment opposite to the adherend with respect to the resin film.
[2] The method for producing a molded article according to [1], wherein the adhesive sheet further contains an acrylic monomer or an acrylic oligomer.
[3] The method for producing a molded article according to [2], wherein the acrylic monomer is a (meth) acrylate monomer containing a hydroxyl group or a polyfunctional acrylate monomer having a hydroxyl group.
[4] The method for producing a molded article according to [2], which contains curable urethane acrylate as at least a part of the acrylic monomer or acrylic oligomer.
[5] The method for producing a molded body according to any one of [1] to [4], wherein the adhesive sheet has a haze value of 1.0% or less and a total light transmittance of 85% or more.
[6] The method for producing a molded body according to any one of [1] to [5], wherein the thickness of the adhesive sheet is 20 μm or more and 200 μm or less.
[7] The method for producing a molded body according to any one of [1] to [6], wherein the adhesive strength of the adhesive sheet after heating is 30 N / 25 mm or more.
[8] The method for producing a molded article according to any one of [1] to [7], wherein the polymerization initiator is a thermal polymerization initiator.
[9] The method for producing a molded article according to [8], wherein a polymerization initiation temperature of the thermal polymerization initiator is lower by 10 ° C. or more and 50 ° C. or less than a heating temperature in the coating step.
[10] Before the step of producing the resin laminate, an acrylic polymer and a polymerization initiator are mixed to produce an adhesive raw material composition, and the adhesive raw material composition is applied onto a separator, Further, the method further includes the step of manufacturing another adhesive sheet sandwiched body by stacking other separators, and the step of manufacturing the resin laminate includes peeling one separator of the adhesive sheet sandwiched body and laminating it on the resin film. And the manufacturing method of the molded object as described in any one of [1]-[9] which is a process of peeling the other separator after that.
[11] The molded body according to any one of [1] to [10], including a step of forming a printed layer or a vapor deposition layer on the resin film before the step of manufacturing the resin laminate. Manufacturing method.
[12] The material for forming the resin film is one or more 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 manufacturing method of the molded object as described in any one.
[13] The method for producing a molded body according to any one of [1] to [12], wherein a surface of the adherend that covers the resin film includes a step having an angle of 90 degrees or more.
[14] Any one of [1] to [13], wherein the material for forming the adherend is at least one selected from the group consisting of carbon fiber reinforced plastic, polycarbonate resin, acrylic resin, and ABS resin. The manufacturing method of the molded object of description.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a molded object which can coat | cover a resin film uniformly on a to-be-adhered body 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 to-be-adhered body which coat | covered the resin film with the manufacturing method of the molded object of this embodiment.

<Method for producing molded body>
The method for producing a molded body of the present embodiment produces a resin laminate in which an adhesive sheet containing an acrylic polymer and a polymerization initiator is laminated on the surface of the resin film, and the resin film and the adhesive sheet are laminated. And pressing the resin laminate against the adherend, and covering the adherend with the resin film while stretching the resin film following the surface shape of the adherend. The shape when the resin laminate is viewed in plan is larger than the shape when the adherend is viewed in plan, and the covering step is performed by heating the resin laminate and planarly in a reduced pressure environment. After the resin laminate is pressed against the adherend, the environment opposite to the adherend is pressed against the resin film.
According to the method for manufacturing a molded body of the present embodiment, for example, the resin film can be coated following the shape of an adherend having a curved surface or a step. For this reason, for example, for the purpose of imparting design properties, a resin film rich in design can be coated following the shape of the adherend having a complicated shape.
Hereinafter, each process of the manufacturing method of the molded object of this embodiment is demonstrated.

≪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, it is preferable to use curable urethane acrylate 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.
When an acrylic monomer or an acrylic oligomer is contained in the adhesive resin composition, the fluidity of the adhesive resin composition is increased. When the flowability of the adhesive resin composition is high, the surface of the adherend in the present invention is well adapted to the surface even if the surface of the adherend is rough and has fine irregularities. Can be smoothed and the appearance after finishing can be improved.

-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 a process for producing a resin laminate described later, one separator of the adhesive sheet sandwiching body is peeled and laminated on a 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, the transparency of the molded body can be ensured.

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.

-Arbitrary structure In this embodiment, it is preferable to provide the process of forming a printing layer or a vapor deposition layer on a resin film 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≫
In the coating step, the resin laminate is heated, and the resin laminate is planarly stacked on the adherend and pressed in a reduced pressure environment, and then the environment opposite to the adherend is pressed against the resin film. It is a process.
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 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. An adherend 33 to be covered with the resin laminate 20 is placed on the table 36. The resin laminate 20 is disposed between the upper molding chamber 31 and the lower molding chamber 32 by being fixed 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 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 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 black solids in the figure) to heat the resin laminate 20. When the resin laminate 20 is heated, it tends to sag due to its own weight (see a two-dot chain line).

 By heating the 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 resin laminate 20 is covered with the adherend 33 through an adhesive sheet as indicated by an arrow by releasing the vacuum in the upper molding chamber 31 and entering the atmosphere.

 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 a valve connected to the gas supply chamber 37 and a valve connected to the gas suction chamber 38, the lower molding chamber is controlled to a reduced pressure environment, and the resin laminate 20 is maintained in a horizontal state. The resin film is stretched following the surface shape of the adherend, and the adherend can be uniformly coated with the resin film.

In the present specification, the “adherent” is a target member that covers a resin film via an adhesive sheet.
According to the method for producing a molded body in the present embodiment, a resin film can be more preferably uniformly coated on an adherend having either one or both of a curved surface and a step.
According to the method for producing a molded body of the present embodiment, even if an adherend having a curved surface is formed by using a vacuum molding apparatus using the resin laminated body, the resin laminated body becomes a concave curved surface or a convex. The resin film can be adhered uniformly and uniformly to the surface of the adherend following the curved surface shape.

According to the present embodiment, the adherend having a step having an angle of 90 degrees or more can be suitably covered with the resin film. "An angle is 90 degrees or more" means that an angle formed by two line segments in contact with the surface in the cross section of the molded body, and an angle outside the molded body is 90 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 the present embodiment, since the resin film can be coated in accordance with the shape of the adherend, even if the adherend has an acute angle of 90 degrees or more, the resin film is evenly and uniformly on the surface of the adherend. Can be glued.

  In this embodiment, the material of the adherend is not particularly limited, but it is one or more selected from the group consisting of carbon fiber reinforced plastic, polycarbonate resin, acrylic resin, ABS resin, polyester resin, and vinyl chloride resin. Preferably there is.

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

Example 1
<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 100 parts by weight of the acrylic polymer is used as the cross-linking agent. It mix | blended in the ratio of 0.2 weight part. In the obtained mixture, 20 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 (made by Fujimori Kogyo Co., Ltd .; product name: 125E-0010DG2.5AS, thickness 125 μm), the adhesive raw material composition was dried. After applying so as to have a thickness of 50 μm, the solvent was dried at 90 ° C. for 2 minutes in a drying step to produce a laminate in which an adhesive resin layer was laminated.
Next, a separator (manufactured by Fujimori Kogyo Co., Ltd .; product name: 38E-0010BDAS, thickness 38 μm) is bonded to the upper surface of the adhesive resin layer of the obtained laminate to produce the resin laminate of Example 1. did.

-Examples 2-3 and Comparative Examples 1-2
About the resin laminated body of Examples 2-3 and Comparative Examples 1-2, the resin laminated body was manufactured by the method similar to Example 1 except having changed the composition as described in Table 1 below.

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). “N-7136” represents the trade name of an acrylic polymer, Coponil (registered trademark) N-7136 (Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 32%). “4HBA” represents 4-hydroxybutyl acrylate, an acrylic monomer of Osaka Organic Chemical Industry Co., Ltd.

  “Coronate HX” represents a trade name of a polyisocyanate curing agent, Coronate (registered trademark) HX (Tosoh Corporation). “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.).

  “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.

 Perocta® O is a thermal polymerization initiator containing 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as an active ingredient. Perbutyl (registered trademark) O is a thermal polymerization initiator containing t-butylperoxy-2-ethylhexanoate as an active ingredient. 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, after reducing the pressure in the upper and lower molding chambers 31 and 32 to 1.0 kPa or less, using a near infrared heater, the laminated film resin laminate 20 is heated until the temperature reaches 120 ° C. Then, the molding substrate was raised, the adherend 33 and the resin laminate 20 were pressure-bonded, and then 300 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.

  The adherend used in this example was a model of a car shape having a curved surface and a level difference of 15 cm in length, 10 cm in width, and 3 cm in height. A schematic cross-sectional view of the model 70 used is shown in FIG. The model 70 has a curved surface at portions indicated by reference numerals 73 and 74. Further, the portion indicated by reference numeral 71 has a bending angle of 90 ° or more.

<Evaluation>
About the resin laminated body manufactured at the said resin laminated body manufacturing process, the plane part was taken out and the haze value and the total light transmittance were measured. The haze and total light transmittance were measured using a Nippon Denshoku haze meter “NDH4000”. The results are listed in Table 2.

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

  With respect to the adherend obtained by the coating step, the adhesiveness, unevenness, and sharpness of the resin laminate were evaluated in accordance with the following items.

-Adhesiveness Adhesiveness was evaluated according to the following evaluation criteria.
A: Even if a stress in the direction opposite to the bonding direction is applied to the bonded end portion of the model 70, none of the samples peels off.
A: Almost no peeling even when stress in the direction opposite to the bonding direction is applied to the bonded end of the model 70.
Δ: When a stress in the direction opposite to the bonding direction is applied to the bonded end portion of the model 70, there is a portion where peeling occurs.
X: When a stress in the direction opposite to the bonding direction is applied to the bonded end portion of the model 70, any sample can be easily peeled off.

Unevenness The unevenness was evaluated according to the following evaluation criteria by making 10 samples of the adherend 60 coated with a resin film.
(Double-circle): There is no difference in adhesiveness with 10 samples.
○: Inferior adhesion was observed in 1 of 10 samples.
Δ: Adhesiveness was observed in 2 to 5 samples out of 10 samples.
X: Adhesiveness of the sample is poor or the adhesiveness varies greatly.

-In the case of a portion with a steep angle Ten samples of the adherend 60 covered with a resin film were prepared, and the portion indicated by reference numeral 71 in FIG.
(Double-circle): The clearness of the resin laminated body 20 is not seen with 10 samples.
○: Resin laminate 20 was observed in 1 of 10 samples.
(Triangle | delta): The peeling of the resin laminated body 20 was seen by 2-5 samples among 10 samples.
×: Resin laminate 20 was observed in 6 or more samples out of 10 samples.

-Adhesion of the vertical part Ten samples of the adherend 60 covered with the resin film were prepared, and the adhesiveness of the resin laminate was evaluated for the part indicated by reference numeral 74 in FIG.
(Double-circle): All 10 samples adhered very finely visually.
◯: All 10 samples were adhered almost visually.
(Triangle | delta): The peeling of the resin laminated body 20 was seen by 1 sample among 10 samples.
X: The peeling of the resin laminated body 20 was seen by 2 samples or more among 10 samples.

  As described in the above results, in Examples 1 to 3 to which the present invention is applied, the resin film is bonded evenly to the adherend having a curved surface and a level difference without even lifting even at a portion where the bending angle is steep. We were able to.

10: laminate, 11: adhesive sheet, 12, 13: separator, 20: resin laminate, 21: resin film, 30: vacuum molding chamber, 31: upper molding chamber, 32: lower molding chamber, 33: adherend 34: drive device, 35: clamp, 36: table, 37: gas supply chamber, 38: gas suction chamber, 60: adherend covered with resin film, 70: model

Claims (14)

Laminating an adhesive sheet containing an acrylic polymer and a polymerization initiator on the surface of the resin film, and manufacturing a resin laminate in which the resin film and the adhesive sheet are laminated,
Covering the adherend with the resin film while pressing the resin laminate against the adherend and stretching the resin film following the surface shape of the adherend,
The shape when the resin laminate is viewed in plan is larger than the shape when the adherend is viewed in plan,
The covering step includes heating the resin laminate, pressing the resin laminate on the adherend in a planar manner in a reduced pressure environment, and then pressing the resin film against the adherend. A method for producing a molded body, comprising pressurizing a side environment.  The manufacturing method of the molded object of Claim 1 in which the said adhesive sheet contains an acrylic monomer or an acrylic oligomer further.  The method for producing a molded article according to claim 2, wherein the acrylic monomer is a (meth) acrylate monomer containing a hydroxyl group or a polyfunctional acrylate monomer having a hydroxyl group.   The manufacturing method of the molded object of Claim 2 which contains curable urethane acrylate as at least one part of the said acrylic monomer or acrylic oligomer.  The haze value of the said adhesive sheet is 1.0% or less, and the total light transmittance is 85% or more, The manufacturing method of the molded object of any one of Claims 1-4.  The method for producing a molded body according to any one of claims 1 to 5, wherein the thickness of the adhesive sheet is 20 µm or more and 200 µm or less.   The method for producing a molded body according to any one of claims 1 to 6, wherein the adhesive strength of the adhesive sheet after heating is 30 N / 25 mm or more.   The method for producing a molded article according to any one of claims 1 to 7, wherein the polymerization initiator is a thermal polymerization initiator.   The method for producing a molded body according to claim 8, wherein a polymerization initiation temperature of the thermal polymerization initiator is lower by 10 ° C or more and 50 ° C or less than a heating temperature in the coating step. Before the step of producing the resin laminate, an acrylic polymer and a polymerization initiator are mixed to produce an adhesive raw material composition, and the adhesive raw material composition is applied onto a separator. Including stacking separators and manufacturing an adhesive sheet sandwich body,
The process of manufacturing the said resin laminated body is a process of peeling one separator of the said adhesive sheet clamping body, laminating | stacking on a resin film, and peeling the other separator after that. The manufacturing method of the molded object of description.  The manufacturing method of the molded object of any one of Claims 1-10 provided with the process of forming a printing layer or a vapor deposition layer on the said resin film before the process of manufacturing the said resin laminated body.  The material for forming 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 manufacturing method of the molded object of description.  The manufacturing method of the molded object of any one of Claims 1-12 in which the surface which coat | covers the resin film in the said adherend contains the level | step difference whose angle is 90 degree | times or more.  The molded body according to any one of claims 1 to 13, wherein a material for forming the adherend is at least one selected from the group consisting of a carbon fiber reinforced plastic, a polycarbonate resin, an acrylic resin, and an ABS resin. Manufacturing method.

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