Resin liquid and molded product forming method

Abstract

The invention provides a resin liquid suitable for manufacturing a molded article containing a metal three-dimensional structure and a method for forming the molded article. The resin liquid contains a radical photocurable resin, a thermosetting resin, and an acid catalyst, and the thermosetting resin contains a melamine-based crosslinking agent or a benzoguanamine-based crosslinking agent, and contains 3-60 wt% of the thermosetting resin.

Description

Technical Field

[0001] The present invention relates to a resin liquid and a method for forming a molded object. Background Art

[0002] Japanese Patent Publication No. 2019-123909 (Patent Document 1) describes a structure to be plated and a circuit structure for chemical plating using a primer, as well as a pretreatment method for chemical plating and a chemical plating method. The structure to be plated for chemical plating is a structure laminated with an insulating substrate, a primer and a catalyst metal layer. In the structure to be plated for chemical plating, the catalyst metal layer is composed of monodisperse metal nanoparticles with a particle size of 2 to 100 nm, the primer has an amino group, and the catalyst metal layer is formed on the primer by uniformly dispersing a group of monodisperse metal nanoparticles in an aqueous solution, and the catalyst metal layer is combined with the primer via the amino group on the primer.

[0003] Japanese Patent Application Laid-Open No. 2012-006234 (Patent Document 2) describes a three-dimensional polymer-metal composite microstructure and a method for manufacturing the same. In the manufacturing method, a photocurable resin having a reactive group X is used to form a polymer structure by a photoforming method, and the polymer structure is immersed in a liquid containing metal nanoparticles having a reactive group X' that is bonded to the reactive group X. A metal-containing layer containing gold or the like is formed on the polymer structure by the combination of the reactive group X and the reactive group X', thereby manufacturing a polymer-metal composite structure having a three-dimensional structure. An example of the reactive group X is an amino group. The amino group is formed so as to be protected in a stable manner during photoforming and to generate an active primary amine by contact with water. Patent Document 2 also discloses the following situation: a method including a process of forming a fine first component having an arbitrary three-dimensional structure by a photoforming method and a process of forming a fine second component having an arbitrary three-dimensional structure and connected to the first component is used to form a fine polymer structure as an integrally formed product including a first component and a second component, and a metal-containing layer is formed only on one of the first component or the second component. In this case, it is shown that the first component and the second component have different reactive groups.

[0004] Japanese Patent Publication No. 2017-218604 (Patent Document 3) describes a method for forming a coating on a photoformed product. The method for forming a coating on a photoformed product includes: a first step of preparing a photoformed product having a three-dimensional structure by curing and laminating epoxy resin in layers by a photoforming method; a second step of using #800 to #2000 abrasives to complete surface processing of the surface of the photoformed product by grinding, grinding, sandblasting, or a combination of mechanical treatments such as the above, so that the arithmetic mean roughness Ra of the surface is greater than 0.141 μm, preferably less than 0.458 μm; a third step of performing chemical nickel plating on the surface of the photoformed product to form a coating without performing an etching step. In the third step, after a pretreatment step including a sensitization step and an activation step is performed, chemical nickel plating is performed on the surface of the photoformed product, wherein the sensitization step is a step of forming a coating film of a tin compound on the surface of the photoformed product using a tin sol solution, and the activation step is a step of using a solution containing palladium ions to adsorb a plating catalyst composed of palladium onto the surface of the photoformed product.

[0005] In Japanese Patent Publication No. 2021-006405 (Patent Document 4), a method for manufacturing a three-dimensional object from a material having a plurality of curing mechanisms is described. The three-dimensional object manufacturing method is performed as follows: a process of preparing an optically transparent member having a carrier and a construction surface; a process of filling a construction area with a polymerizable liquid, wherein the polymerizable liquid comprises a first component of a photopolymerizable liquid and a mixture of a second component having a coagulation property different from the first component; irradiating light to the construction area via the optically transparent member, forming a solid polymer support from the first component, and moving the carrier away from the construction surface to form a three-dimensional intermediate having the same shape as the three-dimensional object or giving the three-dimensional object a shape, the three-dimensional intermediate containing the second component loaded in the support in an unsolidified form and / or uncured form; a process of solidifying and / or curing the second component in the three-dimensional intermediate to form a three-dimensional object simultaneously with or after the irradiation process. The second component comprises, for example, a precursor of polyurethane, polyurea or a copolymer thereof, a silicone resin or a natural rubber, and the solidification and / or curing process is performed by heating or microwave radiation.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2019-123909

[0009] Patent Document 2: Japanese Patent Application Publication No. 2012-006234

[0010] Patent Document 3: Japanese Patent Application Publication No. 2017-218604

[0011] Patent Document 4: Japanese Patent Application Publication No. 2021-006405 Summary of the invention

[0012] Problem that the invention aims to solve

[0013] As described in Patent Document 1, there is a demand for using a plating method to construct a metal structure such as a circuit or a molded product containing the structure. In recent years, there has been a particular demand for constructing a molded product containing a metal three-dimensional structure. The method for manufacturing a structure or a molded product containing a metal described in Patent Document 2 requires the use of two or more photocurable resins with different reactive groups to form a three-dimensional structure and then form a metal-containing layer. The process is complicated and is not very suitable for the construction of a molded product containing a metal three-dimensional structure. Similarly, the method for forming a film on a photomolded product described in Patent Document 3 is not very suitable for the construction of a molded product containing a metal three-dimensional structure because it is impossible to form a suitable film on a portion that cannot be polished. As described above, there is room for improvement in the resin liquid and the method for forming a molded product suitable for the manufacture of a molded product containing a metal three-dimensional structure. Therefore, it is desired to provide a resin liquid and a method for forming a molded product suitable for the manufacture of a molded product containing a metal three-dimensional structure.

[0014] The present invention has been made in view of the above-mentioned actual situation, and an object thereof is to provide a resin liquid suitable for producing a molded product including a three-dimensional metal structure and a method for forming a molded product.

[0015] Technical solutions for solving technical problems

[0016] In order to achieve the above-mentioned object, the resin liquid related to the present invention,

[0017] Contains free radical light curing resin, heat curing resin and acid catalyst,

[0018] As the thermosetting resin, a melamine-based crosslinking agent or a benzoguanamine-based crosslinking agent is included,

[0019] The thermosetting resin is contained in an amount of 3 wt % to 60 wt %.

[0020] In order to achieve the above-mentioned object, the present invention relates to a method for forming a molded article, comprising:

[0021] A molding step, wherein a first molded product is obtained by molding using a resin liquid, wherein the resin liquid comprises a free radical photocurable resin, a thermosetting resin and an acid catalyst, wherein the thermosetting resin comprises a melamine-based crosslinking agent or a benzoguanamine-based crosslinking agent, and further comprises 3 wt % to 60 wt % of the thermosetting resin;

[0022] A final photocuring step, wherein the first molded object is irradiated with light having a wavelength of 300 nm or more to photocure the first molded object to obtain a second molded object;

[0023] The thermal curing step includes heating the second molded product at a temperature of 60° C. to 280° C. to thermally cure the second molded product to obtain a third molded product.

[0024] Effects of the Invention

[0025] A resin solution suitable for producing a molded product including a three-dimensional metal structure and a method for forming a molded product can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is a SEM image of the surface of the third molded product of Example 1 on which the metal nanoparticle catalyst is supported.

[0027] Figure 2 These are photographs of the third formed product and the metal structure involved in Example 1.

[0028] Figure 3 These are photographs of the third formed product and the metal structure involved in Example 3.

[0029] Figure 4 These are photographs of the third formed product and the metal structure involved in Example 4.

[0030] Figure 5 This is a photograph of the molded product of Example 8 (the content of the thermosetting resin is 1%).

[0031] Figure 6 This is a photograph of the molded product of Example 8 (the content of the thermosetting resin is 10%).

[0032] Figure 7 This is a photograph of the molded product of Example 8 (the content of the thermosetting resin is 70%).

[0033] Description of Reference Numerals

[0034] 11: Structure

[0035] 31, 32, 33, 34, 35: Structure

[0036] 40: Spiral Tunnel Space

[0037] 41: Structure. DETAILED DESCRIPTION

[0038] The embodiments of the present invention describe a resin solution and a method for forming a molded product.

[0039] The resin solution involved in this embodiment comprises a free radical photocurable resin, a thermosetting resin and an acid catalyst. In the resin solution, the thermosetting resin comprises a melamine crosslinking agent or a benzoguanamine crosslinking agent. The resin solution comprises 3 wt % to 60 wt % of the thermosetting resin.

[0040] The method for forming a molded object involved in the present embodiment includes: a molding step, in which a first molded object is obtained by molding using the resin liquid involved in the present embodiment; a final photocuring step, in which the first molded object is irradiated with light with a wavelength of more than 300nm to photocure it, thereby obtaining a second molded object; and a thermal curing step, in which the second molded object is heated at a temperature of more than 60°C and less than 280°C to thermally cure it, thereby obtaining a third molded object.

[0041] According to the resin liquid and the method for forming a molded object involved in the present embodiment, a resin liquid and a method for forming a molded object suitable for manufacturing a molded object containing a metal three-dimensional structure can be provided. That is, the first molded object formed using the resin liquid may not have a hardness sufficient to maintain the three-dimensional structure for a long time or to be handled without destroying the shape, but because the resin liquid contains a free radical photocurable resin, it becomes a second molded object with a hardness sufficient to maintain the three-dimensional structure through a photocuring process. Furthermore, the resin liquid contains a thermosetting resin and an acid catalyst, and through a thermosetting process, the second molded object is completely cured and becomes a third molded object having an amino group on the surface of the molded object for loading a catalyst for chemical plating. That is to say, using the resin liquid involved in the present embodiment and providing it to the method for forming a molded object involved in the present embodiment, a third molded object that is a substrate suitable for manufacturing a molded object containing a metal three-dimensional structure can be obtained.

[0042] The resin solution and the method for forming a molded product are described in detail below.

[0043] The resin solution involved in this embodiment includes a free radical photocurable resin, a thermosetting resin and an acid catalyst, and may further include a filler, a pigment and other additives.

[0044] Fillers, pigments and other additives may be used without particular limitation as long as they do not hinder free radical photocuring and thermal curing to the extent that the purpose of this embodiment is impaired, and do not deactivate the amino group of the thermosetting resin to the extent that the purpose of this embodiment is impaired.

[0045] The free radical photocurable resin is a material that forms a molded object through a curing reaction, and the molded object serves as a support for maintaining a metal three-dimensional structure. The concept of the free radical photocurable resin in this embodiment includes a resin with a relatively small molecular weight, specifically a prepolymer or a monomer that can become a free radical photocurable resin. The weight average molecular weight is preferably greater than 150 and less than 20,000.

[0046] The free radical photocurable resin comprises at least one selected from polyurethane acrylate, epoxy acrylate, acrylic acrylate, polyester acrylate, and acrylate monomer.

[0047] The radical photocurable resin preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include alkyl phenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, thioxanthones, and intramolecular hydrogen abstraction-type photopolymerization initiators.

[0048] As the thermosetting resin, an alkylated amino resin, specifically, a melamine-based crosslinking agent or a benzoguanamine-based crosslinking agent can be contained.

[0049] The melamine crosslinking agent includes methylol melamine or a methylol melamine derivative. As the melamine crosslinking agent, melamine, a methylol melamine derivative obtained by condensing melamine with formaldehyde, a compound obtained by reacting a lower alcohol with methylol melamine and partially or completely etherifying it, or a mixture thereof, etc. can be used. As the lower alcohol, a fatty alcohol having a carbon number of 1-4 can be cited. In addition, as the melamine crosslinking agent, any one of the condensates composed of a monomer or a polymer above a dimer can be used, or a mixture thereof can be used. If it is a monomer, hexamethoxymethyl melamine is preferably used. Condensates composed of polymers, specifically, can include imino-type methylated melamine resins, methylol-type melamine resins, methylol-type methylated melamine resins, and fully alkyl-type methylated melamine resins.

[0050] As the benzoguanamine cross-linking agent, hydroxymethylbenzoguanamine or hydroxymethylbenzoguanamine derivatives are included. As the benzoguanamine cross-linking agent, benzoguanamine, hydroxymethylbenzoguanamine derivatives obtained by condensing benzoguanamine with formaldehyde, compounds obtained by reacting lower alcohols with hydroxymethylbenzoguanamine and partially or completely etherifying, or mixtures thereof, etc. can be used. As lower alcohols, fatty alcohols with carbon atoms of 1-4 can be listed. In addition, as the benzoguanamine cross-linking agent, any one of the condensates composed of monomers or polymers above dimers can be used, or mixtures thereof can be used. If it is a monomer, tetramethoxymethylbenzoguanamine is preferably used. Condensates composed of polymers, specifically, butylated benzoguanamine resins, hydroxymethylated benzoguanamine resins, etc. can be listed.

[0051] The benzoguanamine-based crosslinking agent may be used together with the melamine-based crosslinking agent.

[0052] As the acid catalyst, a sulfonic acid catalyst or a phosphoric acid catalyst can be used. For example, a dinonylnaphthalene disulfonic acid catalyst, a dinonylnaphthalene sulfonic acid catalyst, p-toluenesulfonic acid or its blocked acid catalyst, and a phosphoric acid blocked acid catalyst can be used.

[0053] As described above, the resin solution according to this embodiment contains a radical photocurable resin, so that the second molded product can be cured by the photocuring step.

[0054] The resin solution of this embodiment contains 40% to 97%, preferably 50% to 95% of free radical photocurable resin by mass after removing the solvent. Therefore, the second molded product has sufficient and appropriate hardness to maintain the three-dimensional structure through the photocuring process.

[0055] The resin liquid involved in this embodiment includes a thermosetting resin and an acid catalyst, wherein the thermosetting resin includes a melamine-type cross-linking agent or a benzoguanamine-type cross-linking agent. Through a thermal curing process, the second molded product is completely cured and becomes a third molded product having an amino group on the surface of the molded product for loading a catalyst for chemical plating.

[0056] The resin solution according to this embodiment contains 3% to 60% of thermosetting resin, preferably 5% to 50% of thermosetting resin, by mass after removing the solvent. Thus, the third molded product becomes a molded product having appropriate strength as a metal three-dimensional structure through the thermosetting step.

[0057] The resin liquid according to the present embodiment may contain a solvent as necessary for the purpose of adjusting viscosity or the like.

[0058] The molded product forming method according to the present embodiment, as described above, comprises: a molding step in which a first molded product is obtained; a final photocuring step in which a second molded product is obtained from the first molded product; and a thermal curing step in which a third molded product is obtained from the second molded product.

[0059] The molding step is a step of obtaining a first molded product having a shape corresponding to the molded product including the three-dimensional metal structure from the resin solution according to the present embodiment.

[0060] The forming process can be performed by so-called 3D printing. As a method of 3D printing, for example, the following can be used: SLA (Stereolithography Apparatus), in which a point-shaped ultraviolet light or other light is irradiated to a resin liquid, so that the resin is gradually solidified and stacked from a base to construct a three-dimensional shape; DPL (Digital Light Projector), in which a planar ultraviolet light or other light is irradiated to a resin liquid, so that the resin is gradually solidified and stacked from a base to construct a three-dimensional shape; MJ (Material Jetting) method (also called inkjet method), in which a resin liquid is sprayed from a plurality of nozzles, irradiated with ultraviolet light or other light, and solidified and stacked at the same time, thereby constructing a three-dimensional shape.

[0061] The first molded product does not need to have a hardness sufficient to maintain a three-dimensional structure for a long time or to be handled without losing its shape, but only needs to have a strength sufficient to be used in a photocuring step.

[0062] In the forming process, the wavelength of light used to photo-cure the resin liquid is 300 nm to 450 nm, preferably ultraviolet light of 350 nm to 410 nm. By using light with a wavelength of 300 nm or more to photo-cure the resin liquid, the deactivation of the amino group used to support the catalyst for chemical plating can be suppressed.

[0063] The first molded product is finally cured by the final photocuring step to form a second molded product having a hardness sufficient to maintain a three-dimensional structure for a long time or to be handled without losing its shape.

[0064] In the final photocuring step, the first molded product is irradiated with ultraviolet light of 300 nm to 450 nm, preferably 350 nm to 410 nm, so that the first molded product is cured while suppressing the deactivation of the amino group for supporting the catalyst for chemical plating.

[0065] The second molded product is completely cured by thermal curing through a thermal curing process, and a third molded product having an amino group for supporting a catalyst for chemical plating on the surface of the molded product is formed. In the thermal curing process, the second molded product is thermally cured by heating at a temperature of 60°C to 280°C. If the heating temperature in the thermal curing process is too low, the time required for thermal curing may become too long, and if the heating temperature is too high, one of the components of the third molded product may deteriorate or deteriorate. In a case where the time required for thermal curing is allowed to be prolonged, a heating temperature of 60°C or less can be used. Furthermore, a heating temperature of 280°C or more can also be used if none of the components of the third molded product deteriorates or deteriorates. In addition, in most cases, a heating temperature of 80°C to 150°C is appropriate.

[0066] Then, the third formed object is provided to form a catalyst loading process in which the catalyst loading region of the metal nanoparticles is loaded on its surface. In the catalyst loading region, a plating process of reducing chemical plating can be easily performed. As described later, the third formed object becomes a substrate suitable for manufacturing a formed object containing a metal three-dimensional structure.

[0067] In the catalyst loading step, the metal nanoparticles are loaded by being adsorbed by the amino groups present on the surface of the third molded article. Therefore, before the catalyst loading step, a region where the amino groups are deactivated and a region where the amino groups are not deactivated but remain are formed on the surface of the third molded article, so that in the catalyst loading step, the metal nanoparticles can be loaded only on the region where the amino groups are not deactivated but remain. In other words, chemical plating can be performed only on the region where the amino groups are not deactivated but remain.

[0068] As an example of a process for realizing a method of forming, on the surface of a third molded article, a region where the amino groups are inactivated and a region where the amino groups are not inactivated but remain, a pattern forming process can be listed: irradiating a portion of the surface of the third molded article with light (deep ultraviolet light) having a wavelength less than 300 nm to form an irradiated region irradiated with light having a wavelength less than 300 nm and a non-irradiated region not irradiated with light having a wavelength less than 300 nm.

[0069] In the pattern forming step, a portion of the surface of the third molded article is irradiated with light having a wavelength of less than 300 nm (i.e., local irradiation with light having a wavelength of less than 300 nm is performed), thereby forming a region in which the amino groups are inactivated on the surface of the third molded article. In addition, on the surface of the third molded article, the non-irradiated region becomes a region in which the amino groups are not inactivated but remain.

[0070] As shown in the pattern forming step, by forming a region where the amino group is inactivated and a region where the amino group is not inactivated but remains, the shape of the plated portion (i.e., the three-dimensional metal structure) can be drawn in the plating step. That is, through the pattern forming step, the catalyst loading step, and the plating step, a three-dimensional metal structure can be constructed using the third molded object as a substrate.

[0071] In the pattern forming step, in the local irradiation with light having a wavelength of less than 300 nm, a photomask such as a quartz mask or a metal mask may be used, or local irradiation with deep ultraviolet laser may be performed.

[0072] The pretreatment solution for chemical plating used in the catalyst loading step is preferably a colloidal solution containing metal nanoparticles as a reduced chemical plating catalyst. The pretreatment solution for chemical plating is preferably a pretreatment solution for chemical plating composed of metal nanoparticles of Group IB or Group VIIIB of the periodic table, sugar alcohol and water.

[0073] Preferably, the pH of the pretreatment solution for chemical plating is 6.5 to 8.0, and the Zeta potential is -50 mV to -80 mV. Preferably, in the pretreatment solution for chemical plating, the average particle size of the metal nanoparticles is 10 nm to 40 nm, and the metal concentration is 50 mg / L to 200 mg / L. In addition, preferably, in the pretreatment solution for chemical plating, the sugar alcohol concentration is 0.05 g / L to 1.0 g / L.

[0074] Metal nanoparticles are nanoparticles of Group IB or Group VIIIB elements in the periodic table. Specifically, they are gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru), nickel (Ni), cobalt (Co) and iron (Fe). These metals can be dispersed in liquids in a stable colloidal state through sugar alcohols. In particular, metal nanoparticles are preferably colloidal nanoparticles of gold (Au), platinum (Pt) or palladium (Pd).

[0075] The sugar alcohol is preferably at least one selected from the group consisting of propitol, tetritol, pentitol, hexitol, heptitol, octitol, inositol, quercetin and pentaerythritol.

[0076] In addition, preferred combinations are as follows: When the colloidal nanoparticles are platinum (Pt) nanoparticles, palladium (Pd) nanoparticles, or gold (Au) nanoparticles, the sugar alcohol is preferably at least one of glycerol, erythritol, xylitol, mannitol, inositol, or pentaerythritol.

[0077] In the catalyst loading step, the third formed article may be brought into contact with the chemical plating pretreatment solution by immersing the third formed article in the chemical plating pretreatment solution, etc. Thus, the metal nanoparticles are adsorbed and loaded in the non-irradiated area where the amino groups are not deactivated but remain.

[0078] In the plating process, the third molded object with metal nanoparticles adsorbed on the surface is immersed in a reduced chemical plating solution. Thus, the metal nanoparticles become a catalyst for the chemical plating reaction, and the chemical plating reaction proceeds to form a metal film in the non-irradiated area. In this way, a molded object including a metal three-dimensional structure formed along the surface shape of the third molded object can be constructed.

[0079] Example

[0080] Hereinafter, the resin solution and the method for forming a molded product according to the present embodiment will be described by way of examples. In the following description, when "%" is simply described, it means "% by weight".

[0081] (Example 1)

[0082] A resin liquid for forming a molded object is prepared, the resin liquid comprising: 90% of a readily available free radical light-curing type light-curing resin liquid (product name: Clear Resin, manufactured by Formlabs, containing as main components: 15-25% of methacrylate monomer, 55-75% of polyurethane acrylate, 0.9% of acylphosphine oxide type photopolymerization initiator), 9% of a hydroxymethyl melamine crosslinking agent (product name: CYMEL303LF, manufactured by Allnex, containing as main components: 99% or more of alkylated melamine), and 1% of a sulfonic acid catalyst (product name: CYCAT4040, manufactured by Allnex, containing as main components: 40% of p-toluenesulfonic acid, 54% of isopropyl alcohol). In addition, in the resin liquid, the free radical light-curing type light-curing resin is 89%, and the thermosetting resin is 10%. In addition, the acid catalyst is 1%.

[0083] The resin liquid is poured into an SLA-type light-forming 3D printer (product name: Form2, manufactured by Formlabs) and three-dimensionally formed to obtain a first formed object having a cubic mesh shape with a six-sided mesh surface. The light used for light curing during three-dimensional forming is ultraviolet light and blue-violet light with a central wavelength of 405nm, and does not include light with a wavelength less than 300nm.

[0084] After the first molded product was washed with ethanol, it was irradiated with light having a central wavelength of 405 nm (but excluding light having a wavelength of less than 300 nm) to perform secondary curing, thereby obtaining a second molded product.

[0085] The second molded product was placed in a normal pressure oven with an internal ambient temperature of 100° C. and heated. The heating time in the oven (the holding time in the oven) was set to 10 minutes. Thus, the second molded product was thermally cured to obtain a third molded product.

[0086] Next, the third formed article was immersed in a colloidal solution of a gold nanoparticle catalyst for chemical plating (product name: CAT-Au10, manufactured by EEJA) as a pretreatment solution for chemical plating, and pretreatment of reduction-type chemical plating was performed. The temperature of the pretreatment solution for chemical plating during pretreatment was set to 25° C. The immersion time of the third formed article in the pretreatment solution for chemical plating during pretreatment was set to 15 minutes.

[0087] After this pretreatment, the gold nanoparticle catalyst with a particle size of about 20 nm was uniformly adsorbed and supported on the surface of the third molded product (refer to Figure 1 ).

[0088] Next, the pretreated third molded article was immersed in a reduction type chemical gold plating solution (product name: AC FABAu-ACG3000WX, manufactured by EEJA) to perform reduction type chemical plating. The temperature of the chemical gold plating solution during the plating treatment was set to 65° C. The immersion time of the third molded article in the chemical gold plating solution during the plating treatment was set to 20 minutes.

[0089] By this chemical gold plating, a gold film with a thickness of 200 nm can be obtained on the entire surface of the third molded product, that is, a metal three-dimensional structure having a shape along the surface of the third molded product can be obtained (see Figure 2 ). In addition, Figure 2 The grid-shaped cube shown as the structure 11 is a metal structure formed on the surface of the third molded product involved in Example 1. Figure 2 2 is a photograph showing a state in which the structure 11 is held by a base portion (sub-component) during three-dimensional molding.

[0090] (Example 2)

[0091] Example 2 is different from Example 1 in that a hydroxymethyl / n-butylbenzoguanamine crosslinking agent (product name: BX-4000, manufactured by Japan Kabido Industries, containing 99% or more of hydroxymethyl / hydroxyn-butylbenzoguanamine as a main component) is used instead of the hydroxymethylmelamine crosslinking agent, and other than that, Example 2 is the same as Example 1. As in Example 1, a metal three-dimensional structure having a shape along the surface of the third molded product can be obtained by chemical gold plating.

[0092] (Example 3)

[0093] Example 3 is different from Example 1 in that a resin liquid obtained by mixing 89% of a bifunctional acrylate monomer (product name: IRR 214-K, manufactured by Dicel Ornex, containing 99% of tricyclodecane dimethanol diacrylate as a main component) and 1% of an acylphosphine oxide-based photopolymerization initiator (product name: Omnirad 819, manufactured by IGM Resins BV, containing 99% of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a main component) is used instead of an existing free radical photocurable photocurable resin liquid. Furthermore, the resin liquid is prepared in the same manner as in Example 1 except that the acid catalyst (product name: CYCAT4040) is replaced by an acid catalyst (product name: NACURE X49-110, manufactured by Kusumoto Chemical Industry, containing 25% of dinonylnaphthalene disulfonate and 75% of a mixed solvent of isopropyl alcohol and isobutyl alcohol as a main component). In addition, the solid components of the resin liquid are: 90% of the free radical light-curing type photocurable resin and 10% of the heat-curable resin.

[0094] The resin liquid was poured into a SLA-type light-forming 3D printer (product name: Form2, manufactured by Formlabs) and three-dimensionally formed to obtain a first formed object in the shape of a thick disk. The light used for light curing during three-dimensional forming is ultraviolet light and violet light with a central wavelength of 405nm, and does not include light with a wavelength less than 300nm.

[0095] Next, deep ultraviolet light with a central wavelength of 254 nm (light source product name: Deep-UV Lamps UXM-5001MD, manufactured by Ushio Electric) was irradiated onto the surface of the third molded product through a quartz photomask to form irradiated areas and non-irradiated areas. The irradiation dose was 1000 mJ / cm 2 (Value measured at a central wavelength of 254 nm).

[0096] The third molded product after the irradiation region and the non-irradiation region were formed was pretreated in the same manner as in Example 1 using the pretreatment solution for chemical plating.

[0097] Next, the pretreated third molded article was immersed in a reduction type chemical gold plating solution (product name: AC FABAu-ACG3000WX, manufactured by EEJA) to perform reduction type chemical plating treatment. The temperature of the chemical gold plating solution during the plating treatment was set to 65° C. The immersion time of the third molded article in the chemical gold plating solution during the pretreatment was set to 10 minutes.

[0098] By this chemical gold plating, a gold film with a film thickness of 100 nm can be obtained on a part of the surface of the disk-shaped third molded product, that is, a metal wiring pattern structure along the shape of the surface of the third molded product can be obtained (see Figure 3). In addition, Figure 3 , the metal linear patterns shown as structures 31, 32, 33, 34, and 35 are metal structures according to Example 3 formed on the third molded product.

[0099] (Example 4)

[0100] In Example 4, the same ready-made free radical photocurable photocurable resin liquid as in Example 1 is used. Unlike Example 1, a first molded product having a rectangular shape and a spiral (coil-shaped) tunnel space (flow path) formed inside is obtained by molding using a SLA light molding 3D printer in the same manner as in Example 1.

[0101] A second molded product was obtained in the same manner as in Example 1 from the first molded product, and a third molded product was obtained in the same manner as in Example 1 from the second molded product.

[0102] Next, the surface of the third molded product was irradiated with deep ultraviolet light having a central wavelength of 254 nm (light source product name: Deep-UV Lamps UXM-5001MD, manufactured by Ushio Electric). The irradiation dose was 1000 mJ / cm 2 (Value measured at a central wavelength of 254 nm) Since the third molded object does not transmit deep ultraviolet light, the inner surface of the spiral tunnel space in the third molded object becomes a non-irradiated area, and the other surfaces of the third molded object become an irradiated area.

[0103] After the irradiation area and the non-irradiation area are formed, the third formed article is pretreated with a pretreatment solution for chemical plating in the same manner as in Example 1, and further, chemical plating is performed. Thus, a gold film with a thickness of 200 nm can be obtained only on the inner surface of the spiral tunnel space of the third formed article, that is, a tubular spiral metal three-dimensional structure having a shape along the inner surface of the spiral tunnel space of the third formed article is obtained (see Figure 4 ). In addition, Figure 4 In the figure, the tubular spiral structure 41 formed in the spiral tunnel space 40 is the metal structure according to Example 4 formed inside the third molded product.

[0104] (Example 5)

[0105] Example 5 is different from Example 1 in that a resin liquid prepared by mixing 89% of a bifunctional acrylate monomer (product name: HDDA, manufactured by Dicel Ornex, containing 99% of 1,6-hexanediol diacrylate as a main component) and 1% of an acylphosphine oxide-based photopolymerization initiator (product name: Omnirad 819, manufactured by IGM Resins BV) is used as a free radical photocurable photocurable resin liquid instead of the existing free radical photocurable photocurable resin liquid. The resin liquid is hereinafter referred to as a first liquid.

[0106] In Example 5, further, as a free radical photocurable photocurable resin liquid, a resin liquid obtained by mixing 99% of a bifunctional acrylate monomer (product name: HDDA, manufactured by Dicel Ornex) and 1% of an acylphosphine oxide-based photopolymerization initiator (product name: Omnirad 819, manufactured by IGM Resins BV) was prepared as the second liquid.

[0107] The first liquid and the second liquid were poured into an MJ (inkjet) printer (product name: LaboJet, manufactured by Microjet) and three-dimensionally molded to obtain a disk-shaped first molded product similar to Example 3. In Example 5, the first liquid and the second liquid were separated, and the first liquid was used to construct the portion of the first molded product where the metal wiring pattern was desired to be formed. In the three-dimensional molding of the first molded product, each time the first liquid and the second liquid were used to perform two-dimensional drawing, ultraviolet light with a central wavelength of 340 nm using an LED as a light source was irradiated to photocure it, and this operation was repeated to construct the three-dimensional structure of the first molded product.

[0108] The first molded product was washed with ethanol and then irradiated with ultraviolet light having a central wavelength of 340 nm (but excluding light having a wavelength of less than 300 nm) for secondary curing to obtain a second molded product.

[0109] The second molded product was subjected to the same procedure as in Example 1 to obtain a third molded product.

[0110] The third molded product, unlike Example 3, does not form an irradiated area, and is directly subjected to pretreatment with a pretreatment solution for chemical plating and chemical gold plating with a chemical gold plating solution in the same manner as Example 3. Thus, as the metal wiring pattern structure according to Example 5, a metal structure similar to the metal structure according to Example 3 is obtained.

[0111] (Example 6)

[0112] Example 6 is different from Example 1 in that a resin solution obtained by mixing 89% of a bifunctional acrylate monomer (product name: IRR 214-K) and 1% of an acylphosphine oxide photopolymerization initiator (product name: Omnirad TPO H, manufactured by IGM Resins BV, containing 99% of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a main component) is used instead of the existing free radical photocurable photocurable resin solution, and further, a phosphoric acid acid catalyst (product name: NACURE 4167, manufactured by Kusumoto Chemical Industry, containing 25% of a phosphate and 75% of a mixed solvent of isopropyl alcohol and isobutyl alcohol as a main component) is used instead of the sulfonic acid acid catalyst (product name: CYCAT4040). The same as Example 1 is used except that a metal three-dimensional structure having a shape along the surface of the third molded product can be obtained by chemical gold plating.

[0113] (Example 7)

[0114] Example 7 is different from Example 1 in that, instead of the ready-made free radical photocurable photocurable resin liquid (product name: Clear Resin), 90% of other ready-made free radical photocurable photocurable resin liquid (product name: HighTemp, manufactured by formlabs, containing 60-80% of acrylate monomer, 25-45% of polyurethane acrylate and 1.5% of acylphosphine oxide photopolymerization initiator as main components) is used. Apart from this, the resin liquid for forming the molded object is prepared in the same manner as in Example 1.

[0115] In the three-dimensional molding of the first molded product, an SLA-based optical molding 3D printer (product name: Space Art, manufactured by TKR) was used, which was different from that in Example 1. In the same manner as in Example 1, the first molded product and the second molded product were obtained.

[0116] Different from Example 1, the second molded product was heated in a normal pressure oven with an internal ambient temperature of 280° C. The heating time in the oven (the holding time in the oven) was set to 3 minutes. The second molded product was thermally cured to obtain a third molded product.

[0117] Furthermore, similarly to Example 1, chemical gold plating was performed to obtain a three-dimensional metal structure having a shape along the surface of the third molded product.

[0118] (Example 8)

[0119] In Example 8, the formulation amounts of the radical photocurable photocurable resin liquid and the thermosetting resin were changed to confirm the influence on the metal structure.

[0120] In Example 8, unlike Example 1, instead of the ready-made free radical photocurable photocurable resin liquid, a resin liquid prepared by mixing 80% of a difunctional acrylate monomer (product name: IRR 214-K), 19% of a difunctional acrylate monomer (product name: HDDA) and 1% of an acylphosphine oxide-based photopolymerization initiator (product name: Omnirad TPO H, manufactured by IGM Resins BV, containing 99% of 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a main component) is used as the free radical photocurable photocurable resin liquid.

[0121] As the thermosetting resin, similarly to Example 1, a methylol melamine crosslinking agent (product name: CYMEL303LF) was used.

[0122] The acid catalyst was also used in the same manner as in Example 1 (product name: CYCAT4040).

[0123] The formula of the free radical photocurable photocurable resin liquid, thermosetting resin and acid catalyst is shown in Table 1 below. Resin liquids 1 to 7 for forming molded products having different contents of methylol melamine crosslinking agent (thermosetting resin) were prepared with this formula.

[0124] [Table 1]

[0125]

[0126] In the three-dimensional forming of the first molded product, an SLA-type light forming 3D printer (product name: Space Art, manufactured by TKR) different from that in Example 1 is used to make the molded shape a cubic frame (12 sides). Apart from this, after obtaining the third molded product using resin liquids 1 to 7 in the same manner as in Example 1, chemical gold plating is performed on each third molded product in the same manner as in Example 1.

[0127] The third molded products using the resin solutions 1 to 7 and the chemical gold plating applied thereto were evaluated for moldability and whether the plating was good or not.

[0128] The evaluation of the formability of the third molded product is performed by measuring the length of the four sides. The evaluation adopts three levels. The evaluation is good and A is the case that the moldable product can be formed according to the design information data (drawing) used by the 3D printer; the case that the dimensional error of 10% to 20% from the design information data is observed on the third molded product is evaluated as B; the case that the deformation is more serious than the evaluation B and is evaluated as a defect that cannot be formed is evaluated as C. In other words, the case that the moldable product can be formed well compared with the evaluation B is evaluated as A.

[0129] The evaluation of the plating involved in the third molded product was carried out by measuring the gold film thickness at six points using a fluorescent X-ray film thickness measuring device (SFT9550, manufactured by Hitachi HiTech Science). The evaluation was carried out in three levels, with the gold film with an average film thickness of 150 to 250 nm formed on the surface of the molded product being considered good and evaluated as A; the case where a gold film with an average film thickness of 50 to 150 nm was formed was evaluated as an uneven plating film, and the case where only an average film thickness of less than 50 nm was detected was evaluated as no plating precipitation, evaluated as C.

[0130] Table 2 below shows the evaluation results of formability and plating of the third molded products using resin solutions 1 to 7 and the chemical gold plating applied thereto. Figure 5 , Figure 6 and Figure 7 2 shows photographs of third molded products using resin solutions 1, 3, and 7, that is, molded products having thermosetting resin contents of 1%, 10%, and 70%, respectively.

[0131] [Table 2]

[0132]

[0133] As shown in Table 2, when the resin liquid for forming the molded product is resin liquid 2 to 6 (the thermosetting resin content is 5% to 50%) (for example, refer to Figure 6 ), the formability and plating properties are good. In contrast, when the thermosetting resin content is 1%, it is confirmed that the base is exposed and the plating is poor (for example, refer to Figure 5 ). In addition, when the thermosetting resin content was 70%, the molding was irregular, resulting in a dimensional error of more than 20%, poor molding, and inability to plate (for example, see Figure 7 ). Therefore, the content of the thermosetting resin in the resin solution for forming the molded product may be 3% by weight or more and 60% by weight or less, and preferably 5% by weight or more and 50% by weight or less.

[0134] As shown in the above embodiments, according to the resin liquid and the molded product forming method involved in this embodiment, a molded product including a metal three-dimensional structure can be easily constructed. The metal three-dimensional structure that can be constructed by the resin liquid and the molded product forming method involved in this embodiment can be used as an electrical wiring pattern, for example.

[0135] As described above, it is possible to provide a resin solution and a method for forming a molded product which are suitable for producing a molded product including a three-dimensional metal structure.

[0136] In addition, the structure disclosed in the above-mentioned embodiment (including other embodiments, the same below) can be combined with the structure disclosed in other embodiments as long as no contradiction occurs. In addition, the embodiments disclosed in this specification are only illustrative, and the embodiments of the present disclosure are not limited thereto, and can be appropriately changed within the scope of the purpose of the present disclosure.

[0137] Industrial Applicability

[0138] The present invention can be applied to a resin liquid and a method for forming a molded product.

Claims

1. A resin solution comprising a free radical photocurable resin, a thermosetting resin and an acid catalyst, The thermosetting resin contains a melamine crosslinking agent or a benzoguanamine crosslinking agent, The thermosetting resin is contained in an amount of 3 wt % to 60 wt %. 2 . The resin solution according to claim 1 , wherein the free radical photocurable resin comprises at least one selected from polyurethane acrylate, epoxy acrylate, acrylic acrylate, polyester acrylate, and acrylate monomer. 3 . The resin solution according to claim 1 , wherein the melamine-based crosslinking agent comprises methylol melamine or a methylol melamine derivative. 4 . The resin solution according to claim 1 , wherein the benzoguanamine-based crosslinking agent comprises hydroxymethylbenzoguanamine or a hydroxymethylbenzoguanamine derivative. 5 . The resin solution according to claim 1 , wherein the radical light-curing resin is contained in an amount of 40% to 97% both inclusive, based on a mass ratio of solid components. 6 . The resin solution according to claim 1 , wherein the acid catalyst comprises a sulfonic acid catalyst or a phosphoric acid catalyst.

7. A method for forming a formed object, the method comprising: A molding step, wherein a first molded product is obtained by molding using a resin liquid, wherein the resin liquid comprises a free radical photocurable resin, a thermosetting resin and an acid catalyst, wherein the thermosetting resin comprises a melamine-based crosslinking agent or a benzoguanamine-based crosslinking agent, and further comprises 3 wt % to 60 wt % of the thermosetting resin; A final photocuring step, wherein the first molded object is irradiated with light having a wavelength of 300 nm or more to photocure the first molded object to obtain a second molded object; The thermal curing step includes heating the second molded product at a temperature of 60° C. to 280° C. to thermally cure the second molded product to obtain a third molded product.

8. The method for forming a molded object according to claim 7 further comprises a pattern forming step: irradiating a portion of the surface of the third molded object with light having a wavelength less than 300 nm to form an irradiated area irradiated with light having a wavelength less than 300 nm and a non-irradiated area not irradiated with light having a wavelength less than 300 nm.

9. The method for forming a formed object according to claim 7 or 8, further comprising a catalyst loading step: contacting the surface of the third formed object with a pretreatment solution for chemical plating containing metal nanoparticles and water, so that the metal nanoparticles are loaded on the surface of the third formed object to form a catalyst loading area. 10 . The method for forming a formed article according to claim 9 , further comprising a plating step of performing chemical plating on the catalyst supporting region.

Images