3D modeling ink set, cured resin, and method for manufacturing the cured resin

Abstract

To provide a three-dimensional modeling ink set that can be mixed relatively easily and has relatively excellent shape retention, a resin cured product of the three-dimensional modeling ink set, and a method for producing a resin cured product using the three-dimensional modeling ink set. [Solution] The three-dimensional modeling ink set comprises a first ink and a second ink. The first ink contains a first curable component and a first filler. The second ink contains a second curable component and a second filler. The first curable component has a hydrogen-bonding functional group. The second curable component may or may not have a hydrogen-bonding functional group. The hydrogen-bonding functional group value of the second curable component is smaller than the hydrogen-bonding functional group value of the first curable component, and the difference in hydrogen-bonding functional group value is 0.0001 mol / g or more. The pH at the isoelectric point of the first filler is 9.0 or less, the pH at the isoelectric point of the second filler is 9.0 or less, and the difference in pH at these isoelectric points is 1.0 or less.

Description

[Technical Field]

[0001] The present invention relates to a three-dimensional modeling ink set, a cured resin, and a method for producing the cured resin. [Background technology]

[0002] In the field of three-dimensional modeling, active energy ray-curable and / or thermosetting resin compositions are used. For example, the following method for producing a photocurable three-dimensional object has been proposed. In this method, a photocurable resin composition is dispensed using a non-contact dispenser to obtain a coating film. The coating film is then irradiated with light to cure it, thereby obtaining a photocurable three-dimensional object (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 018525 Summary of the Invention [Problem to be solved by the invention]

[0004] On the other hand, in the field of three-dimensional modeling, there are cases where adjustment of the mechanical properties and / or color tone of the cured resin product is required.

[0005] Therefore, for example, a method has been considered in which two or more resin compositions are mixed in an arbitrary mixing ratio and the resulting mixture is cured. By adjusting the mixing ratio of the resin compositions, it is possible to adjust the mechanical properties and color tone of the cured resin product.

[0006] However, resin compositions used for three-dimensional modeling usually have relatively high thixotropy in order to maintain a desired shape after dispensing and before curing. In such cases, mixing the resin composition may be difficult. On the other hand, if the thixotropy of the resin composition is reduced in order to mix the resin composition, the thixotropy of the resin composition mixture is also reduced. As a result, the shape retention before curing may be insufficient, making three-dimensional modeling difficult.

[0007] The present invention relates to a three-dimensional modeling ink set that is relatively easy to mix and has relatively good shape retention when mixed, a cured resin product of the three-dimensional modeling ink set, and a method for producing a cured resin product using the three-dimensional modeling ink set. [Means for solving the problem]

[0008] The present invention [1] is a three-dimensional modeling ink set comprising a first ink and a second ink, wherein the first ink contains a first curable component that is curable by actinic radiation and / or heat, and a first filler dispersed in the first curable component, and the second ink contains a second curable component that is curable by actinic radiation and / or heat, and a second filler dispersed in the second curable component, wherein the first curable component has a hydrogen-bonding functional group, and the second curable component has a hydrogen-bonding functional group or a hydrogen-bonding functional group. the hydrogen-bonding functional group value of the second curable component is smaller than the hydrogen-bonding functional group value of the first curable component, the difference between the hydrogen-bonding functional group value of the first curable component and the hydrogen-bonding functional group value of the second curable component is 0.0001 mol / g or more, the pH at the isoelectric point of the first filler is 8.0 or less, the pH at the isoelectric point of the second filler is 8.0 or less, and the difference between the pH at the isoelectric point of the first filler and the pH at the isoelectric point of the second filler is 1.0 or less.

[0009] The present invention [2] includes the three-dimensional modeling ink set described in [1] above, in which the thixotropic index of the first ink at 25°C is 8.0 or less, and the thixotropic index of the second ink at 25°C is 8.0 or less.

[0010] The present invention [3] includes the three-dimensional modeling ink set according to the above [2], in which the first curable component contains urethane (meth)acrylate.

[0011] The present invention [4] includes the three-dimensional modeling ink set according to any one of the above [1] to [3], wherein the second curable component does not have a hydrogen-bonding functional group.

[0012] The present invention [5] includes the three-dimensional modeling ink set according to any one of the above [1] to [4], wherein the pH at the isoelectric point of the first filler is 3.0 or less, and the pH at the isoelectric point of the second filler is 3.0 or less.

[0013] The present invention [6] includes the three-dimensional modeling ink set according to any one of the above [1] to [5], in which the first filler and the second filler are the same type.

[0014] The present invention [7] includes a resin cured product containing a cured product of a mixture of the first ink and the second ink of the three-dimensional modeling ink set described in any one of [1] to [6] above.

[0015] The present invention [8] includes the cured resin according to the above [7], which has a storage modulus E' at 25°C of 0.1 MPa or more and 2000 MPa or less.

[0016] The present invention [9] is a method for producing a cured resin product by three-dimensional modeling, and includes a preparation step of preparing the three-dimensional modeling ink set described in any one of [1] to [6] above, a mixing step of mixing the first ink and the second ink of the three-dimensional modeling ink set to obtain a mixed ink, and a curing step of curing the mixed ink to obtain the cured resin product, wherein the mixing step includes ejecting the first ink and the second ink from dispensers, respectively, and bringing the ejected first ink into contact with the ejected second ink. [Effects of the Invention]

[0017] In the ink set for three-dimensional modeling of the present invention, the first ink contains a first curable component curable by actinic radiation and / or heat and a first filler dispersed in the first curable component, and the second ink contains a second curable component curable by actinic radiation and / or heat and a second filler dispersed in the second curable component.

[0018] In such a three-dimensional modeling ink set, the hydrogen-bonding functional group value of the second curable component is smaller than the hydrogen-bonding functional group value of the first curable component. Furthermore, the difference between the hydrogen-bonding functional group value of the second curable component and the hydrogen-bonding functional group value of the second curable component is equal to or greater than a predetermined value. In other words, the electrical properties of the first curable component and the second curable component are different from each other. More specifically, the polarity of the first curable component is higher than the polarity of the second curable component.

[0019] On the other hand, the difference between the pH at the isoelectric point of the first filler and the pH at the isoelectric point of the second filler is equal to or less than a predetermined value. In other words, the electrical properties of the first filler and the electrical properties of the second filler are comparable. More specifically, the polarity of the first filler and the polarity of the second filler are comparable.

[0020] In this case, the first curable component is bound to the first filler in the first ink, electrically neutralizing the first filler. Because the first curable component has a relatively high polarity, the amount of the first curable component bound to the first filler is relatively small.

[0021] In the second ink, the second curable component is bound to the second filler, electrically neutralizing the second filler. Because the second curable component has a relatively low polarity, the amount of the second curable component bound to the second filler is relatively large.

[0022] In such a three-dimensional modeling ink set, when the first ink and the second ink are mixed, both the first curable component and the second curable component are bound to the first filler, and both the first curable component and the second curable component are bound to the second filler. In particular, in the early stages of mixing the first ink and the second ink, the balance of the electrical stability of the mixture is disrupted, and the first filler and the second filler bind the first curable component and the second curable component in amounts exceeding those required for electrical neutralization.

[0023] As a result, the thixotropy of the mixture temporarily increases in the early stage of mixing the first ink and the second ink, i.e., the mixture temporarily has a relatively high thixotropy.

[0024] In other words, in the initial stage of mixing the first ink and the second ink, the mixture has relatively good shape retention. That is, the above-described three-dimensional modeling ink set has relatively good shape retention.

[0025] Furthermore, after mixing the first ink and the second ink, the mixture becomes electrically stable over time. Therefore, the amount of the first curable component and the second curable component bound by the first filler and the second filler decreases over time. Ultimately, the first filler and the second filler bind the first curable component and the second curable component in an amount necessary for electrical neutralization. In other words, the thixotropy of the mixture decreases over time.

[0026] In this way, the ink set for three-dimensional printing can temporarily increase the thixotropy of the mixture, eliminating the need to increase the thixotropy of each of the first and second inks. Therefore, the ink set for three-dimensional printing can be mixed relatively easily. In other words, the ink set for three-dimensional printing has excellent ease of mixing.

[0027] Furthermore, the cured resin product of the present invention is obtained using the above-mentioned three-dimensional modeling ink set, and therefore, the first ink and the second ink can be mixed relatively easily during production of the cured resin product, and the cured resin product can have relatively good shape retention.

[0028] The method for producing a cured resin product of the present invention uses the above-described ink set for three-dimensional modeling. More specifically, the first ink and the second ink are each ejected by a dispenser. The ejected first ink and the ejected second ink then come into contact with each other after ejection, and are mixed by mutual diffusion of the first ink and the second ink.

[0029] Therefore, in the above-described method for producing a cured resin, the first ink and the second ink can be mixed relatively easily, and relatively good shape retention can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0030] 1. 3D modeling ink set The three-dimensional modeling ink set is a multi-component resin composition used for three-dimensional modeling (described later). The three-dimensional modeling ink set includes a first ink and a second ink, and preferably consists of the first ink and the second ink.

[0031] 1) First ink The first ink contains a first curable component and a first filler. As will be described in detail later, the first ink is an ink that can be cured by actinic radiation and / or heat (i.e., an actinic radiation and / or heat curable ink).

[0032] (1) First curable component The first curable component is a component that can be cured by actinic radiation and / or heat. The first curable component is an uncured polymer or a raw material monomer.

[0033] The first curable component contains a first curable compound that can be cured by actinic radiation and / or heat, that is, the first ink contains the first curable compound.

[0034] [First curable compound] The first curable compound has predetermined electrical properties. More specifically, the first curable compound has a hydrogen-bonding functional group, as will be described in detail later. Examples of the hydrogen-bonding functional group include a hydroxyl group (OH), a mercapto group (SH), and a primary or secondary amino group (NH). The hydrogen-bonding functional group can be used alone or in combination of two or more types. Examples of the hydrogen-bonding functional group include preferably a hydroxyl group and a primary or secondary amino group, more preferably a primary or secondary amino group, and even more preferably a secondary amino group. The hydrogen-bonding functional group may be a part of a known functional group. For example, a hydroxyl group may be a part of a carboxyl group (COOH). Furthermore, for example, a secondary amino group may be a part of a urethane group (NHCO). Preferably, the first curable compound has a urethane group (NHCO), and a secondary amino group as part of the urethane group.

[0035] Examples of the first curable compound include a compound curable by active energy rays (hereinafter referred to as an active energy ray-curable compound) and a compound curable by heat (hereinafter referred to as a thermosetting compound). These can be used alone or in combination of two or more. A preferred example of the first curable compound is an active energy ray-curable compound. That is, the first curable compound preferably contains an active energy ray-curable compound, and more preferably consists of an active energy ray-curable compound. Examples of the active energy ray-curable compound include an active energy ray-radical polymerizable compound and an active energy ray-cationically polymerizable compound. These can be used alone or in combination of two or more. A preferred example of the first curable compound is an active energy ray-radical polymerizable compound.

[0036] Examples of active energy ray radical polymerizable compounds include urethane (meth)acrylates, which are compounds having a urethane group and a (meth)acryloyl group.

[0037] It should be noted that (meth)acrylate refers to acrylate and / or methacrylate, (meth)acryloyl refers to acryloyl group and / or methacryloyl, and (meth)acrylic refers to acrylic and / or methacrylic.

[0038] The first curable compound preferably contains a urethane (meth)acrylate, more preferably consists of a urethane (meth)acrylate. In other words, the first curable component preferably contains a urethane (meth)acrylate as the first curable compound.

[0039] The urethane (meth)acrylate is, for example, a reaction product of a polyisocyanate component, an active hydrogen group-containing component, and a hydrogen group-containing (meth)acrylate.

[0040] The polyisocyanate component includes, for example, a polyisocyanate monomer and / or a polyisocyanate derivative.

[0041] Examples of polyisocyanate monomers include linear aliphatic polyisocyanate monomers, alicyclic polyisocyanate monomers, aromatic polyisocyanate monomers, and araliphatic polyisocyanate monomers. Examples of linear aliphatic polyisocyanate monomers include linear aliphatic diisocyanates. Examples of linear aliphatic diisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), and hexamethylene diisocyanate (HDI). Examples of alicyclic polyisocyanate monomers include alicyclic diisocyanates. Examples of alicyclic diisocyanates include cyclohexane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), and methylenebis(cyclohexyl isocyanate) (H 12 Examples of aromatic polyisocyanate monomers include aromatic diisocyanates. Examples of aromatic diisocyanates include diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), toluidine diisocyanate (TODI), paraphenylene diisocyanate, and naphthalene diisocyanate (NDI). Examples of araliphatic polyisocyanate monomers include araliphatic diisocyanates. Examples of araliphatic diisocyanates include 1,3-xylylene diisocyanate (1,3-XDI), 1,4-xylylene diisocyanate (1,4-XDI), and tetramethylxylylene diisocyanate (TMXDI). These can be used alone or in combination of two or more types.

[0042] Examples of polyisocyanate derivatives include modified products obtained by modifying the above polyisocyanate monomers using known methods. More specifically, examples of polyisocyanate derivatives include polymers, isocyanurate-modified products, allophanate-modified products, polyol-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, and carbodiimide-modified products. Polyisocyanate derivatives also include polymethylene polyphenylene polyisocyanate. These can be used alone or in combination of two or more types.

[0043] The polyisocyanate component can be used alone or in combination of two or more kinds. As the polyisocyanate component, preferably, a polyisocyanate monomer is used, and more preferably, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), and 1,3-xylylene diisocyanate (1,3-XDI) are used.

[0044] Furthermore, as the polyisocyanate component, preferably, an alicyclic polyisocyanate is used, more preferably, an alicyclic diisocyanate is used, even more preferably, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI) and 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI) are used, and particularly preferably, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI) is used.

[0045] The active hydrogen group-containing component is an organic compound having one or more active hydrogen groups in the molecule. Examples of the active hydrogen group include a hydroxyl group, a mercapto group, and an amino group. More specifically, the active hydrogen group-containing component includes a hydroxyl group-containing compound, a mercapto group-containing compound, and an amino group-containing compound, and preferably includes a hydroxyl group-containing compound.

[0046] The hydroxyl group-containing compound is an organic compound having one or more hydroxyl groups in the molecule. Examples of the hydroxyl group-containing compound include polyol compounds. Examples of the polyol compound include low molecular weight polyols and high molecular weight polyols.

[0047] Examples of low-molecular-weight polyols include organic compounds having two or more hydroxyl groups in the molecule and having a relatively low molecular weight. The molecular weight of the low-molecular-weight polyol is, for example, 40 or more and less than 400, preferably 50 or more and 300 or less.

[0048] Examples of low-molecular-weight polyols include dihydric alcohols, trihydric alcohols, and tetrahydric or higher alcohols. Examples of dihydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of trihydric alcohols include glycerin and trimethylolpropane. Examples of tetrahydric or higher alcohols include pentaerythritol and diglycerin. These may be used alone or in combination.

[0049] Examples of high molecular weight polyols include organic compounds having two or more hydroxyl groups in the molecule and having a relatively high molecular weight. The number average molecular weight of the high molecular weight polyol (polystyrene equivalent molecular weight measured by GPC) is, for example, 400 to 50,000, preferably 500 to 20,000, more preferably 600 to 10,000, even more preferably 800 to 5,000, and particularly preferably 1,000 to 2,000.

[0050] Examples of high molecular weight polyols include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols. These can be used alone or in combination of two or more.

[0051] The hydroxyl group-containing compound can be used alone or in combination of two or more kinds. As the hydroxyl group-containing compound, preferably, a polyol compound is used, more preferably, a high molecular weight polyol is used, and further preferably, a polyether polyol is used.

[0052] Examples of polyether polyols include polyoxyalkylene (C2-3) polyols and polytetramethylene ether polyols.

[0053] Examples of polyoxyalkylene (C2-3) polyols include polyoxyethylene polyols, polyoxypropylene polyols, polyoxytriethylene polyols, and polyoxyethylene-polyoxypropylene polyols (random or block copolymers). These can be used alone or in combination of two or more. Preferred examples of polyoxyalkylene (C2-3) polyols include polyoxypropylene polyols, and more preferred examples include polyoxypropylene glycol.

[0054] Examples of polytetramethylene ether polyols include polytetramethylene ether glycols. Examples of polytetramethylene ether glycols include crystalline polytetramethylene ether glycols obtained by ring-opening polymerization of tetrahydrofuran. Examples of polytetramethylene ether glycols also include amorphous polytetramethylene ether glycols obtained by copolymerization of tetrahydrofuran and low-molecular-weight polyols.

[0055] These may be used alone or in combination of two or more. Preferred examples of the polyether polyol include polyoxypropylene polyol and polytetramethylene ether polyol, more preferred examples include polyoxypropylene glycol and polytetramethylene ether glycol, and even more preferred examples include polyoxypropylene glycol.

[0056] The number average molecular weight of the polyether polyol (polystyrene equivalent molecular weight measured by GPC) is, for example, 400 or more and 50,000 or less, preferably 500 or more and 20,000 or less, more preferably 600 or more and 10,000 or less, even more preferably 800 or more and 5,000 or less, and particularly preferably 1,000 or more and 2,000 or less.

[0057] The active hydrogen group-containing (meth)acrylate is an organic compound having one or more (meth)acroyl groups and one or more active hydrogen groups in the molecule. Examples of the active hydrogen group-containing (meth)acrylate include hydroxyl group-containing (meth)acrylate, mercapto group-containing (meth)acrylate, and amino group-containing (meth)acrylate. These can be used alone or in combination of two or more. The active hydrogen group-containing (meth)acrylate is preferably a hydroxyl group-containing (meth)acrylate.

[0058] Examples of hydroxyl group-containing (meth)acrylates include monohydroxymono(meth)acrylate, polyhydroxymono(meth)acrylate, monohydroxypoly(meth)acrylate, and polyhydroxypoly(meth)acrylate. These can be used alone or in combination of two or more.

[0059] Monohydroxymono(meth)acrylate is a compound having one hydroxyl group and one (meth)acryloyl group in one molecule. Examples of monohydroxymono(meth)acrylate include 2-hydroxyethyl(meth)acrylate, 3-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 2-phenoxypropyl(meth)acrylate, 4-hydroxycyclohexyl(meth)acrylate, 3-chloro-2-hydroxypropyl(meth)acrylate, 2-hydroxy-3-phenyloxypropyl(meth)acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethylphthalate, 2-hydroxyalkyl(meth)acryloylphosphate, pentanediol mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate. These can be used alone or in combination of two or more types.

[0060] Polyhydroxymono(meth)acrylate is a compound having multiple hydroxyl groups and one (meth)acryloyl group in one molecule. Examples of polyhydroxymono(meth)acrylate include trimethylolpropane mono(meth)acrylate, glycerin mono(meth)acrylate, and pentaerythritol mono(meth)acrylate. These can be used alone or in combination of two or more.

[0061] Monohydroxypoly(meth)acrylate is a compound having one hydroxyl group and multiple (meth)acryloyl groups in one molecule. Examples of monohydroxypoly(meth)acrylate include trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate. These can be used alone or in combination of two or more.

[0062] Polyhydroxypoly(meth)acrylate is a compound having multiple hydroxyl groups and multiple (meth)acryloyl groups in one molecule. Examples of polyhydroxypoly(meth)acrylate include pentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and bisphenol A diglycidyl ether-(meth)acrylic acid adduct. These can be used alone or in combination of two or more.

[0063] The active hydrogen group-containing (meth)acrylate can be used alone or in combination of two or more kinds. As the active hydrogen group-containing (meth)acrylate, preferably, a hydroxyl group-containing (meth)acrylate can be used, more preferably, a monohydroxymono(meth)acrylate can be used, still more preferably, a hydroxyalkyl(meth)acrylate can be used, and particularly preferably, 2-hydroxyethyl(meth)acrylate can be used.

[0064] The method for obtaining the urethane (meth)acrylate is not particularly limited. For example, first, a polyisocyanate component is reacted with an active hydrogen group-containing component to obtain an isocyanate group-terminated prepolymer.

[0065] In the synthesis of the isocyanate group-terminated prepolymer, the polyisocyanate component and the active hydrogen group-containing component are mixed in a predetermined ratio. More specifically, the equivalent ratio of the isocyanate groups in the polyisocyanate component to the active hydrogen groups in the active hydrogen group-containing component (isocyanate groups / active hydrogen groups) is, for example, greater than 1, preferably 1.1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.

[0066] A known polymerization method is used for the urethane reaction between the polyisocyanate component and the active hydrogen group-containing component. Examples of the polymerization method include bulk polymerization and solution polymerization. In bulk polymerization, for example, the above components are blended under a nitrogen atmosphere and reacted at a reaction temperature of 75 to 85°C for about 1 to 20 hours. In solution polymerization, for example, the above components are added to a known organic solvent under a nitrogen atmosphere and reacted at a reaction temperature of 20 to 80°C for about 1 to 20 hours.

[0067] In the urethane reaction between the polyisocyanate component and the active hydrogen group-containing component, a known urethane catalyst is added as needed. After the reaction is completed, the unreacted polyisocyanate component is removed as needed by a known method. This results in an isocyanate-terminated prepolymer.

[0068] The average number of functional isocyanate groups in the isocyanate group-terminated prepolymer is, for example, 1.5 to 4.0, or preferably 2.0 to 3.0.

[0069] Furthermore, the above reaction produces a composition containing an isocyanate-terminated prepolymer and an unreacted polyisocyanate component (hereinafter referred to as a crude prepolymer product).

[0070] The crude prepolymer product is preferably purified by distillation, that is, unreacted polyisocyanate components are removed from the crude prepolymer product to obtain a purified isocyanate-terminated prepolymer (hereinafter referred to as purified prepolymer).

[0071] The distillation method is not particularly limited, and examples thereof include batch distillation and continuous distillation. Examples of continuous distillation include thin film distillation (Smith thin film distillation). Examples of distillation methods include thin film distillation (Smith thin film distillation). The distillation conditions are set according to the purpose and application.

[0072] Next, in this method, an isocyanate-terminated prepolymer (preferably a purified prepolymer) is reacted with an active hydrogen group-containing (meth)acrylate to obtain a urethane (meth)acrylate.

[0073] In the urethane reaction, the equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group in the isocyanate group-terminated prepolymer to the active hydrogen group in the active hydrogen group-containing (meth)acrylate is, for example, 0.7 to 1.5, or preferably 0.9 to 1.2.

[0074] The reaction conditions for the urethanization reaction are not particularly limited. For example, the environmental conditions are, for example, an inert gas atmosphere. The reaction temperature is, for example, 40 to 120°C, preferably 50 to 100°C, and more preferably 60 to 80°C. The reaction time is, for example, 0.5 to 24 hours, preferably 1.0 to 20 hours.

[0075] In addition, in the urethanization reaction, a known urethanization catalyst is added as needed. The amount of the urethanization catalyst added is appropriately determined depending on the purpose and application. After the reaction is completed, if necessary, unreacted isocyanate-terminated prepolymer and / or active hydrogen group-containing (meth)acrylate are removed by a known method.

[0076] As a result of the above, a urethane (meth)acrylate is obtained as a reaction product between the isocyanate group-terminated prepolymer and the active hydrogen group-containing (meth)acrylate.

[0077] The urethane (meth)acrylate may be a commercially available product, such as urethane prepolymer manufactured by Kyoeisha Chemical Co., Ltd. and UV-curable urethane acrylate manufactured by Mitsubishi Chemical Corporation. Examples of urethane prepolymers manufactured by Kyoeisha Chemical Co., Ltd. include AH-600 (phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer), UA-306H (pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer), UA-306T (pentaerythritol triacrylate toluene diisocyanate urethane prepolymer), UA-306I (pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer), UA-510H (dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymer), UF-8001G (non-yellowing oligourethane acrylate (high hardness, medium elongation)), and DAUA-167 (carboxylic acid-containing urethane acrylate oligomer). Examples of UV-curable urethane acrylates manufactured by Mitsubishi Chemical Corporation include UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, and UV-7650B. These can be used alone or in combination of two or more types.

[0078] The first curable compound is not limited to urethane (meth)acrylate. Examples of the first curable compound other than urethane (meth)acrylate include hydroxyl group-containing (meth)acrylate and amino group-containing (meth)acrylate.

[0079] Examples of the hydroxyl group-containing (meth)acrylate include the above-mentioned hydroxyl group-containing (meth)acrylates, more specifically, the above-mentioned monohydroxymono(meth)acrylate, polyhydroxymono(meth)acrylate, monohydroxypoly(meth)acrylate, and polyhydroxypoly(meth)acrylate. The hydroxyl group-containing (meth)acrylate may be a commercially available product. An example of a commercially available product is Viscoat 540 manufactured by Osaka Organic Chemical Industry Co., Ltd. These can be used alone or in combination of two or more types.

[0080] Examples of amino group-containing (meth)acrylates include aminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, and dimethylaminomethyl (meth)acrylate. The amino group-containing (meth)acrylate may be a commercially available product. An example of a commercially available product is CN371 manufactured by Sartomer. These may be used alone or in combination of two or more types.

[0081] From the viewpoints of shape retention before curing and molding accuracy, the first curable compound is preferably a urethane (meth)acrylate, and more preferably a reaction product of an isocyanate group-terminated prepolymer and an active hydrogen group-containing (meth)acrylate.

[0082] As described above, the first curable compound has a hydrogen-bonding functional group.

[0083] From the viewpoint of shape retention before curing, the hydrogen-bonding functional group value of the first curable compound (when two or more first curable compounds are used in combination, a weighted average value based on mass (the same applies hereinafter)) is, for example, 0.0001 mol / g or more, preferably 0.0002 mol / g or more, more preferably 0.0003 mol / g or more, and even more preferably 0.00035 mol / g or more. Also, from the viewpoint of shape retention before curing, the hydrogen-bonding functional group value of the first curable compound is, for example, 0.01 mol / g or less, preferably 0.05 mol / g or less, more preferably 0.001 mol / g or less, and even more preferably 0.0005 mol / g or less. That is, the hydrogen-bonding functional group value of the first curable compound is, for example, 0.0001 mol / g or more and 0.01 mol / g or less, preferably 0.0002 mol / g or more and 0.05 mol / g or less, more preferably 0.0003 mol / g or more and 0.001 mol / g or less, and even more preferably 0.00035 mol / g or more and 0.0005 mol / g or less.

[0084] The hydrogen-bonding substituent value (mol / g) of the first curable compound is the number of moles (mol) of hydrogen-bonding substituents in 1 g of the first curable compound. The hydrogen-bonding substituent value of the first curable compound is calculated, for example, from the molecular structure of the first curable compound.

[0085] More specifically, the hydrogen-bonding substituent value of the urethane (meth)acrylate is calculated, for example, by the following method.

[0086] That is, urethane (meth)acrylate may be produced, for example, by reacting 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), a high molecular weight polyol having an average functionality of 2, and 2-hydroxyethyl (meth)acrylate. In another example, the amount of high molecular weight polyol is 10,000 g, the amount of 1,3-H6XDI is 388.46 g (2 mol), and the amount of 2-hydroxyethyl (meth)acrylate is 232.24 g (2 mol).

[0087] In the above reaction, the mass of the resulting urethane (meth)acrylate is 10,620.7 g (= 10,000 g + 388.46 g + 232.24 g). Furthermore, in the above reaction, when 2 moles of 1,3-H6HDI (i.e., 4 moles of isocyanate groups) undergo a urethane reaction, 4 moles of hydrogen-bonding functional groups (NH groups) are produced. In this case, the hydrogen-bonding functional group value of the urethane (meth)acrylate is 0.000377 mol / g (= 4 moles / 10,620.7 g). The hydrogen-bonding substituent value of the urethane (meth)acrylate can be calculated using the above method.

[0088] The hydrogen-bonding substituent value of the first curable compound can also be calculated by gas chromatography. That is, an aqueous solution appropriate for the object to be measured is used to hydrolyze the object to be measured, and the hydrolysis is performed by gas chromatography to detect fragments corresponding to the hydrogen-bonding substituents. The hydrogen-bonding substituent value can then be calculated from the detection results.

[0089] More specifically, when the object to be measured is, for example, urethane (meth)acrylate, the urethane (meth)acrylate is hydrolyzed using an aqueous sodium hydroxide solution, and then the decomposition product is extracted using dicyclomethane, and the extract is subjected to gas chromatography. Then, the fragments corresponding to the hydrogen-bonding substituents are detected, and the hydrogen-bonding substituent value can be calculated.

[0090] The method for calculating the hydrogen-bonding substituent value of the first curable compound is not limited to the above. The hydrogen-bonding substituent value can be calculated by a known method depending on the type of the first curable compound. For example, when the number of hydrogen-bonding substituents per molecule of the first curable compound is known, the molecular weight of the first curable compound can be calculated from the molecular structure, and the hydrogen-bonding substituent value can be calculated. The molecular weight of the first curable compound can also be determined by gel permeation chromatography.

[0091] [Other curable compounds] The first curable component can contain other curable compounds as optional components, if necessary. The other curable compounds are curable compounds other than the first curable compound. The first curable component preferably contains the other curable compounds. That is, the first curable component preferably contains the first curable compound and the other curable compounds, and more preferably consists of the first curable compound and the other curable compounds.

[0092] Other curable compounds include, for example, curable compounds without hydrogen-bonding functional groups, more specifically, polymerizable diluents. Examples of polymerizable diluents include polymerizable compounds with aromatic hydrocarbon skeletons, polymerizable compounds with alicyclic hydrocarbon skeletons, polymerizable compounds with chain aliphatic hydrocarbon skeletons, polymerizable compounds with chain ether skeletons, and polymerizable compounds with alicyclic ether skeletons. Examples of polymerizable compounds with aromatic hydrocarbon skeletons include 3-phenoxybenzyl (meth)acrylate, styrene, vinyltoluene, divinylbenzene, and α-methylstyrene. Examples of polymerizable compounds with alicyclic hydrocarbon skeletons include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Examples of polymerizable compounds having a chain aliphatic hydrocarbon skeleton include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate. Examples of polymerizable compounds having a chain ether skeleton include 2-ethylhexyl-diglycol (meth)acrylate. Examples of polymerizable compounds having an alicyclic ether skeleton include cyclic trimethylolpropane formal (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl acrylate, and 4-(meth)acryloylmorpholine. These can be used alone or in combination of two or more. Preferred are polymerizable compounds having an alicyclic hydrocarbon skeleton, and more preferred is isobornyl (meth)acrylate.

[0093] [Content percentage] In the first curable component, the ratio of the first curable compound and the other curable compounds is appropriately set depending on the purpose and application.

[0094] For example, the content of the first curable compound is, for example, 10 to 100 mass%, preferably 20 to 90 mass%, more preferably 30 to 80 mass%, and even more preferably 40 to 70 mass%, relative to the total amount of the first curable component. The content of the other curable compounds is, for example, 0 to 90 mass%, preferably 10 to 80 mass%, more preferably 20 to 70 mass%, and even more preferably 30 to 60 mass%, relative to the total amount of the first curable component.

[0095] The content ratio of the other curable compounds is, for example, 0 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 50 to 200 parts by mass, and even more preferably 80 to 130 parts by mass, relative to 100 parts by mass of the total amount of the first curable compounds.

[0096] The total content of the first curable components relative to the total amount of the first ink is, for example, 50 to 99 mass %, preferably 60 to 95 mass %, and more preferably 70 to 90 mass %.

[0097] The content of the first curable compound is, for example, 10 to 100 mass%, preferably 20 to 90 mass%, more preferably 30 to 80 mass%, and even more preferably 40 to 70 mass%, relative to the total amount of the first ink. The content of the other curable compounds is, for example, 0 to 90 mass%, preferably 10 to 80 mass%, more preferably 20 to 70 mass%, and even more preferably 30 to 60 mass%, relative to the total amount of the first ink.

[0098] [Physical properties of the first curable component] The first curable component contains a first curable compound, and therefore has a hydrogen-bonding functional group.

[0099] From the viewpoint of shape retention before curing, the hydrogen-bonding functional group value (weighted average value based on mass (hereinafter the same)) of the first polymerizable component is, for example, 0.00005 mol / g or more, preferably 0.0001 mol / g or more, more preferably 0.00015 mol / g or more, and even more preferably 0.00017 mol / g or more. Also, from the viewpoint of shape retention before curing, the hydrogen-bonding functional group value of the first curable compound is, for example, 0.01 mol / g or less, preferably 0.05 mol / g or less, more preferably 0.001 mol / g or less, and even more preferably 0.0005 mol / g or less. That is, the hydrogen-bonding functional group value of the first curable compound is, for example, 0.00005 mol / g or more and 0.01 mol / g or less, preferably 0.0001 mol / g or more and 0.05 mol / g or less, more preferably 0.00015 mol / g or more and 0.001 mol / g or less, and even more preferably 0.00017 mol / g or more and 0.0005 mol / g or less. The hydrogen-bonding functional group value of the first polymerizable component is calculated based on the mass and hydrogen-bonding functional group value of the first curable compound and the masses and hydrogen-bonding functional group values ​​of the other curable compounds using a known weighted average method.

[0100] (2) First filler The first filler is a thixotropic agent for adjusting the thixotropy of the first ink. The first filler is dispersed in the first curable component. That is, the first filler is dispersed in the first curable compound (and other curable compounds).

[0101] The first filler has a predetermined electrical property. More specifically, from the viewpoints of shape retention before curing and molding accuracy, the pH at the isoelectric point of the first filler (when two or more types of first fillers are used in combination, the weighted average value based on mass (same applies hereinafter)) is, for example, 1.0 or more, preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.7 or more. The pH at the isoelectric point of the first filler is 9.0 or less, preferably 7.5 or less, more preferably 5.0 or less, and even more preferably 3.0 or less. That is, the pH at the isoelectric point of the first filler is, for example, 1.0 or more and 9.0 or less, preferably 1.2 or more and 7.5 or less, more preferably 1.5 or more and 5.0 or less, and even more preferably 1.7 or more and 3.0 or less. The pH at the isoelectric point is measured in accordance with JIS R 1638 (1999) "Method for measuring the isoelectric point of fine ceramic powders" (same applies hereinafter).

[0102] Examples of the first filler having the above electrical properties include SiO2 (pH at isoelectric point = 1.8), kaolin (pH at isoelectric point = 5.1), silicone (pH at isoelectric point = 5.8), mullite (pH at isoelectric point = 6.3), and polypropylene (pH at isoelectric point = 7.1). These can be used alone or in combination of two or more. Preferred examples of the first filler include SiO2, kaolin, silicone, mullite, and polypropylene, and more preferred examples include SiO2.

[0103] The shape and size of the first filler are not particularly limited and are appropriately selected depending on the purpose and application. For example, the average particle size (median size) of the first filler is, for example, 0.001 to 100 μm, preferably 0.005 to 20 μm.

[0104] The content ratio of the first filler is not particularly limited, and is appropriately selected so that the viscosity and thixotropy index of the first ink fall within the desired ranges.

[0105] The content ratio of the first filler is, for example, 0.1 to 50 parts by mass (phr), preferably 1 to 20 parts by mass (phr), more preferably 2 to 10 parts by mass (phr), and even more preferably 3 to 5 parts by mass (phr) relative to 100 parts by mass of the total amount of the first curable component (uncured polymer or resin raw material monomer in the first ink).

[0106] The content of the first filler relative to the total amount of the first ink is, for example, 0.1 to 50 mass %, preferably 1 to 20 mass %, more preferably 2 to 10 mass %, and even more preferably 3 to 5 mass %.

[0107] (3) Polymerization initiator The first ink may further contain a polymerization initiator, and preferably contains a polymerization initiator.

[0108] The polymerization initiator is selected depending on the first curable component. For example, when the first curable component contains an active energy ray-curable compound, the polymerization initiator may be, for example, an active energy ray polymerization initiator. When the first curable component contains a thermosetting compound, the polymerization initiator may be, for example, a thermal polymerization initiator.

[0109] Preferably, the first curable component contains an active energy ray-curable compound, and the polymerization initiator contains an active energy ray polymerization initiator.

[0110] Examples of the active energy ray polymerization initiator include an active energy ray radical polymerization initiator and an active energy ray cationic polymerization initiator.

[0111] The active energy ray polymerization initiator is selected depending on the active energy ray curable compound. For example, when the active energy ray curable compound is an active energy ray radical polymerizable compound, the active energy ray polymerization initiator may be an active energy ray radical polymerization initiator. Furthermore, when the active energy ray curable compound is an active energy ray cationically polymerizable compound, the active energy ray polymerization initiator may be an active energy ray cationically polymerizable compound.

[0112] Particularly preferably, the first curable component contains an active energy ray radical polymerizable compound, and the polymerization initiator contains an active energy ray radical polymerization initiator.

[0113] Examples of active energy ray radical polymerization initiators include photoradical polymerization initiators. Examples of photoradical polymerization initiators include benzophenone-based photopolymerization initiators, carbazole-phenone-based photopolymerization initiators, acridine-based photopolymerization initiators, triazine-based photopolymerization initiators, and benzoyl-based photopolymerization initiators. The active energy ray radical polymerization initiator may be a commercially available product. An example of a commercially available product is Omnirad 184 manufactured by IGM resins B.V. These can be used alone or in combination of two or more types.

[0114] The content of the polymerization initiator is, for example, 0.1 to 20 parts by mass (phr), preferably 0.5 to 15 parts by mass (phr), more preferably 1 to 10 parts by mass (phr), and even more preferably 2 to 5 parts by mass (phr), relative to 100 parts by mass of the total amount of the first curable component (uncured polymer or resin raw material monomer in the first ink).

[0115] The content of the polymerization initiator relative to the total amount of the first ink is, for example, 0.1 to 20 mass %, preferably 0.5 to 15 mass %, more preferably 1 to 10 mass %, and even more preferably 2 to 5 mass %.

[0116] (4) Additives The first ink may contain additives as needed. Examples of additives include colorants, antioxidants, ultraviolet absorbers, fluorescent whitening agents, plasticizers, volatile substances, internal mold release agents, lubricants, sensitizers, antiblocking agents, heat stabilizers, light stabilizers, catalysts, lubricants, fillers, and hydrolysis inhibitors. A preferred additive is a colorant. Examples of colorants include pigments and dyes. These can be used alone or in combination of two or more. The amount and timing of addition of the additives are determined appropriately depending on the purpose and application.

[0117] (5) Manufacturing method of the first ink The method for producing the first ink is not particularly limited. For example, the first curable component (preferably the first curable compound and other curable compounds) and the first filler are mixed by a known method. If necessary, the first curable component and the first filler are mixed with the above-mentioned polymerization initiator and / or the above-mentioned additives by a known method. As a result, the first ink is obtained.

[0118] (6) Physical properties of the first ink The viscosity of the first ink at 25° C. is, for example, 100 to 50,000 mPa·s, preferably 500 to 10,000 mPa·s, and more preferably 1,000 to 5,000 mPa·s. The viscosity is measured in accordance with the examples described later (the same applies hereinafter).

[0119] The thixotropic index of the first ink is, for example, 1.0 or more, preferably 1.1 or more, more preferably 1.2 or more, even more preferably 1.3 or more, and particularly preferably 1.5 or more. The thixotropic index of the first ink is, for example, 10.0 or less, preferably 8.0 or less, more preferably 5.0 or less, even more preferably 3.0 or less, and particularly preferably 2.0 or less. That is, the thixotropic index of the first ink is, for example, 1.0 or more and 10.0 or less, preferably 1.1 or more and 8.0 or less, more preferably 1.2 or more and 5.0 or less, even more preferably 1.3 or more and 3.0 or less, and particularly preferably 1.5 or more and 2.0 or less. The thixotropic index is measured in accordance with the examples described below (the same applies hereinafter).

[0120] The first ink is cured by irradiation with active energy rays and / or by heating.

[0121] For example, when the first curable component contains an active energy ray-curable compound, when the first ink is irradiated with active energy rays, the first ink is cured to form a single cured product of the first ink.

[0122] Examples of active energy rays include ultraviolet rays, visible light rays, electron beams, X-rays, and radioactive rays, and ultraviolet rays are preferred. The irradiation conditions are not particularly limited. For example, the irradiation dose (cumulative light amount) is, for example, 100 to 600,000 mJ / cm. 2 , preferably 300 to 30,000 mJ / cm 2 The output of the active energy rays is, for example, 1.0 to 1000 mW / cm 2 , preferably 10 to 1000 mW / cm 2 is.

[0123] Furthermore, for example, when the first curable component contains a thermosetting compound, when the first ink is heated, the first ink cures and a single cured product of the first ink is formed.

[0124] The heating conditions are not particularly limited. For example, the heating temperature is, for example, 30 to 200° C., preferably 50 to 150° C. The heating time is 1 to 48 hours, preferably 2 to 24 hours.

[0125] The storage modulus E' of the first ink alone at 25°C is, for example, 0.01 MPa to 5000 MPa, preferably 0.1 MPa to 2000 MPa, more preferably 0.5 MPa to 1000 MPa, and even more preferably 1 MPa to 100 MPa. The storage modulus E' is measured in accordance with the examples described later (the same applies hereinafter).

[0126] 2) Second ink The second ink contains a second curable component and a second filler. As will be described in detail later, the second ink is an ink that can be cured by actinic radiation and / or heat (i.e., an actinic radiation and / or heat curable ink).

[0127] (1)Second curable component The second curable component is a component that can be cured by actinic radiation and / or heat. The second curable component is an uncured polymer or a raw material monomer.

[0128] The second curable component contains a second curable compound that can be cured by actinic radiation and / or heat. In other words, the second ink contains a second curable compound.

[0129] [Second curable compound] The second curable compound has a predetermined electrical property. More specifically, the second curable compound has a hydrogen-bonding functional group or does not have a hydrogen-bonding functional group, as described in detail below. That is, the second curable compound may or may not have the above-mentioned hydrogen-bonding functional group. From the viewpoint of shape retention before curing, preferably, the second curable compound does not have the above-mentioned hydrogen-bonding functional group.

[0130] Examples of the second curable compound include active energy ray-curable compounds and thermosetting compounds. These can be used alone or in combination of two or more. Preferred examples of the second curable compound include active energy ray-curable compounds. That is, the second curable compound preferably contains an active energy ray-curable compound, and more preferably consists of an active energy ray-curable compound. Preferred examples of the active energy ray-curable compound include active energy ray-radical polymerizable compounds and active energy ray-cationically polymerizable compounds. These can be used alone or in combination of two or more. Preferred examples of the second curable compound include active energy ray-cationically polymerizable compounds.

[0131] Examples of active energy ray radical polymerizable compounds include compounds containing epoxy groups and / or oxetanyl groups. In other words, the second curable compound preferably contains a compound containing epoxy groups and / or oxetanyl groups. More preferably, the second curable compound is a compound containing epoxy groups and / or oxetanyl groups.

[0132] Examples of epoxy group- and / or oxetanyl group-containing compounds include epoxy group-containing compounds, oxetanyl group-containing compounds, and epoxy group-oxetanyl group-combined compounds. These can be used alone or in combination of two or more. Preferred examples of epoxy group- and / or oxetanyl group-containing compounds include epoxy group-containing compounds and oxetanyl group-containing compounds.

[0133] An epoxy group-containing compound (hereinafter referred to as an epoxy compound) is an organic compound that has one or more epoxy groups in the molecule but does not have an oxetanyl group. Examples of epoxy compounds include aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds. These can be used alone or in combination of two or more types.

[0134] Examples of aromatic epoxy compounds include bisphenol-type epoxy compounds, naphthalene-type epoxy compounds, novolac-type epoxy compounds, halogenated epoxy compounds, and other polyfunctional aromatic epoxy compounds. Examples of bisphenol-type epoxy compounds include butyl glycidyl ether, phenyl glycidyl ether, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol AD-type epoxy compounds, and bisphenol S-type epoxy compounds. Examples of naphthalene-type epoxy compounds include 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane. Examples of novolac-type epoxy compounds include phenol novolac-type epoxy compounds and cresol novolac-type epoxy compounds. Examples of halogenated epoxy compounds include brominated epoxy compounds (tetrabromobisphenol A diglycidyl ether and brominated bisphenol). Examples of other polyfunctional epoxy compounds include glycidyl ethers of tetra(hydroxyphenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenone, and epoxidized polyvinylphenol. These can be used alone or in combination of two or more types.

[0135] Examples of the aromatic epoxy compound include commercially available aromatic epoxy compounds, such as jER828 (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation, the EPICLON series manufactured by DIC Corporation, and the OGSOL series manufactured by Osaka Gas Chemicals Co., Ltd.

[0136] Examples of aliphatic epoxy compounds include polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts. Examples of polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,12-dodecanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether.

[0137] Examples of the aliphatic epoxy compound include commercially available aliphatic epoxy compounds. Examples of commercially available aliphatic epoxy compounds include Epolite 100MF (trimethylolpropane triglycidyl ether) manufactured by Kyoeisha Chemical Co., Ltd. These can be used alone or in combination of two or more types.

[0138] Examples of alicyclic epoxy compounds include hydrogenated products of the above-mentioned aromatic epoxy compounds (e.g., hydrogenated bisphenol A-type epoxy compounds). Examples of alicyclic epoxy compounds include cyclohexane-type epoxy compounds, cyclohexyl methyl ester-type epoxy compounds, cyclohexyl methyl ether-type epoxy compounds, spiro-type epoxy compounds, and tricyclodecane-type epoxy compounds. More specific examples of alicyclic epoxy compounds include 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2:8,9-diepoxylimonene, 1,2-epoxy-4-vinylcyclohexane, and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. These compounds can be used alone or in combination.

[0139] Examples of the alicyclic epoxy compound include commercially available alicyclic epoxy compounds. Examples of commercially available alicyclic epoxy compounds include KRM-2408 (hydrogenated bisphenol A epoxy compound) manufactured by ADEKA Corporation, YX-8034 (hydrogenated bisphenol A epoxy compound) manufactured by Mitsubishi Chemical Corporation, and CELLOXIDE 2021P (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) and EHPE3150 (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol) manufactured by Daicel Corporation. These can be used alone or in combination of two or more types.

[0140] In addition to the above, examples of epoxy compounds include heterocyclic epoxy compounds, glycidyl ether epoxy compounds, glycidyl ester epoxy compounds, glycidyl amine epoxy compounds, rubber-modified epoxy compounds, urethane-modified epoxy compounds, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymers, epoxy group-containing polyester compounds, epoxy group-containing polyurethane compounds, epoxy group-containing acrylic compounds, partially acrylated epoxy compounds, and epoxy-modified silicones. Commercially available products include the KF series manufactured by Shin-Etsu Chemical Co., Ltd. Examples of the KF series manufactured by Shin-Etsu Chemical Co., Ltd. include KF-101 (epoxy-modified silicone), KF-102 (epoxy-modified silicone), KF-1002 (epoxy-modified silicone), and KF-1005 (epoxy-modified silicone).

[0141] The epoxy compounds can be used alone or in combination of two or more. Preferred examples of the epoxy compounds include aromatic epoxy compounds and alicyclic epoxy compounds, and more preferred examples include bisphenol A epoxy compounds and 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate.

[0142] As the epoxy compound, an aromatic epoxy compound and an alicyclic epoxy compound are preferably used in combination. The content ratio of the aromatic epoxy compound and the alicyclic epoxy compound is appropriately set depending on the purpose and application.

[0143] When an aromatic epoxy compound and an alicyclic epoxy compound are used in combination, the content of the aromatic epoxy compound relative to the total amount of the aromatic epoxy compound and the alicyclic epoxy compound is, for example, 1 to 99 mass%, preferably 10 to 90 mass%, more preferably 30 to 80 mass%, and even more preferably 50 to 70 mass%. Also, the content of the alicyclic epoxy compound relative to the total amount of the aromatic epoxy compound and the alicyclic epoxy compound is, for example, 1 to 99 mass%, preferably 10 to 90 mass%, more preferably 20 to 70 mass%, and even more preferably 30 to 50 mass%.

[0144] [Oxetanyl group-containing compounds] An oxetanyl group-containing compound (hereinafter referred to as an oxetanyl compound) is an organic compound that has one or more oxetanyl groups in its molecule but does not have an epoxy group. Examples of oxetanyl compounds include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol, 2-ethylhexyloxetane, xylylene bisoxetane, 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, oxetanyl silsesquioxetane, silsesquioxane, phenol novolac oxetane, 3-ethyl-3-phenoxymethyloxetane, and 3-ethyl-3-allyloxymethyloxetane. These compounds can be used alone or in combination.

[0145] The oxetanyl compound may be a commercially available product, for example, an oxetanyl compound manufactured by Toagosei Co., Ltd. Examples of oxetanyl compounds manufactured by Toagosei Co., Ltd. include OXT-101 (3-ethyl-3-hydroxymethyloxetane (oxetane alcohol)), OXT-212 (2-ethylhexyloxetane), OXT-121 (xylylene bisoxetane), OXT-221 (3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane), OXT-191 (oxetanyl silsesquioxetane), OX-SQ SI20 (silsesquioxane), PHOX (phenol novolac oxetane), OXT-211 (3-ethyl-3-phenoxymethyloxetane), and OXT-212 (2-ethylhexyloxetane). Furthermore, examples of commercially available oxetanyl compounds include AL-EOX (3-ethyl-3-allyloxymethyloxetane) manufactured by Yokkaichi Synthetic Co., Ltd.

[0146] The oxetanyl group-containing compound can be used alone or in combination of two or more kinds. A preferred example of the oxetanyl group-containing compound is 2-ethylhexyloxetane.

[0147] The epoxy group- and / or oxetanyl group-containing compound may be used alone or in combination of two or more. From the viewpoints of ease of mixing, shape retention before curing, and molding accuracy, the epoxy group- and / or oxetanyl group-containing compound is preferably an epoxy group-containing compound or an oxetanyl group-containing compound, and more preferably a combination of these.

[0148] That is, from the viewpoints of ease of mixing, shape retention before curing, and molding accuracy, the second curable compound preferably contains an epoxy group-containing compound and / or an oxetanyl group-containing compound, more preferably contains both an epoxy group-containing compound and an oxetanyl group-containing compound, and even more preferably consists of an epoxy group-containing compound and an oxetanyl group-containing compound.

[0149] When the second curable compound contains an epoxy group-containing compound and an oxetanyl group-containing compound, their content ratios are appropriately set depending on the purpose and application. For example, the content ratio of the epoxy group-containing compound relative to the total amount of the epoxy group-containing compound and the oxetanyl group-containing compound is, for example, 50 to 99.9 mass%, preferably 60 to 99 mass%, more preferably 70 to 97 mass%, and even more preferably 80 to 95 mass%. Furthermore, the content ratio of the oxetanyl group-containing compound relative to the total amount of the epoxy group-containing compound and the oxetanyl group-containing compound is, for example, 0.1 to 50 mass%, preferably 1 to 40 mass%, more preferably 3 to 30 mass%, and even more preferably 5 to 20 mass%.

[0150] As described above, the second curable compound either has a hydrogen-bonding functional group or does not have a hydrogen-bonding functional group.

[0151] From the viewpoint of shape retention before curing, the hydrogen-bonding functional group value of the second curable compound (when two or more second curable compounds are used in combination, a weighted average value based on mass (the same applies hereinafter)) is, for example, 0 mol / g or more. Furthermore, from the viewpoint of shape retention before curing, the hydrogen-bonding functional group value of the second curable compound is, for example, 0.01 mol / g or less, preferably 0.05 mol / g or less, more preferably 0.001 mol / g or less, and even more preferably 0.0005 mol / g or less. That is, the hydrogen-bonding functional group value of the second curable compound is, for example, 0 mol / g or more and 0.01 mol / g or less, preferably 0 mol / g or more and 0.05 mol / g or less, more preferably 0 mol / g or more and 0.001 mol / g or less, and even more preferably 0 mol / g or more and 0.0005 mol / g or less.

[0152] As described above, the second curable compound preferably does not have a hydrogen-bonding functional group, that is, the hydrogen-bonding functional group value of the second curable compound is particularly preferably 0 mol / g.

[0153] The hydrogen-bonding substituent value (mol / g) of the second curable compound is the number of moles (mol) of hydrogen-bonding substituents in 1 g of the second curable compound. The hydrogen-bonding substituent value of the second curable compound is calculated from the molecular structure of the second curable compound, similar to the hydrogen-bonding substituent value of the first curable compound.

[0154] The hydrogen-bonding substituent value of the second curable compound can also be calculated by gas chromatography, similarly to the hydrogen-bonding substituent value of the first curable compound.

[0155] In addition to the above, the hydrogen-bonding substituent value of the second curable compound can be calculated by a known method depending on the type of hydrogen-bonding substituent.

[0156] The hydrogen-bonding functional group value of the second curable compound is smaller than the hydrogen-bonding functional group value of the first curable compound.

[0157] From the viewpoint of shape retention before curing, the difference between the hydrogen-bonding functional group value of the first curable compound and the hydrogen-bonding functional group value of the second curable compound is, for example, 0.0001 mol / g or more, preferably 0.0002 mol / g or more, more preferably 0.0003 mol / g or more, and even more preferably 0.00035 mol / g or more. Also, from the viewpoint of shape retention before curing, the difference between the hydrogen-bonding functional group value of the first curable compound and the hydrogen-bonding functional group value of the second curable compound is, for example, 0.01 mol / g or less, preferably 0.05 mol / g or less, more preferably 0.001 mol / g or less, and even more preferably 0.0005 mol / g or less. That is, the difference between the hydrogen-bonding functional group value of the first curable compound and the hydrogen-bonding functional group value of the second curable compound is, for example, 0.0001 mol / g or more and 0.01 mol / g or less, preferably 0.0002 mol / g or more and 0.05 mol / g or less, more preferably 0.0003 mol / g or more and 0.001 mol / g or less, and even more preferably 0.00035 mol / g or more and 0.0005 mol / g or less.

[0158] [Other curable compounds] The second curable component may contain other curable compounds as optional components, as needed. The other curable compounds are curable compounds other than the above-mentioned second curable compound.

[0159] Examples of the other curable compounds include curable compounds having a hydrogen-bonding substituent valence higher than that of the first curable compound.

[0160] The second curable component preferably does not contain any other curable compounds, i.e., the second curable component preferably consists of the above-mentioned second curable compound, more preferably consists of an epoxy group- and / or oxetanyl group-containing compound, and even more preferably consists of an epoxy group-containing compound and an oxetanyl group-containing compound.

[0161] [Content percentage] In the second curable component, the ratio of the second curable compound to the other curable compounds is appropriately set depending on the purpose and application.

[0162] For example, the content of the second curable compound is, for example, 10 to 100 mass%, preferably 50 to 100 mass%, more preferably 80 to 100 mass%, even more preferably 90 to 100 mass%, and particularly preferably 100 mass%, relative to the total amount of the second curable component. The content of the other curable compounds is, for example, 0 to 90 mass%, preferably 0 to 50 mass%, more preferably 0 to 20 mass%, even more preferably 0 to 10 mass%, and particularly preferably 0 mass%, relative to the total amount of the second curable component.

[0163] The content ratio of the other curable compounds is, for example, 0 to 500 parts by mass, preferably 0 to 300 parts by mass, more preferably 0 to 100 parts by mass, even more preferably 0 to 10 parts by mass, and particularly preferably 0 parts by mass, relative to 100 parts by mass of the total amount of the second curable compounds.

[0164] The total content of the second curable components relative to the total amount of the second ink is, for example, 50 to 99 mass %, preferably 60 to 95 mass %, and more preferably 70 to 90 mass %.

[0165] The content of the second curable compound is, for example, 50 to 99 mass%, preferably 60 to 95 mass%, more preferably 70 to 90 mass%, relative to the total amount of the second ink. The content of the other curable compounds is, for example, 0 to 10 mass%, preferably 0 to 5 mass%, more preferably 0 to 1 mass%, and even more preferably 0 mass%, relative to the total amount of the second ink.

[0166] [Physical properties of the second curing component] The second curable component contains a second curable compound. Therefore, the second curable component has a hydrogen-bonding functional group or does not have a hydrogen-bonding functional group. The second curable component preferably does not have a hydrogen-bonding functional group.

[0167] From the viewpoint of shape retention before curing, the hydrogen-bonding functional group value (weighted average value based on mass (hereinafter the same)) of the second polymerizable component is, for example, 0 mol / g or more. Furthermore, from the viewpoint of shape retention before curing, the hydrogen-bonding functional group value of the second polymerizable component is, for example, 0.01 mol / g or less, preferably 0.05 mol / g or less, more preferably 0.001 mol / g or less, and even more preferably 0.0005 mol / g or less. That is, the hydrogen-bonding functional group value of the second polymerizable component is, for example, 0 mol / g or more and 0.01 mol / g or less, preferably 0 mol / g or more and 0.05 mol / g or less, more preferably 0 mol / g or more and 0.001 mol / g or less, and even more preferably 0 mol / g or more and 0.0005 mol / g or less. The hydrogen-bonding functional group value of the second polymerizable component is particularly preferably 0 mol / g. The hydrogen-bonding functional group value of the second polymerizable component is calculated based on the mass and hydrogen-bonding functional group value of the second curable compound and the masses and hydrogen-bonding functional group values ​​of the other curable compounds using a known weighted average method.

[0168] The hydrogen-bonding functional group value of the second polymerizable component is smaller than the hydrogen-bonding functional group value of the first polymerizable component.

[0169] From the viewpoint of shape retention before curing, the difference between the hydrogen-bonding functional group value of the first polymerizable component and the hydrogen-bonding functional group value of the second polymerizable component is 0.0001 mol / g or more, preferably 0.0002 mol / g or more, more preferably 0.0003 mol / g or more, and even more preferably 0.00035 mol / g or more. Also, from the viewpoint of shape retention before curing, the difference between the hydrogen-bonding functional group value of the first polymerizable component and the hydrogen-bonding functional group value of the second polymerizable component is, for example, 0.01 mol / g or less, preferably 0.05 mol / g or less, more preferably 0.001 mol / g or less, and even more preferably 0.0005 mol / g or less. That is, the difference between the hydrogen-bonding functional group value of the first polymerizable component and the hydrogen-bonding functional group value of the second polymerizable component is, for example, 0.0001 mol / g or more and 0.01 mol / g or less, preferably 0.0002 mol / g or more and 0.05 mol / g or less, more preferably 0.0003 mol / g or more and 0.001 mol / g or less, and even more preferably 0.00035 mol / g or more and 0.0005 mol / g or less.

[0170] (2) Second filler The second filler is a thixotropic agent for adjusting the thixotropy of the second ink. The second filler is dispersed in the second curable component. That is, the second filler is dispersed in the second curable compound (and other curable compounds).

[0171] The second filler has predetermined electrical properties. More specifically, from the viewpoints of shape retention before curing and molding accuracy, the pH at the isoelectric point of the second filler (when two or more types of second fillers are used in combination, the weighted average value based on mass (the same applies hereinafter)) is, for example, 1.0 or more, preferably 1.2 or more, more preferably 1.5 or more, and even more preferably 1.7 or more. The pH at the isoelectric point of the second filler is 9.0 or less, preferably 7.5 or less, more preferably 5.0 or less, and even more preferably 3.0 or less. That is, the pH at the isoelectric point of the second filler is, for example, 1.0 or more and 9.0 or less, preferably 1.2 or more and 7.5 or less, more preferably 1.5 or more and 5.0 or less, and even more preferably 1.7 or more and 3.0 or less.

[0172] Furthermore, from the viewpoint of shape retention before hardening and molding accuracy, the pH at the isoelectric point of the second filler is approximately the same as the pH at the isoelectric point of the first filler.

[0173] More specifically, the difference between the pH at the isoelectric point of the first filler and the pH at the isoelectric point of the second filler is, for example, 0 or more. The difference between the pH at the isoelectric point of the first filler and the pH at the isoelectric point of the second filler is 1.0 or less, preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less. That is, the pH at the isoelectric point of the second filler is, for example, 0 or more and 1.0 or less, preferably 0 or more and 0.5 or less, more preferably 0 or more and 0.3 or less, and even more preferably 0 or more and 0.1 or less. Particularly preferably, the pH at the isoelectric point of the first filler and the pH at the isoelectric point of the second filler are the same.

[0174] Examples of second fillers having the above electrical properties include SiO2 (pH at isoelectric point = 1.8), kaolin (pH at isoelectric point = 5.1), silicone (pH at isoelectric point = 5.8), mullite (pH at isoelectric point = 6.3), and polypropylene (pH at isoelectric point = 7.1). These can be used alone or in combination of two or more. Preferred examples of the second filler include SiO2, kaolin, silicone, mullite, and polypropylene, and more preferred examples include SiO2.

[0175] From the viewpoint of shape retention before hardening and molding accuracy, it is particularly preferable that the first filler and the second filler are the same type.

[0176] The shape and size of the second filler are not particularly limited and are appropriately selected depending on the purpose and application. For example, the average particle size (median size) of the second filler is, for example, 0.001 to 100 μm, preferably 0.005 to 20 μm.

[0177] The content of the second filler is not particularly limited, and is appropriately selected so that the viscosity and thixotropy index of the second ink fall within the desired ranges.

[0178] The content ratio of the second filler is, for example, 0.01 to 30 parts by mass (phr), preferably 0.1 to 10 parts by mass (phr), more preferably 0.5 to 5 parts by mass (phr), and even more preferably 1 to 3 parts by mass (phr) relative to 100 parts by mass of the total amount of the second curable component (uncured polymer or resin raw material monomer in the second ink).

[0179] The content of the second filler relative to the total amount of the second ink is, for example, 0.01 to 30 mass %, preferably 0.1 to 10 mass %, more preferably 0.5 to 5 mass %, and even more preferably 1 to 3 mass %.

[0180] (3) Polymerization initiator The second ink may further contain a polymerization initiator, and preferably contains a polymerization initiator.

[0181] The polymerization initiator is selected depending on the second curable component. For example, when the second curable component contains an active energy ray curable compound, the polymerization initiator may be, for example, an active energy ray polymerization initiator. When the second curable component contains a thermosetting compound, the polymerization initiator may be, for example, a thermal polymerization initiator.

[0182] Preferably, the second curable component contains an active energy ray-curable compound, and the polymerization initiator contains an active energy ray polymerization initiator.

[0183] Examples of the active energy ray polymerization initiator include an active energy ray radical polymerization initiator and an active energy ray cationic polymerization initiator.

[0184] The active energy ray polymerization initiator is selected depending on the active energy ray curable compound. For example, when the active energy ray curable compound is an active energy ray radical polymerizable compound, the active energy ray polymerization initiator may be an active energy ray radical polymerization initiator. Furthermore, when the active energy ray curable compound is an active energy ray cationically polymerizable compound, the active energy ray polymerization initiator may be an active energy ray cationically polymerizable compound.

[0185] It is particularly preferred that the second curable component contains an active energy ray cationic polymerizable compound, and the polymerization initiator contains an active energy ray cationic polymerization initiator.

[0186] Examples of the active energy ray cationic polymerization initiator include photo-cationic polymerization initiators. Examples of the photo-cationic polymerization initiator include iodonium salt-based photo-polymerization initiators and sulfonium salt-based photo-polymerization initiators. The photo-cationic polymerization initiator may also be a commercially available product. An example of a commercially available product is CPI-210 manufactured by San-Apro Co., Ltd. These can be used alone or in combination of two or more types.

[0187] The content of the polymerization initiator is, for example, 0.1 to 20 parts by mass (phr), preferably 0.5 to 15 parts by mass (phr), more preferably 1 to 10 parts by mass (phr), and even more preferably 2 to 5 parts by mass (phr), relative to 100 parts by mass of the total amount of the second curable component (uncured polymer or resin raw material monomer in the second ink).

[0188] The content of the polymerization initiator relative to the total amount of the second ink is, for example, 0.1 to 20 mass %, preferably 0.5 to 15 mass %, more preferably 1 to 10 mass %, and even more preferably 2 to 5 mass %.

[0189] (4) Additives The second ink may contain the above-mentioned additives as needed. The additives are preferably the above-mentioned colorants. The amount and timing of the additives to be added are determined appropriately depending on the purpose and application.

[0190] From the viewpoint of obtaining cured resin products (described below) with various color tones, the color tone of the cured product of the first ink alone is preferably different from the color tone of the cured product of the second ink alone (described below). In other words, the colorant preferably is a colorant of a different type from the colorant contained in the first ink.

[0191] If the colorant contained in the first ink and the colorant contained in the second ink are different from each other, the color tone of the mixed ink can be adjusted by mixing the first ink and the second ink in any ratio, and the color tone of the cured resin (described below) can also be adjusted.

[0192] (5) Manufacturing method of second ink The method for producing the second ink is not particularly limited. For example, the second curable component (preferably the second curable compound and other curable compounds) and the second filler are mixed by a known method. If necessary, the second curable component and the second filler are mixed with the above-mentioned polymerization initiator and / or the above-mentioned additives by a known method. As a result, the second ink is obtained.

[0193] (6) Physical properties of the second ink The viscosity of the second ink at 25° C. is, for example, 100 to 50,000 mPa·s, preferably 500 to 10,000 mPa·s, or more preferably 1,000 to 5,000 mPa·s.

[0194] Furthermore, the difference in viscosity between the first ink at 25°C and the second ink at 25°C is, for example, 0 mPa·s or more and 10,000 mPa·s or less, preferably 10 mPa·s or more and 5,000 mPa·s or less, more preferably 50 mPa·s or more and 1,000 mPa·s or less, and even more preferably 100 mPa·s or more and 1,000 mPa·s or less.

[0195] The thixotropic index of the second ink is, for example, 1.0 or more, preferably 1.1 or more, more preferably 1.2 or more, even more preferably 1.3 or more, and particularly preferably 1.5 or more. The thixotropic index of the second ink is, for example, 10.0 or less, preferably 8.0 or less, more preferably 5.0 or less, even more preferably 3.0 or less, and particularly preferably 2.0 or less. That is, the thixotropic index of the second ink is, for example, 1.0 or more and 10.0 or less, preferably 1.1 or more and 8.0 or less, more preferably 1.2 or more and 5.0 or less, even more preferably 1.3 or more and 3.0 or less, and particularly preferably 1.5 or more and 2.0 or less.

[0196] Furthermore, the thixotropy index of the second ink is, for example, approximately the same as the thixotropy index of the first ink.

[0197] More specifically, the difference between the thixotropic index of the first ink and the thixotropic index of the second ink is, for example, 0 or more and 3.0 or less, preferably 0 or more and 2.0 or less, more preferably 0 or more and 1.0 or less, and even more preferably 0 or more and 0.1 or less.

[0198] The second ink is cured by irradiation with actinic energy rays and / or by heating.

[0199] For example, when the second curable component contains an active energy ray-curable compound, when the second ink is irradiated with active energy rays, the second ink is cured to form a single cured product of the second ink.

[0200] Examples of active energy rays include ultraviolet rays, visible light rays, electron beams, X-rays, and radioactive rays, and ultraviolet rays are preferred. The irradiation conditions are not particularly limited. For example, the irradiation dose (cumulative light amount) is, for example, 100 to 600,000 mJ / cm. 2 , preferably 300 to 30,000 mJ / cm 2 The output of the active energy rays is, for example, 1.0 to 1000 mW / cm 2 , preferably 10 to 1000 mW / cm 2 is.

[0201] Furthermore, for example, when the second curable component contains a thermosetting compound, when the second ink is heated, the second ink cures and a single cured product of the second ink is formed.

[0202] The heating conditions are not particularly limited. For example, the heating temperature is, for example, 30 to 200° C., preferably 50 to 150° C. The heating time is 1 to 48 hours, preferably 2 to 24 hours.

[0203] The storage modulus E' of the second ink alone at 25°C is, for example, 1 MPa or more and 100,000 MPa or less, preferably 10 MPa or more and 50,000 MPa or less, more preferably 50 MPa or more and 10,000 MPa or less, and even more preferably 100 MPa or more and 5,000 MPa or less.

[0204] Furthermore, from the viewpoint of obtaining cured resin products (described below) with various mechanical properties, the mechanical properties of the cured product of the first ink alone and the mechanical properties of the cured product of the second ink alone differ from each other.

[0205] If the mechanical properties of the first ink alone cured product and the mechanical properties of the second ink alone cured product are different from each other, the mechanical properties of the cured resin product (described below) can be adjusted by mixing the first ink and the second ink in any ratio.

[0206] For example, the storage modulus E' at 25°C of a cured product of the second ink alone is greater than the storage modulus E' at 25°C of a cured product of the first ink alone.

[0207] More specifically, the difference between the storage modulus E' at 25°C of the first ink alone cured product and the storage modulus E' at 25°C of the second ink alone cured product is, for example, 1 MPa or more and 100,000 MPa or less, preferably 10 MPa or more and 50,000 MPa or less, more preferably 50 MPa or more and 10,000 MPa or less, and even more preferably 100 MPa or more and 5,000 MPa or less.

[0208] 3) Manufacturing method for 3D modeling ink set There are no particular limitations on the method for producing the three-dimensional modeling ink set. For example, the first ink and the second ink are prepared and then combined as described above. In this way, the three-dimensional modeling ink set is produced.

[0209] The three-dimensional modeling ink set is suitably used for producing a cured resin product by three-dimensional modeling.

[0210] 2.Cured resin material The cured resin product is a cured product of the three-dimensional modeling ink set. More specifically, the cured resin product contains a cured product of a mixture of the first ink and the second ink (i.e., a composite cured product), and preferably consists of a cured product of a mixture of the first ink and the second ink.

[0211] The cured resin is produced by three-dimensional modeling. The method for producing a cured resin by three-dimensional modeling is not particularly limited, but examples include additive manufacturing and cutting modeling, and preferably additive manufacturing. In additive manufacturing, a dispense-type three-dimensional modeling device (i.e., a 3D printer) is used to three-dimensionally model a three-dimensional modeling ink set to produce a cured resin. The method for producing a cured resin is described in detail below.

[0212] In this method, first, the three-dimensional modeling ink set is prepared (preparation step), that is, the first ink and the second ink are prepared.

[0213] Next, in this method, the first ink and the second ink of the three-dimensional modeling ink set are mixed using a dispense-type three-dimensional modeling device to obtain a mixed ink (mixing step).

[0214] The dispense-type three-dimensional modeling apparatus includes, for example, at least two dispensers, a table, and a curing device.

[0215] The dispenser includes, for example, a first dispenser that dispenses the first ink and a second dispenser that dispenses the second ink. Examples of the dispenser include an air pump dispenser, an aerojet dispenser, an air pulse dispenser, a gear pump dispenser, and a mechanical dispenser, and preferably, an air pump dispenser or an aerojet dispenser.

[0216] The table is a base on which the first ink and the second ink are placed at any position and mixed together. The table is not particularly limited, and examples thereof include known platform tables.

[0217] The curing device is a device that cures the mixture of the first ink and the second ink. Examples of the curing device include a known active energy ray irradiation device and a known heating device. The curing device is appropriately selected depending on the type of the first ink and the type of the second ink.

[0218] When a dispenser-type three-dimensional modeling device is used, for example, a first ink is contained in a first dispenser, and a second ink is contained in a second dispenser different from the first dispenser.

[0219] In this method, the first ink and the second ink are each ejected by a dispenser, and the ejected first ink and the ejected second ink are brought into contact with each other.

[0220] More specifically, for example, a first ink is ejected from a first dispenser toward a desired position on the table. Furthermore, a second ink is ejected from a second dispenser toward a desired position on the table. In this method, the ejected first ink and the ejected second ink come into contact with each other in an uncured state at the desired position on the table. When the first ink and the second ink come into contact with each other, they diffuse and mix. As a result, a mixed ink is obtained at the desired position on the table.

[0221] The timing of ejection of the first ink and the timing of ejection of the second ink are not particularly limited. For example, the first ink and the second ink may be ejected simultaneously toward the same position. Alternatively, the first ink may be ejected first, and then the second ink may be ejected toward the ejected first ink. Alternatively, the second ink may be ejected first, and then the first ink may be ejected toward the ejected second ink.

[0222] In the mixed ink, the mass ratio of the first ink to the second ink is appropriately selected depending on the purpose and application. More specifically, the mass ratio of the first ink to the second ink is adjusted depending on the properties (e.g., mechanical properties and / or color tone) required of the cured resin.

[0223] In other words, the ejection amounts of the first ink and the second ink are adjusted so as to obtain a cured resin product with desired properties (e.g., mechanical properties and / or color tone), resulting in a mixed ink containing the first ink and the second ink in any desired ratio.

[0224] For example, in a mixed ink, the mass ratio of the second ink relative to 100 parts by mass of the first ink is, for example, 1 part by mass or more and 1000 parts by mass or less, preferably 10 parts by mass or more and 500 parts by mass or less, more preferably 50 parts by mass or more and 200 parts by mass or less, and even more preferably 70 parts by mass or more and 150 parts by mass or less.

[0225] The ratio (total amount) of the first curable component to the total amount of the first curable component (uncured polymer or raw material monomer) and the second curable component (uncured polymer or raw material monomer) is, for example, 1% by mass to 99% by mass, preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, even more preferably 30% by mass to 70% by mass, and particularly preferably 40% by mass to 60% by mass. The ratio (total amount) of the second curable component to the total amount of the first curable component (uncured polymer or raw material monomer) and the second curable component (uncured polymer or raw material monomer) is, for example, 1% by mass to 99% by mass, preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass, even more preferably 30% by mass to 70% by mass, and particularly preferably 40% by mass to 60% by mass.

[0226] The mass proportion of the second curable compound is, for example, 1 part by mass or more and 5000 parts by mass or less, preferably 10 parts by mass or more and 1000 parts by mass or less, more preferably 200 parts by mass or more and 800 parts by mass or less, and even more preferably 100 parts by mass or more and 500 parts by mass or less, relative to 100 parts by mass of the first curable compound.

[0227] The amount of the second filler is, for example, 1 part by mass or less and 1,000 parts by mass or more, preferably 5 parts by mass or less and 500 parts by mass or more, more preferably 10 parts by mass or less and 100 parts by mass or more, and even more preferably 20 parts by mass or less and 50 parts by mass or more, per 100 parts by mass of the first filler.

[0228] The viscosity of the mixed ink at 25°C 60 seconds after mixing the first ink and the second ink is, for example, 100 mPa·s or more and 50,000 mPa·s or less, preferably 500 mPa·s or more and 10,000 mPa·s or less, and more preferably 1,000 mPa·s or more and 5,000 mPa·s or less.

[0229] Furthermore, the difference between the viscosity of the mixed ink 60 seconds after mixing the first ink and the second ink and the viscosity of the first ink at 25°C is, for example, 0 mPa·s or more and 10,000 mPa·s or less, preferably 10 mPa·s or more and 5,000 mPa·s or less, more preferably 50 mPa·s or more and 1,000 mPa·s or less, and even more preferably 100 mPa·s or more and 1,000 mPa·s or less.

[0230] Furthermore, the difference between the viscosity of the mixed ink 60 seconds after mixing the first ink and the second ink and the viscosity of the second ink at 25°C is, for example, 0 mPa·s or more and 10,000 mPa·s or less, preferably 10 mPa·s or more and 5,000 mPa·s or less, more preferably 50 mPa·s or more and 1,000 mPa·s or less, and even more preferably 100 mPa·s or more and 1,000 mPa·s or less.

[0231] The thixotropic index of the mixed ink 60 seconds after mixing the first ink and the second ink is, for example, 1.1 or more, preferably 1.2 or more, more preferably 1.3 or more, even more preferably 1.4 or more, and particularly preferably 1.5 or more. The thixotropic index of the mixed ink 60 seconds after mixing the first ink and the second ink is, for example, 15.0 or less, preferably 10.0 or less, more preferably 8.0 or less, even more preferably 3.0 or less, and particularly preferably 2.0 or less. That is, the thixotropic index of the mixed ink 60 seconds after mixing the first ink and the second ink is, for example, 1.1 or more and 15.0 or less, preferably 1.2 or more and 10.0 or less, more preferably 1.3 or more and 8.0 or less, even more preferably 1.4 or more and 3.0 or less, and particularly preferably 1.5 or more and 2.0 or less.

[0232] Furthermore, the thixotropy index of the mixed ink 60 seconds after mixing the first ink and the second ink is higher than the thixotropy index of the first ink, for example.

[0233] For example, the difference between the thixotropic index of the mixed ink 60 seconds after mixing the first ink and the second ink and the thixotropic index of the first ink is, for example, 0.1 or more and 5.0 or less, preferably 0.2 or more and 4.0 or less, more preferably 0.3 or more and 3.0 or less, and even more preferably 0.3 or more and 1.0 or less.

[0234] Furthermore, the thixotropy index of the mixed ink 60 seconds after mixing the first ink and the second ink is higher than the thixotropy index of the second ink, for example.

[0235] For example, the difference between the thixotropic index of the mixed ink 60 seconds after mixing the first ink and the second ink and the thixotropic index of the second ink is, for example, 0.1 or more and 5.0 or less, preferably 0.2 or more and 4.0 or less, more preferably 0.3 or more and 3.0 or less, and even more preferably 0.3 or more and 1.0 or less.

[0236] Thereafter, in this method, the mixed ink is cured to obtain a cured resin (curing step).

[0237] That is, in this method, the mixed ink is irradiated with active energy rays and / or heated on the stage using the above-mentioned curing device.

[0238] More specifically, for example, when the first curable component contains an active energy ray-curable compound and / or when the second curable component contains an active energy ray-curable compound, the mixed ink is irradiated with active energy rays.

[0239] The method of irradiating with active energy rays is not particularly limited, and a known active energy ray irradiator can be used. Examples of active energy rays include ultraviolet rays, visible light, electron beams, X-rays, and radioactive rays, and ultraviolet rays are preferred. The irradiation conditions are not particularly limited. For example, the irradiation dose (cumulative light amount) can be, for example, 100 to 600,000 mJ / cm. 2 , preferably 300 to 30,000 mJ / cm 2 The output of the active energy rays is, for example, 1.0 to 1000 mW / cm 2 , preferably 10 to 1000 mW / cm 2 is.

[0240] Furthermore, for example, when the first curable component contains a thermosetting compound and / or when the second curable component contains a thermosetting compound, the mixed ink is heated.

[0241] The heating method is not particularly limited, and a known heating device can be used. The heating conditions are not particularly limited. For example, the heating temperature is, for example, 30 to 200°C, preferably 50 to 150°C. The heating time is 1 to 48 hours, preferably 2 to 24 hours.

[0242] Although not described in detail, when an active energy ray-curable compound and a thermosetting compound are used in combination, irradiation with active energy rays and heating can also be used in combination.

[0243] The mixed ink is then irradiated with active energy rays and / or heated to cure the mixed ink, thereby obtaining a cured resin product.

[0244] The storage modulus E' of the cured resin at 25°C is, for example, 0.1 MPa or more and 10,000 MPa or less, preferably 0.1 MPa or more and 2,000 MPa or less, more preferably 1 MPa or more and 1,000 MPa or less, and even more preferably 100 MPa or more and 1,000 MPa or less.

[0245] The storage modulus E' of the cured resin at 25°C is greater than the storage modulus E' of the first cured resin at 25°C, for example.

[0246] For example, the difference between the storage modulus E' of the first cured resin at 25°C and the storage modulus E' of the cured resin at 25°C is, for example, 0.1 MPa or more and 10,000 MPa or less, preferably 0.1 MPa or more and 2,000 MPa or less, more preferably 1 MPa or more and 1,000 MPa or less, and even more preferably 100 MPa or more and 1,000 MPa or less.

[0247] The storage modulus E' of the cured resin at 25°C is smaller than the storage modulus E' of the second cured resin at 25°C, for example.

[0248] For example, the difference between the storage modulus E' of the second resin cured product at 25°C and the storage modulus E' of the resin cured product at 25°C is, for example, 0.1 MPa or more and 10,000 MPa or less, preferably 0.1 MPa or more and 2,000 MPa or less, more preferably 1 MPa or more and 1,000 MPa or less, and even more preferably 100 MPa or more and 1,000 MPa or less.

[0249] 3. Effects In the three-dimensional modeling ink set, the first ink contains a first curable component curable by actinic radiation and / or heat and a first filler dispersed in the first curable component, and the second ink contains a second curable component curable by actinic radiation and / or heat and a second filler dispersed in the second curable component.

[0250] In such a three-dimensional modeling ink set, the hydrogen-bonding functional group value of the second curable component is smaller than the hydrogen-bonding functional group value of the first curable component. Furthermore, the difference between the hydrogen-bonding functional group value of the second curable component and the hydrogen-bonding functional group value of the second curable component is equal to or greater than a predetermined value. In other words, the electrical properties of the first curable component and the second curable component are different from each other. More specifically, the polarity of the first curable component is higher than the polarity of the second curable component.

[0251] On the other hand, the difference between the pH at the isoelectric point of the first filler and the pH at the isoelectric point of the second filler is equal to or less than a predetermined value. In other words, the electrical properties of the first filler and the electrical properties of the second filler are comparable. More specifically, the polarity of the first filler and the polarity of the second filler are comparable.

[0252] In this case, the first curable component is bound to the first filler in the first ink, electrically neutralizing the first filler. Because the first curable component has a relatively high polarity, the amount of the first curable component bound to the first filler is relatively small.

[0253] In the second ink, the second curable component is bound to the second filler, electrically neutralizing the second filler. Because the second curable component has a relatively low polarity, the amount of the second curable component bound to the second filler is relatively large.

[0254] In such a three-dimensional modeling ink set, when the first ink and the second ink are mixed, both the first curable component and the second curable component are bound to the first filler, and both the first curable component and the second curable component are bound to the second filler. In particular, in the early stages of mixing the first ink and the second ink, the balance of the electrical stability of the mixture is disrupted, and the first filler and the second filler bind the first curable component and the second curable component in amounts exceeding those required for electrical neutralization.

[0255] As a result, the thixotropy of the mixture temporarily increases in the early stage of mixing the first ink and the second ink, i.e., the mixture temporarily has a relatively high thixotropy.

[0256] In other words, in the initial stage of mixing the first ink and the second ink, the mixture has relatively good shape retention. That is, the above-described three-dimensional modeling ink set has relatively good shape retention.

[0257] After the first ink and the second ink are mixed, the mixture becomes electrically stable over time. Therefore, the amounts of the first and second curable components bound by the first and second fillers decrease over time. Ultimately, the first and second fillers bind the first and second curable components in amounts necessary for electrical neutralization. In other words, the thixotropy of the mixture decreases over time.

[0258] In this way, the ink set for three-dimensional printing can temporarily increase the thixotropy of the mixture, eliminating the need to increase the thixotropy of each of the first and second inks. Therefore, the ink set for three-dimensional printing can be mixed relatively easily. In other words, the ink set for three-dimensional printing has excellent ease of mixing.

[0259] The cured resin product of the present invention is obtained using the above-described ink set for three-dimensional modeling. Therefore, the first ink and the second ink can be mixed relatively easily during production, and the cured resin product can have relatively excellent shape retention. Furthermore, the mechanical properties and / or color of the cured resin product can be adjusted as desired depending on the mixing ratio of the first ink and the second ink.

[0260] The method for producing a cured resin product of the present invention uses the above-described ink set for three-dimensional modeling. More specifically, the first ink and the second ink are each ejected by a dispenser. The ejected first ink and the ejected second ink then come into contact with each other after ejection, and are mixed by mutual diffusion of the first ink and the second ink.

[0261] Therefore, the above-described method for producing a cured resin product allows the first ink and the second ink to be mixed relatively easily, and provides relatively good shape retention. Furthermore, the mechanical properties and / or color of the cured resin product can be adjusted as desired depending on the mixing ratio of the first ink and the second ink.

[0262] 4. Variations In the above description, the three-dimensional modeling ink set includes two inks, the first ink and the second ink, but the three-dimensional modeling ink set can include other inks as needed. Also, the first ink and the second ink can be mixed with other inks to obtain a mixed ink.

[0263] In the above description, an inkjet 3D modeling device is used for 3D modeling, but the modeling device is not limited to this. Any known 3D modeling device can be used depending on the purpose and application.

[0264] 5.Applications The above-described 3D modeling ink set, cured resin product, and method for producing the cured resin product are suitable for use in various industrial fields where 3D modeling is employed, such as pseudo-biomaterials, robot components, android components, wearable components, clothing, hygiene products, cosmetics, furniture, food packaging, sporting goods, leisure goods, medical supplies, nursing care products, housing components, acoustic components, lighting components, vibration-damping components, soundproofing components, daily necessities, miscellaneous goods, cushions, bedding, stress absorbers, stress relaxation materials, automotive interior materials, automotive exterior materials, railway components, aircraft components, optical components, office automation equipment components, miscellaneous surface protection materials, semiconductor encapsulants, self-repairing materials, health appliances, eyeglass lenses, toys, packing, cable sheaths, wire harnesses, telecommunications cables, automotive wiring, computer wiring, industrial goods, shock absorbers, and semiconductor products, with pseudo-biomaterials being preferred. [Example]

[0265] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited thereto. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, and parameters described in the above "Modes for Carrying Out the Invention."

[0266] 1.Raw materials A) Curable component Preparation example A1 (1,3-H6XDI / PPG10000 / HEA) Under a nitrogen atmosphere, polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000 and 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI) were charged into a separable glass flask. The amounts charged were adjusted so that the equivalent ratio (NCO / OH) of the isocyanate groups of 1,3-bis(isocyanatomethyl)cyclohexane to the hydroxyl groups of the polyoxypropylene glycol (PPG) was 8.0.

[0267] Next, a mixture of polyoxypropylene glycol (PPG) and 1,3-bis(isocyanatomethyl)cyclohexane was heated to 80°C. Next, a urethane-forming catalyst (tin(II) ethylhexanoate) was added to the mixture. The amount added was adjusted so that the urethane-forming catalyst was 10 ppm relative to the mixture. Thereafter, the mixture was reacted at 80°C for 4 hours to obtain a crude product containing an isocyanate-terminated prepolymer and unreacted 1,3-bis(isocyanatomethyl)cyclohexane. Next, the crude product was subjected to thin-film distillation under the following conditions to purify the isocyanate-terminated prepolymer.

[0268] Temperature conditions: 160~170℃ Pressure conditions: 70 to 100 Pa Supply flow rate: 3.5-4g / min

[0269] Next, the isocyanate-terminated prepolymer and 2-hydroxyethyl acrylate (HEA) were added to the separable flask, with the amount adjusted so that the equivalent ratio (NCO / OH) of the isocyanate groups of the isocyanate-terminated prepolymer to the hydroxyl groups of the 2-hydroxyethyl acrylate was 1.0.

[0270] Next, the mixture of the isocyanate group-terminated prepolymer and 2-hydroxyethyl acrylate was heated to 70°C. Next, a urethane-forming catalyst (tin(II) ethylhexanoate) was added to the mixture. The amount added was adjusted so that the urethane-forming catalyst was 200 ppm relative to the mixture. Thereafter, the mixture was heated to 70°C, and the isocyanate group-terminated prepolymer and 2-hydroxyethyl acrylate were reacted until the isocyanate group concentration reached 0.01% or less. In this manner, a urethane (meth)acrylate was produced.

[0271] That is, polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), and 2-hydroxyethyl acrylate (HEA) were reacted to obtain urethane (meth)acrylate (1) (hereinafter, UA(1)).

[0272] The hydrogen-bonding functional group value of UA(1) was 0.000377 mol / g. The hydrogen-bonding functional group value of UA(1) was calculated by the following method.

[0273] In other words, from the viewpoint of molecular equivalent, it was inferred that UA(1) is produced from the following raw materials. Polyoxypropylene glycol 1 mol 1,3-bis(isocyanatomethyl)cyclohexane 2mol 2-Hydroxyethyl acrylate 2mol

[0274] In the above reaction, if the amount of polyoxypropylene glycol is 10,000.00 g (1 mol), the amount of 1,3-bis(isocyanatomethyl)cyclohexane is 388.46 g (2 mol), and the amount of 2-hydroxyethyl acrylate is 232.24 g (2 mol), the mass of UA(1) produced is 10,620.7 g (= 10,000.00 g + 388.46 g + 232.24 g).

[0275] In the above reaction, 2 moles of 1,3-bis(isocyanatomethyl)cyclohexane are converted into urethane, and 4 moles of amino groups (NH groups) are generated as hydrogen-bonding functional groups.

[0276] Therefore, the hydrogen-bonding functional group value of UA(1) is 0.000377 mol / g (= 4 mol / 10620.7 g).

[0277] Preparation example A2 (1,4-H6XDI / PPG10000 / HEA) Instead of 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI) was used.

[0278] Except for the above, polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000, 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6XDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (2) (hereinafter, UA(2)).

[0279] The hydrogen-bonding functional group value of UA(2) was calculated in the same manner as in Preparative Example A1 and was found to be 0.000377 mol / g.

[0280] Preparation example A3 (TDI / PPG10000 / HEA) Tolylene diisocyanate (TDI) was used instead of 1,3-bis(isocyanatomethyl)cyclohexane.

[0281] Except for the above, polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000, tolylene diisocyanate (TDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (3) (hereinafter, UA(3)).

[0282] The hydrogen-bonding functional group value of UA(3) was calculated in the same manner as in Preparative Example A1 and was found to be 0.000378 mol / g.

[0283] Preparation example A4 (MDI / PPG10000 / HEA) Diphenylmethane diisocyanate (MDI) was used instead of 1,3-bis(isocyanatomethyl)cyclohexane.

[0284] Except for the above, polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000, diphenylmethane diisocyanate (MDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (4) (hereinafter, UA(4)).

[0285] The hydrogen-bonding functional group value of UA(4) was calculated in the same manner as in Preparative Example A1 and was found to be 0.000373 mol / g.

[0286] Preparation example A5 (1,3-XDI / PPG10000 / HEA) Instead of 1,3-bis(isocyanatomethyl)cyclohexane, 1,3-xylylene diisocyanate (1,3-XDI) was used.

[0287] Except for the above, polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000, 1,3-xylylene diisocyanate (1,3-XDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (5) (hereinafter, UA(5)).

[0288] The hydrogen-bonding functional group value of UA(5) was calculated in the same manner as in Preparative Example A1 and was found to be 0.000377 mol / g.

[0289] Preparation example A6 (HDI / PPG10000 / HEA) Hexamethylene diisocyanate (HDI) was used instead of 1,3-bis(isocyanatomethyl)cyclohexane.

[0290] Except for the above, polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000, hexamethylene diisocyanate (HDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (6) (hereinafter, UA(6)).

[0291] The hydrogen-bonding functional group value of UA(6) was calculated in the same manner as in Preparative Example A1 and was found to be 0.000378 mol / g.

[0292] Preparation example A7 (PDI / PPG10000 / HEA) Pentamethylene diisocyanate (PDI) was used instead of 1,3-bis(isocyanatomethyl)cyclohexane.

[0293] Except for the above, polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000, pentamethylene diisocyanate (PDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (7) (hereinafter, UA(7)).

[0294] The hydrogen-bonding functional group value of UA(7) was calculated in the same manner as in Preparative Example A1 and was found to be 0.000379 mol / g.

[0295] Preparation example A8 (1,3-H6XDI / PPG1000 / HEA) Instead of polyoxypropylene glycol having a number average molecular weight of 10,000 (PPG10000), polyoxypropylene glycol having a number average molecular weight of 1,000 (PPG1000) was used.

[0296] Except for the above, polyoxypropylene glycol (PPG1000) having a number average molecular weight of 1000, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (8) (hereinafter, UA(8)).

[0297] The hydrogen-bonding functional group value of UA(8) was calculated in the same manner as in Preparative Example A1 and was found to be 0.00247 mol / g.

[0298] Preparation example A9 (1,3-H6XDI / PPG19000 / HEA) Instead of polyoxypropylene glycol having a number average molecular weight of 10,000 (PPG10000), polyoxypropylene glycol having a number average molecular weight of 19,000 (PPG19000) was used.

[0299] Except for the above, polyoxypropylene glycol (PPG19000) having a number average molecular weight of 19,000, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (9) (hereinafter, UA(9)).

[0300] The hydrogen-bonding functional group value of UA(9) was calculated in the same manner as in Preparative Example A1 and was found to be 0.000204 mol / g.

[0301] Preparation example A10 (1,3-H6XDI / PTMG1000 / HEA) Instead of polyoxypropylene glycol (PPG10000) having a number average molecular weight of 10,000, polyoxytetramethylene glycol (PTMG1000) having a number average molecular weight of 1,000 was used.

[0302] Except for the above, polyoxytetramethylene glycol (PTMG1000) having a number average molecular weight of 1000, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), and 2-hydroxyethyl acrylate (HEA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (10) (hereinafter, UA(10)).

[0303] The hydrogen-bonding functional group value of UA(10) was calculated in the same manner as in Preparative Example A1 and was found to be 0.00247 mol / g.

[0304] Preparation example A11 (1,3-H6XDI / PPG10000 / HBA) 4-hydroxybutyl acrylate (HBA) was used instead of 2-hydroxyethyl acrylate (HEA).

[0305] Except for the above, polyoxytetramethylene glycol (PTMG10000) having a number average molecular weight of 10,000, 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H6XDI), and 4-hydroxybutyl acrylate (HBA) were reacted in the same manner as in Preparative Example A1 to obtain urethane (meth)acrylate (11) (hereinafter, UA(11)).

[0306] The hydrogen-bonding functional group value of UA(3) was calculated in the same manner as in Preparative Example A1 and was found to be 0.000375 mol / g.

[0307] Preparation example A12 (CN371) As the amino group-containing (meth)acrylate (1), a product name CN371 (manufactured by Sartomer Co.) was prepared. The hydrogen-bonding functional group value was calculated from the amine value of the amino group-containing (meth)acrylate (1).

[0308] The hydrogen-bonding functional group value of the amino group-containing (meth)acrylate (1) was 0.0024 mol / g.

[0309] Preparation example A13 (Viscoat 540) A hydroxyl group-containing (meth)acrylate (1) with the trade name Viscoat 540 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was prepared. The hydrogen-bonding functional group value of the hydroxyl group-containing (meth)acrylate (1) was calculated based on the number average molecular weight (polystyrene equivalent molecular weight measured by GPC) and molecular structure of the hydroxyl group-containing (meth)acrylate (1).

[0310] The hydrogen-bonding functional group value of the hydroxyl group-containing (meth)acrylate (1) was 0.0028 mol / g.

[0311] Preparation example A14 (Viscoat 700) As the hydroxyl group-containing (meth)acrylate (2), a product named Viscoat 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was prepared. Based on the molecular structure of the hydroxyl group-containing (meth)acrylate (2), the hydrogen-bonding functional group value of the hydroxyl group-containing (meth)acrylate (2) was calculated.

[0312] The hydrogen-bonding functional group value of the hydroxyl group-containing (meth)acrylate (2) was 0 mol / g.

[0313] Preparation example A15 (Viscoat 310HP) As the hydroxyl group-containing (meth)acrylate (3), a product name Viscoat 310HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.) was prepared. Based on the molecular structure of the hydroxyl group-containing (meth)acrylate (3), the hydrogen-bonding functional group value of the hydroxyl group-containing (meth)acrylate (3) was calculated.

[0314] The hydrogen-bonding functional group value of the hydroxyl group-containing (meth)acrylate (3) was 0 mol / g.

[0315] Preparation example A16 (jER828) As the epoxy group-containing compound (1), a product name jER828 (bisphenol A type epoxy compound, manufactured by Mitsubishi Chemical Corporation) was prepared. Based on the molecular structure of the epoxy group-containing compound (1), the hydrogen bond functional group value of the epoxy group-containing compound (1) was calculated.

[0316] The hydrogen-bonding functional group value of the epoxy group-containing compound (1) was 0 mol / g.

[0317] Preparation Example A17 (Celloxide 2021P) As the epoxy group-containing compound (2), a product named Celloxide 2021P (3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel) was prepared. Based on the molecular structure of the epoxy group-containing compound (2), the hydrogen-bonding functional group value of the epoxy group-containing compound (2) was calculated.

[0318] The hydrogen-bonding functional group value of the epoxy group-containing compound (2) was 0 mol / g.

[0319] Preparation example A18 (OXT-212) Aron Oxetane OXT-212 (2-ethylhexyl oxetane, manufactured by Toagosei Co., Ltd.) was prepared as the oxetanyl group-containing compound (1). Based on the molecular structure of the oxetanyl group-containing compound (1), the hydrogen-bonding functional group value of the oxetanyl group-containing compound (1) was calculated.

[0320] The hydrogen-bonding functional group value of the oxetanyl group-containing compound (1) was 0 mol / g.

[0321] Preparation Example A19 (IBXA) Isobornyl acrylate (IBXA) was prepared as the polymerizable diluent (1). Based on the molecular structure of the polymerizable diluent (1), the hydrogen-bonding functional group value of the polymerizable diluent (1) was calculated.

[0322] The hydrogen-bonding functional group value of the polymerizable diluent (1) was 0 mol / g.

[0323] B) Filler Preparation example B1 (SiO2) Powdered SiO2 was prepared as the filler. The average particle size (median size) of the SiO2 was 0.007 μm.

[0324] The pH at the isoelectric point of SiO2 was measured in accordance with the isoelectric point measurement method for fine ceramic powders of JIS R 1638 (1999). The pH at the isoelectric point of SiO2 was 1.8.

[0325] Preparation example B2 (kaolin) Powdered kaolin was prepared as a filler. The average particle size (median size) of the kaolin was 0.4 μm.

[0326] The pH at the isoelectric point of kaolin was measured in the same manner as in Preparative Example B1, and was found to be 5.1.

[0327] Preparation example B3 (silicone) Powdered silicone was prepared as the filler, and the average particle size (median size) of the silicone was 0.3 μm.

[0328] The pH at the isoelectric point of the silicone was measured in the same manner as in Preparative Example B1 and was found to be 5.8.

[0329] Preparation example B4 (mullite) Powdered mullite was prepared as the filler, and the average particle size (median size) of the mullite was 1.9 μm.

[0330] The pH at the isoelectric point of mullite was measured in the same manner as in Preparative Example B1 and was found to be 6.3.

[0331] Preparation example B5 (polypropylene) Powdered polypropylene was prepared as the filler. The average particle size (median diameter) of the polypropylene was 15 μm.

[0332] The pH at the isoelectric point of polypropylene was measured in the same manner as in Preparative Example B1 and was found to be 7.1.

[0333] Preparation example B6 (alumina) Powdered Al2O3 was prepared as the filler. The average particle size (median diameter) of Al2O3 was 0.5 μm.

[0334] The pH at the isoelectric point of Al2O3 was measured in the same manner as in Preparative Example B1 and was found to be 9.1.

[0335] Preparation example B7 (beryllia) Powdered beryllia was prepared as the filler. The average particle size (median size) of the beryllia was 14 μm.

[0336] The pH at the isoelectric point of beryllia was measured in the same manner as in Preparative Example B1 and was found to be 10.1.

[0337] Preparation example B8 (Mn(OH)2) Powdered Mn(OH)2 was prepared as the filler. The average particle size (median diameter) of Mn(OH)2 was 8 μm.

[0338] The pH at the isoelectric point of Mn(OH)2 was measured in the same manner as in Preparative Example B1. The pH at the isoelectric point of Mn(OH)2 was 12.0.

[0339] Preparation Example B9 (MgOH) Powdered MgOH was prepared as the filler. The average particle size (median diameter) of the MgOH was 5.0 μm.

[0340] The pH at the isoelectric point of MgOH was measured in the same manner as in Preparative Example B1 and was found to be 12.4.

[0341] C) Additives Preparation example C1 The following additives were prepared: Omnirad 184: Product name, photoradical polymerization initiator, manufactured by IGM resins B.V. CPI-210: Product name, cationic photopolymerization initiator, manufactured by San-Apro Irganox 245: Trade name, antioxidant, manufactured by BASF

[0342] Red: FTR 5530 Red, a red pigment manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Yellow: Product name FTR 5516 Yellow, yellow pigment, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Blue: Product name: FTR MIT 3001 Blue, blue pigment, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.

[0343] 2. Inks and mixed inks Examples 1 to 23 and Comparative Examples 1 to 7 (1) First ink A first ink was obtained by mixing a first curable component, a polymerization initiator, an antioxidant, a first filler, and a pigment according to the formulations shown in Tables 1 to 11. In Comparative Example 8, the first filler was not blended. The hydrogen-bonding functional group value of the first polymerizable component was calculated based on the blending formulation of the first curable component.

[0344] (2) Second ink A second ink was obtained by mixing a second curable component, a polymerization initiator, an antioxidant, a second filler, and a pigment according to the formulations shown in Tables 1 to 11. In Comparative Example 8, no second filler was blended. The hydrogen-bonding functional group value of the first polymerizable component was calculated based on the blending formulation of the second curable component.

[0345] (3) Mixed ink According to the formulations shown in Tables 1 to 11, the first ink and the second ink were ejected onto a table using a dispenser (product name: AeroJet, medium-high viscosity non-contact jet dispenser, manufactured by Musashi Engineering Co., Ltd.). The first ink and the second ink were then allowed to collide and come into contact with each other on the table, causing the first ink and the second ink to diffuse into each other. The first ink and the second ink were mixed in this manner to obtain a mixed ink. The difference between the hydrogen-bonding functional group value of the first polymerizable component and the hydrogen-bonding functional group value of the second polymerizable component was also calculated.

[0346] The discharge amount was controlled according to the formulations shown in Tables 1 to 11. More specifically, in Examples 1 to 21 and Comparative Examples 1 to 8, the blending ratio (total amount) of the first curable component was 50 mass % and the blending ratio (total amount) of the second curable component was 50 mass % relative to the total amount of the first curable component and the second curable component.

[0347] In addition, in Example 22, the blending ratio (total amount) of the first curable component was 75 mass% and the blending ratio (total amount) of the second curable component was 25 mass% relative to the total amount of the first curable component and the second curable component.

[0348] In addition, in Example 23, the blending ratio (total amount) of the first curable component was 25 mass% and the blending ratio (total amount) of the second curable component was 75 mass% relative to the total amount of the first curable component and the second curable component.

[0349] (4) Cured resin product The first ink and the second ink were ejected and mixed to obtain a cured resin product having a cubic shape of 1 cm square. The mixed ink was then irradiated with active energy rays to cure the mixed ink. This resulted in a cured resin product having a cubic shape of 1 cm square.

[0350] Furthermore, a cured resin product having a rectangular shape of 100 mm x 5 mm x 2 mm was obtained by the same method as above.

[0351] The wavelength of the active energy rays is 365 nm and the output is 500 mW / cm 2 (Measurement illuminance meter: UIT-201, Ushio Inc., measurement wavelength: 365 nm, cumulative light intensity: 2500 mJ / cm 2 It was.

[0352] 3. Physical property measurements (1) Viscosity The viscosity of the first ink and the viscosity of the second ink were measured using an E-type viscometer, trade name TVE-25H, manufactured by Toki Sangyo Co., Ltd., with rotor number 1, at 25°C and a rotation speed of 5 rpm in accordance with JIS Z 8809 (2011).

[0353] Furthermore, the first ink and the second ink were mixed to prepare a mixed ink. The viscosity of the mixed ink was measured 60 seconds after mixing under the above conditions. The results are shown in Tables 1 to 11.

[0354] (2) Thixotropy index The viscosity of the first ink and the viscosity of the second ink were measured using an E-type viscometer, trade name TVE-25H, manufactured by Toki Sangyo Co., Ltd., with rotor number 1, at 25°C and a rotation speed of 5 rpm in accordance with JIS Z 8809 (2011).

[0355] The first ink and the second ink were mixed to prepare a mixed ink. The viscosity of the mixed ink was measured under the above conditions 60 seconds after mixing. The measurement result was designated as viscosity A.

[0356] Furthermore, the viscosity of the first ink, the second ink, and the mixed ink were each measured in the same manner as above, except that the rotation speed was changed to 10 times the above (50 rpm). The measurement result was designated as viscosity B.

[0357] Using the following formula, the thixotropic index of the first ink, the thixotropic index of the second ink, and the thixotropic index of the mixed ink were calculated from the viscosities A and B. The results are shown in Tables 1 to 11.

[0358] Thixotropy index = Viscosity A / Viscosity B

[0359] (3) Elastic modulus A cured resin having a rectangular shape of 100 mm x 5 mm x 2 mm was used to obtain a dynamic viscoelasticity spectrum of the cured resin under the following conditions. The storage modulus E' of the cured resin at 25°C was then measured based on the dynamic viscoelasticity spectrum. The measurement conditions are as follows:

[0360] Measuring device: Model DVA-220, manufactured by IT Measurement and Control Co., Ltd. Measurement temperature: -100~250℃ Heating rate: 5℃ / min Tensile mode Length between gauge lines 20mm Static / dynamic stress ratio 1.8 Measurement frequency 10Hz

[0361] 4. Evaluation (1) Modeling accuracy The length of one side of a 1 cm cube-shaped cured resin was measured using a microscope, and the average value of the lengths of each side was taken as the actual measurement value.

[0362] Then, using the following formula, the molding accuracy was calculated based on the measured value of the length of one side and the reference value (1 cm). The results are shown in Tables 1 to 11. The evaluation criteria are as follows:

[0363] Modeling accuracy = Actual measurement value / Reference value (1 cm)

[0364] A: The molding accuracy is in the range of 95% to 105%. B: The molding accuracy is in the range of 90% or more but less than 95%, or more than 105% but less than 110%. C: The molding accuracy is in the range of 80% or more but less than 90%, or more than 110% but less than 120%. D: The modeling accuracy is less than 80% or more than 120%.

[0365] It was determined that the higher the modeling accuracy, the better the shape retention of the 3D modeling ink set.

[0366] (2) Color tone The cured resin product, which had a cube shape of 1 cm square, was visually observed to confirm the degree of mixing of the first ink and the second ink. The results are shown in Tables 1 to 11. The evaluation criteria are as follows:

[0367] A: The color tone of the cured resin was uniform. In other words, the first ink and the second ink were thoroughly mixed by simply dispensing from the dispenser. B: The color tone of the cured resin was slightly uneven, i.e., the mixing of the first ink and the second ink was slightly insufficient. C: The color tone of the cured resin was non-uniform, i.e., the first ink and the second ink were not mixed properly.

[0368] It was determined that the more uniform the color tone, the better the ease of mixing of the 3D modeling ink set.

[0369] [Table 1]

[0370] [Table 2]

[0371] [Table 3]

[0372] [Table 4]

[0373] [Table 5]

[0374] [Table 6]

[0375] [Table 7]

[0376] [Table 8]

[0377] [Table 9]

[0378] [Table 10]

[0379] [Table 11]

[0380] Details of the abbreviations in the table are given below. UA(1): Urethane (meth)acrylate of Preparation Example A1 (1,3-H6XDI / PPG10000 / HEA) UA(2): Urethane (meth)acrylate of Preparation Example A2 (1,4-H6XDI / PPG10000 / HEA) UA (3): Urethane (meth)acrylate (TDI / PPG10000 / HEA) of Preparation Example A3 UA (4): Urethane (meth)acrylate (MDI / PPG10000 / HEA) of Preparation Example A4 UA(5): Urethane (meth)acrylate of Preparation Example A5 (1,3-XDI / PPG10000 / HEA) UA(6): Urethane (meth)acrylate (HDI / PPG10000 / HEA) of Preparation Example A6 UA(7): Urethane (meth)acrylate (PDI / PPG10000 / HEA) of Preparation Example A7 UA(8): Urethane (meth)acrylate of Preparation Example A8 (1,3-H6XDI / PPG1000 / HEA) UA(9): Urethane (meth)acrylate (1,3-H6XDI / PPG19000 / HEA) of Preparation Example A9 UA(10): Urethane (meth)acrylate of Preparation Example A10 (1,3-H6XDI / PTMG1000 / HEA) UA(11): Urethane (meth)acrylate (1,3-H6XDI / PPG10000 / HBA) of Preparation Example A11 CN371: amino group-containing (meth)acrylate of Preparation Example A12, trade name CN371, manufactured by Sartomer Corporation Viscoat 540: Hydroxyl group-containing (meth)acrylate (1) of Preparation Example A13, trade name Viscoat 540, bisphenol A diglycidyl ether-(meth)acrylic acid adduct, manufactured by Osaka Organic Chemical Industry Ltd. Viscoat 700: Hydroxyl group-containing (meth)acrylate (2) of Preparation Example A14, trade name Viscoat 700, manufactured by Osaka Organic Chemical Industry Co., Ltd. Viscoat 310HP: Hydroxyl group-containing (meth)acrylate (3) of Preparation Example A15, trade name Viscoat 310HP, manufactured by Osaka Organic Chemical Industry Co., Ltd. jER828: Epoxy group-containing compound (1) of Preparation Example A16, trade name jER828, bisphenol A type epoxy compound, manufactured by Mitsubishi Chemical Corporation Celloxide 2021P: Epoxy group-containing compound (2) of Preparation Example A17, trade name Celloxide 2021P, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, manufactured by Daicel OXT-212: Oxetanyl group-containing compound (1) of Preparation Example A18, trade name Aron Oxetane OXT-212, 2-ethylhexyl oxetane, manufactured by Toagosei IBXA: Polymerizable diluent (1) of Preparative Example A19, isobornyl acrylate

[0381] Omnirad 184: Product name: Omnirad 184, photoradical polymerization initiator, manufactured by IGM resins B.V. CPI-210: Product name CPI-210, photocationic polymerization initiator, manufactured by San-Apro Irganox245: Trade name Irganox245, antioxidant, manufactured by BASF

[0382] Red: FTR 5530 Red, a red pigment manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Yellow: Product name FTR 5516 Yellow, yellow pigment, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. Blue: Product name: FTR MIT 3001 Blue, blue pigment, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.

Claims

1. a three-dimensional modeling ink set including a first ink and a second ink; The first ink is a first curable component that is curable by active energy rays and / or heat; a first filler dispersed in the first curable component; Contains The second ink is a second curable component that is curable by active energy rays and / or heat; a second filler dispersed in the second curable component; Contains the first curable component has a hydrogen-bonding functional group, the second curable component has a hydrogen-bonding functional group or does not have a hydrogen-bonding functional group; the hydrogen-bonding functional group value of the second curable component is smaller than the hydrogen-bonding functional group value of the first curable component; a difference between the hydrogen-bonding functional group value of the first curable component and the hydrogen-bonding functional group value of the second curable component is 0.0001 mol / g or more; the pH at the isoelectric point of the first filler is 9.0 or less; the pH at the isoelectric point of the second filler is 9.0 or less; a difference between a pH at the isoelectric point of the first filler and a pH at the isoelectric point of the second filler being 1.0 or less;

2. the thixotropy index of the first ink at 25°C is 8.0 or less; The three-dimensional modeling ink set according to claim 1 , wherein the second ink has a thixotropic index at 25° C. of 8.0 or less.

3. The three-dimensional modeling ink set according to claim 2 , wherein the first curable component contains a urethane (meth)acrylate.

4. The three-dimensional modeling ink set according to claim 1 , wherein the second curable component does not have a hydrogen-bonding functional group.

5. the pH at the isoelectric point of the first filler is 3.0 or less; The three-dimensional modeling ink set according to claim 1 , wherein the second filler has a pH of 3.0 or less at its isoelectric point.

6. The three-dimensional modeling ink set according to claim 1 , wherein the first filler and the second filler are of the same type.

7. A resin cured product comprising a cured product of a mixture of the first ink and the second ink of the three-dimensional modeling ink set according to any one of claims 1 to 6.

8. The cured resin product according to claim 7, which has a storage modulus E' at 25°C of 0.1 MPa or more and 2000 MPa or less.

9. A method for producing a cured resin product by three-dimensional modeling, A preparation step of preparing the three-dimensional modeling ink set according to any one of claims 1 to 6; a mixing step of mixing the first ink and the second ink of the three-dimensional modeling ink set to obtain a mixed ink; a curing step of curing the mixed ink to obtain the cured resin product, In the mixing step, A method for producing a cured resin product, comprising: discharging the first ink and the second ink from a dispenser; and bringing the discharged first ink into contact with the discharged second ink.

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