JPWO2019176139A1 - Composition for model material and composition for stereolithography - Google Patents

Abstract

An object of the present invention is to provide a composition for a model material capable of forming a hard three-dimensional model having excellent dimensional accuracy, surface hardness and abrasion resistance in order to have low curing shrinkage and excellent curability. The means for solving the problem is a composition for a model material used for modeling an optical model by the material jet stereolithography method, and is a monofunctional ethylenically unsaturated simple substance with respect to 100 parts by weight of the entire resin composition. A metric (A), 15 to 50 parts by weight of a bifunctional or higher polyfunctional ethylenically unsaturated monomer (B), 2 to 40 parts by weight of a (meth) acrylicized amine compound (C), and 5 A model material containing ~ 40 parts by weight of the oligomer (D), 3 to 15 parts by weight of the stereolithography initiator (E), and 0.005 to 3.0 parts by weight of the surface conditioner (F). Composition for use.

Description

The present invention is a material jet stereolithography used in a material jet stereolithography method, which is a combination of a composition for a model material used in the material jet stereolithography method and a composition for the model material and a composition for a water-soluble support material. For composition set.

A stereolithography method by a material jet (injection) method that forms a cured layer having a predetermined shape by ejecting a photocurable resin composition from a nozzle and immediately irradiating it with ultraviolet rays or the like to cure it (hereinafter, "" "Material jet stereolithography") is known. The material jet stereolithography method is attracting attention as a modeling method realized by a 3D printer capable of freely creating a three-dimensional model based on CAD (Computer Aided Design) data.

In the present specification, the material of the three-dimensional model is referred to as "model material". A three-dimensional model formed by the material jet stereolithography method is called a "stereolithography". In order to form a three-dimensional model that accurately corresponds to the shape designed by CAD or the like, the composition for the model material is smoothly ejected from the 3D printer to form droplets having an appropriate size and viscosity, and then ejected. It is required that the dimensions do not change after wearing.

Among the stereolithographic objects, hard ones may be used as industrial products or parts, and excellent physical properties such as dimensional accuracy, strength and abrasion resistance are required. Therefore, a composition for a model material for such an application is required to have excellent curability.

Patent Document 1 describes an active energy ray for an inkjet ink that has low viscosity even when the composition is solvent-free, has excellent ejection properties, is excellent in curability, and is excellent in adhesion, hardness, and scratch resistance of the cured product of the composition. Curable compositions are described. The active energy ray-curable composition for an inkjet ink of Patent Document 1 contains a (meth) acrylate mixture (A) containing glycerin tri (meth) acrylate as a main component. The curable composition of Patent Document 1 uses a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups to increase the number of cross-linking points in the curable composition and enhance its curability. Has been done.

However, when the number of cross-linking points in the curable composition is increased, shrinkage occurs when the contained resin is cured, and as a result, the stereolithography is warped or deformed, resulting in three-dimensional modeling corresponding to the shape designed by CAD or the like. Becomes difficult to obtain. Further, the curable composition containing the polyfunctional monomer tends to increase in viscosity, resulting in insufficient storage stability.

Patent Document 2 describes an ink composition for forming a clear layer, which has both adhesiveness and curability suitable for forming a clear layer of a thick film. The ink composition of Patent Document 2 contains an amine-modified reactive oligomer and a monofunctional (meth) acrylate. In the ink composition of Patent Document 2, the curability of the ink is enhanced by using an amine-modified reactive oligomer.

However, the ink composition of Patent Document 2 tends to shrink when a three-dimensional model is produced by an inkjet stereolithography method, and its dimensional stability during curing is insufficient. Further, the surface hardness and abrasion resistance are insufficient for a hard three-dimensional model used as an industrial product or a part.

JP-A-2017-39917 Japanese Unexamined Patent Publication No. 2014-37542

The present invention solves the above-mentioned conventional problems, and an object of the present invention is a hard three-dimensional model having excellent dimensional accuracy, surface hardness and abrasion resistance in order to have low curing shrinkage and excellent curability. The present invention is to provide a composition for a model material capable of forming the above. Another object of the present invention is to provide a material jet stereolithography composition set in which the model material composition and the support material composition are combined.

The present invention is a composition for a model material used for modeling an optical model by a material jet stereolithography method.
For 100 parts by weight of the entire resin composition
With the monofunctional ethylenically unsaturated monomer (A),
With 15 to 50 parts by weight of a bifunctional or higher polyfunctional ethylenically unsaturated monomer (B),
With 2 to 40 parts by weight of the (meth) acrylated amine compound (C),
With 10 to 40 parts by weight of oligomer (D),
With 1 to 15 parts by weight of the photopolymerization initiator (E),
0.005 to 3.0 parts by weight of the surface conditioner (F)
A composition for a model material to be contained is provided.

In one embodiment, the component (A) contains 19 to 49 parts by weight of the monofunctional ethylenically unsaturated monomer (A-2) with respect to 100 parts by weight of the entire resin composition.

In one form, the component (C) has a tertiary amino group in the molecule.

In one form, the component (C) has the same number of hydroxyl groups as the tertiary amino group in the molecule.

In one embodiment, the content of the component (B) is 20 to 45 parts by weight with respect to 100 parts by weight of the entire resin composition.

In one embodiment, the content of the component (C) is 5 to 30 parts by weight with respect to 100 parts by weight of the entire resin composition.

In one embodiment, the content of the component (E) is 2 to 13 parts by weight with respect to 100 parts by weight of the entire resin composition.

Further, the present invention is a material jet stereolithography composition set used in a material jet stereolithography method having any of the above-mentioned composition for a model material and a composition for a water-soluble support material.
The composition for a water-soluble support material provides a material jet stereolithography composition set containing a polyalkylene glycol, a water-soluble monofunctional ethylenically unsaturated monomer, and a photopolymerization initiator.

In one form, the polyalkylene glycol is a polyalkylene glycol having an oxybutylene group.

In one form, the composition for the water-soluble support material
The polyalkylene glycol containing the oxybutylene group is contained in an amount of 15 parts by weight or more and 75 parts by weight or less with respect to 100 parts by weight of the entire composition for a support material.

In one embodiment, the content of the water-soluble monofunctional ethylenically unsaturated monomer is 19 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the entire composition for the water-soluble support material. The content of the photopolymerization initiator is 1 part by weight or more and 20 parts by weight or less.

In one form, the composition for the water-soluble support material
Further contains a water-soluble organic solvent,
The content of the water-soluble organic solvent is 30 parts by weight or less with respect to 100 parts by weight of the entire composition for the water-soluble support material.

The present invention also provides an optical model including a model material obtained by photocuring any of the above-mentioned composition for a model material by a material jet stereolithography method.

Further, the present invention is a method for manufacturing the stereolithography by the material jet stereolithography method.
A model material is obtained by photo-curing any of the above-mentioned composition for a model material, and a water-soluble support material is obtained by photo-curing the composition for a water-soluble support material of any of the above-mentioned material jet stereolithography composition sets. Obtaining step (I) and
Step (II) of removing the water-soluble support material by contacting it with water, and
Provided is a method for manufacturing a stereolithography product.

According to the present invention, a composition for a model material and a material for jet stereolithography capable of forming a hard three-dimensional model having excellent dimensional accuracy, surface hardness and abrasion resistance because it is hard to shrink at the time of curing and has excellent curability. A composition set is provided.

It is a schematic side view which shows the state which the composition for a model material and the composition for a support material are discharged and irradiated with the energy ray in the manufacturing method of the stereolithography thing which concerns on this embodiment. It is a schematic side view which shows the state which discharges the composition for a model material and the composition for a support material in the manufacturing method of a stereolithography thing which concerns on this embodiment. It is a schematic side view which shows the state which irradiates the composition for a model material and the composition for a support material with energy rays in the manufacturing method of a stereolithography thing which concerns on this embodiment. It is a schematic side view of the stereolithography precursor (stereolithography) which consists of a support material and a model material. It is a schematic side view of a stereolithography product.

Hereinafter, one embodiment of the present invention (hereinafter, also referred to as the present embodiment) will be described in detail. The present invention is not limited to the following contents. In the present invention, "(meth) acrylate" is a general term for acrylate and methacrylate, and means one or both of acrylate and methacrylate. The same applies to "(meth) acryloyl" and "(meth) acrylic".

1. 1. Composition for model material The composition for model material according to the present embodiment contains at least the components (A) to (F) described below.

<Monofunctional ethylenically unsaturated monomer (A)>
The monofunctional ethylenically unsaturated monomer (A) is a component that polymerizes by light irradiation and cures the composition for a model material. The content of the component (A) is 19 to 49 parts by weight with respect to 100 parts by weight of the entire resin composition. When the content of the component (A) is less than 19 parts by weight, the photo-molded product obtained by photo-curing the composition for the model material has a large curing shrinkage. As a result, the dimensional accuracy of the stereolithography is deteriorated. On the other hand, when the content of the component (A) exceeds 49 parts by weight, the photo-molded product obtained by photo-curing the composition for a model material has insufficient curability. As a result, the dimensional accuracy of the stereolithography is deteriorated. The content of the component (A) is preferably 25 parts by weight or more, and preferably 47 parts by weight or less.

The component (A) is a polymerizable monomer having one ethylenic double bond in the molecule having a property of being cured by energy rays. Examples of the component (A) include linear or branched alkyl (meth) acrylates having 1 to 30 carbon atoms [for example, methyl (meth) acrylate, ethyl (meth) acrylate, isobutyl (meth) acrylate, and lauryl (meth). ) Acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, t-butyl (meth) acrylate, etc.],
Acrylate-containing (meth) acrylate having 6 to 20 carbon atoms [for example, cyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclo Pentenyl (meth) acrylicate, dicyclopentenyloxyethyl (meth) acrylicate, dicyclopentanyloxyethyl (meth) acrylicate, 3,5,5-trimethylcyclohexyl (meth) acrylate, adamantyl (meth) Acrylate, etc.],
Heterocyclic ring-containing (meth) acrylate having 5 to 20 carbon atoms [for example, tetrahydrofurfuryl (meth) acrylate, 4- (meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-( Meta) Acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, cyclic trimethylolpropanformal (meth) acrylate, etc.],
Aromatic ring-containing (meth) acrylate [for example, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxyethyl-3-funoxypropyl (meth) acrylate, ethoxylated phenylphenol (meth) acrylate, benzyl (meth) ) Acrylate, etc.],
Can be mentioned. These may be used alone or in combination of two or more. When two or more kinds of the component (A) are contained, the content is defined as the total content of each component (A).

The component (A) may contain 5 to 40 parts by weight of the water-soluble monofunctional ethylenically unsaturated monomer (A-2) with respect to 100 parts by weight of the entire resin composition. When the content of the component (A-2) is not more than the above upper limit value, swelling deformation of the model material (stereolithographic product) due to water or moisture absorption during or after photocuring can be suppressed.

Examples of the component (A-2) include hydroxyl group-containing (meth) acrylates having 5 to 15 carbon atoms [hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. ];
Alkylene oxide adduct-containing (meth) acrylate with number average molecular weight (Mn) of 200 to 1000 [polyethylene glycol mono (meth) acrylate, monoalkoxy (C1-4) polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate , Monoalkoxy (C1-4) polypropylene glycol mono (meth) acrylate and PEG-PPG block polymer mono (meth) acrylate, etc.];
C3-15 (meth) acrylamide derivatives [(meth) acrylamide, N-methyl (meth) acrylamide, N- (ethylmeth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N' -Dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, etc.];
N-vinyl compounds [N-vinylpyrrolidone, N-vinylcaprolactam, etc.]; and (meth) acryloylmorpholine, etc. can be used. The component (A-2) may be used alone or in combination of two or more.

Among these, isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate are preferable from the viewpoint of improving the curability of the composition for the model material. Further, the composition for a model material may be an isobornyl (meth) acrylate from the viewpoint of improving the dimensional accuracy of the stereolithographic object by having heat resistance that can withstand the temperature (50 to 90 ° C.) at the time of photocuring. More preferred.

<Difunctional or higher polyfunctional ethylenically unsaturated monomer (B)>
The composition for a model material of the present invention preferably contains a polyfunctional ethylenically unsaturated monomer (B) as a polymerizable compound. The polyfunctional ethylenically unsaturated monomer (B) is a component having a property of polymerizing and curing by irradiation with active energy rays, and is a polymerizable monomer having two or more ethylenically double bonds in the molecule. .. Only one type may be used as the polyfunctional ethylenically unsaturated monomer (B), or two or more types may be used in combination.

The content of the component (B) is 15 to 50 parts by weight with respect to 100 parts by weight of the entire resin composition. If the content of the component (B) is less than 15 parts by weight, the photo-molded product obtained by photo-curing the composition for the model material has insufficient curability. As a result, the dimensional accuracy of the stereolithography is deteriorated. On the other hand, when the content of the component (B) exceeds 50 parts by weight, the photo-molded product obtained by photo-curing the composition for the model material has a large curing shrinkage. As a result, the dimensional accuracy of the stereolithography is deteriorated. The content of the component (B) is preferably 20 parts by weight or more, and preferably 45 parts by weight or less.

The component (B) is, for example, a linear or branched alkylene glycol di (meth) acrylate or alkylene glycol tri (meth) acrylate, alkylene glycol tetra (meth) acrylate, or alkylene glycol penta (meth) having 10 to 25 carbon atoms. As acrylate and alkylene glycol hexa (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 -Nonandiol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 2-n butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 3-methyl-1,5- Pentandiol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (200) di (meth) acrylate, polyethylene glycol (400) di (Meta) acrylate, polyethylene glycol (600) di (meth) acrylate, polyethylene glycol (1000) di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol (400) Di (meth) acrylate, polypropylene glycol (700) di (meth) acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, trimethylol Propanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin propoxytri (meth) acrylate, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate As a cyclic structure-containing di (meth) acrylate having 10 to 30 carbon atoms such as pentaerythritol hexa (meth) acrylate or tri (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, dimethylol tricyclodecandi (meth) acrylate , Bisphenol A ethylene oxide adduct di (meth) acrylic Examples thereof include rate, bisphenol A propylene oxide adduct di (meth) acrylate, vinyl ether group-containing (meth) acrylic acid esters, and bifunctional or higher functional amino acrylates. Of these, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tripropylene glycol di (meth) acrylate are preferable.

Examples of vinyl ether group-containing (meth) acrylic acid esters include 2- (vinyloxyethoxy) ethyl (meth) acrylic acid.

Among these, from the viewpoint of improving the curability of the composition for the model material, a (meth) acrylate-based monomer is preferable, and dipropylene glycol di (meth) acrylate and tripropylene glycol di (meth) acrylate are preferable. , Glycerin propoxytri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate and bifunctional or higher functional amino acrylate are more preferable, and dipropylene glycol di (meth) acrylate. , Tripropylene glycol di (meth) acrylate, glycerin propoxytri (meth) acrylate and bifunctional or higher functional amino acrylates are more preferable, and dipropylene glycol diacrylate, tripropylene glycol diacrylate and bifunctional or higher functional amino acrylates are particularly preferable. preferable.

<(Meta) Acrylicated Amine Compound (C)>
The (meth) acrylated amine compound (C) can be rephrased as an amino (meth) acrylate compound. When the composition for a model material of the present invention contains a (meth) acrylicized amine compound, the composition for a model material is less likely to shrink during curing, and a hard three-dimensional model having excellent dimensional accuracy can be formed. Further, when the composition for a model material of the present invention contains a (meth) acrylicized amine compound, the polymerization inhibition that occurs in the presence of oxygen is alleviated, and the curability on the surface of the model agent is improved. As a result, a hard three-dimensional model having excellent surface hardness and abrasion resistance can be formed. Examples of amino acrylates include amino (meth) acrylate, amine-modified polyether (meth) acrylate, amine-modified polyester (meth) acrylate, amine-modified epoxy (meth) acrylate, and amine-modified urethane (meth) acrylate.

The (meth) acrylated amine compound is a compound having one or more amino groups and one or more (meth) acryloyl groups. The (meth) acryloyl group photopolymerizes with the ethylenically unsaturated monomer component, whereby the (meth) acrylicated amine compound is fixed to the resin skeleton of the stereolithography. As the (meth) acrylated amine compound, a (meth) acrylated amine compound obtained by reacting a polyfunctional (meth) acrylate with an amine compound is preferable.

Specific examples of the bifunctional (meth) acrylate include 1,6-hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 2,4-dimethyl. -1,5-Pentanediol di (meth) acrylate, butylethylpropanediol (meth) acrylate, ethoxylated cyclohexane methanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi ( Meta) acrylate, polypropylene glycol di (meth) acrylate, oligopropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 2-ethyl-2-butylpropanediol di (meth) acrylate, 1, Examples thereof include 9-nonandi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, and tricyclodecandi (meth) acrylate.

Specific examples of the trifunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, alkylene oxide-modified tri (meth) acrylate of trimethylolpropane, and pentaerythritol tri (meth) acrylate. , Dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, isocyanuric acid alkylene oxide-modified tri (meth) acrylate, dipentaerythritol tri (meth) acrylate propionate, tri ((meth) ) Acryloyloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylolpropane tri (meth) acrylate, sorbitol tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin triacrylate, etc. it can.

Specific examples of the tetrafunctional (meth) acrylate include pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate propionate, and penta ethoxylated. Examples thereof include erythritol tetra (meth) acrylate.

Specific examples of the pentafunctional (meth) acrylate include sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate.

Specific examples of the hexafunctional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, phosphazene alkylene oxide-modified hexa (meth) acrylate, and captolactone-modified dipentaerythritol hexa (meth) acrylate. And so on.

Further, the amine compound is not limited to the following, and for example, benzylamine, phenethylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, n-pentylamine, isopentylamine, n-hexylamine. , Cyclohexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine, 2, Monofunctional amine compounds such as −aminoethanol, 3-amino-1-propanol, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,6-hexamethylenediamine, 1,8-octamethylenediamine, 1,12-dodeca Methylenediamine, o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, o-xylylenediamine, p-xylylenediamine, m-xylylene diamine, mentandiamine, bis (4-amino-3-methylcyclohexylno) Polyfunctional amine compounds such as methane, isophoronediamine, 1,3-diaminocyclohexane, ethanoldiamine, and spiroacetal diamines can be mentioned, as well as high molecular weight types such as polyethyleneimine, polyvinylamine, and polyallylamine. Polyfunctional amine compounds may also be mentioned. As the monofunctional amine, it is preferable to have the same number of hydroxyl groups as the amino group in the molecule of 2-aminoethanol, 3-amino-1-propanol and the like, and polyfunctional (meth). The amine compound to be reacted with the acrylate is preferably a primary amine compound, and more preferably a primary amine compound having one hydroxyl group in the molecule.

The (meth) acrylated amine compound is not particularly limited, but is obtained, for example, by reacting a polyfunctional (meth) acrylate with a primary amine compound. The (meth) acrylated amine compound thus obtained has a tertiary amino group in the molecule. When 2-aminoethanol, 3-amino-1-propanol or the like is used as the amine compound, a (meth) acrylicated amine compound having the same number of hydroxyl groups as the tertiary amino group in the molecule can be obtained.

Among the above, the (meth) acrylicated amine compound preferably has a tertiary amino group in its molecule, particularly from the viewpoint of suppressing curing shrinkage of the composition for a model material, and has a tertiary amino group in the molecule. It is more preferable to have the same number of hydroxyl groups. It is preferable that 1 to 10 tertiary amino groups are present in the molecule, and 2 to 6 are preferably present. Commercially available products of (meth) acrylicated amine compounds having a tertiary amino group include, for example, "CN371" (trade name) manufactured by Sartmer, "EBECRYL 7100" (trade name) manufactured by Cytec, and "GC1100Z" manufactured by Qualipoli Chemical Corporation. "(Product name) and the like. The (meth) acrylated amine compound may be used alone or in combination of two or more.

The content of the (meth) acrylicated amine compound is 2 to 45 parts by weight, preferably 2 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the entire composition for the model material. If the content of the (meth) acrylated amine compound is less than 2 parts by weight with respect to 100 parts by weight of the entire composition for the model material, the curability of the composition for the model material is insufficient, and if it exceeds 45 parts by weight, The composition for the model material exceeds the viscosity range that imparts the suitability for inkjet, and the water solubility increases, and there is a risk of swelling and deformation when impregnated with water when the support material is removed.

<Oligomer (D)>
The oligomer (D) is a component that polymerizes by light irradiation to cure the composition for a model material and enhances the breaking strength of the model material obtained by the curing. The content of the component (D) is 5 to 40 parts by weight with respect to 100 parts by weight of the entire resin composition. When the content of the component (D) is less than 5 parts by weight, the curing shrinkage of the model material obtained by photocuring the composition for the model material becomes slightly large. As a result, the dimensional accuracy of the model material may deteriorate. In addition, the breaking strength of the model material obtained by photo-curing the composition for the model material is inferior. On the other hand, when the content of the component (D) exceeds 45 parts by weight, the viscosity of the composition for the model material becomes high. Therefore, when the composition for the model material is discharged from the inkjet head, the jetting characteristics may deteriorate and flight bending may occur. As a result, the dimensional accuracy of the model material obtained by photocuring the composition for the model material may deteriorate. The content of the component (D) is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, and preferably 30 parts by weight or less.

Examples of the component (D) include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and polyether (meth) acrylate oligomers. Among these, at least one selected from urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, and polyester (meth) acrylate oligomers from the viewpoint of improving the curability of the composition for model materials. Is preferable. Further, the composition for the model material is a urethane (meth) acrylate oligomer from the viewpoint of improving the dimensional accuracy of the model material by having heat resistance that can withstand the temperature (50 to 90 ° C.) at the time of photocuring. More preferred. These may be used alone or in combination of two or more. When two or more kinds of the component (D) are contained, the content is defined as the total content of each component (D).

In the present specification, the "oligomer" has a weight average molecular weight of 800 to 10,000. The weight average molecular weight means a polystyrene-equivalent weight average molecular weight measured by GPC (Gel Permeation Chromatography).

<Photopolymerization initiator (E)>
The composition for a model material of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that promotes a radical reaction when irradiated with light having a wavelength in the ultraviolet, near-ultraviolet, or visible light region. The photopolymerization initiator is not particularly limited as long as it can initiate polymerization with low energy, but is an acylphosphine oxide compound, an α-aminoalkylphenone compound, an α-hydroxyquinone compound, a thioxanthone compound, a benzoin compound, and an anthraquinone compound. And it is preferable to use a photopolymerization initiator containing at least one compound selected from the group consisting of Ketal compounds.

Specific examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide. , 2,3,5,6-Tetramethylbenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, 4-methylbenzoyldiphenylphosphine oxide, 4-ethylbenzoyldiphenylphosphine oxide, 4-isopropylbenzoyl Diphenylphosphine oxide, 1-methylcyclohexanoylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2 , 4,6-trimethylbenzoylphenylphosphinic acid isopropyl ester, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like. These may be used alone or in admixture. Examples of the acylphosphine oxide compound available on the market include "DAROCURE TPO" manufactured by BASF.

Specific examples of the α-aminoalkylphenone compound include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1. -(4-Molholinophenyl) butanone-1, 2-methyl-1- [4- (methoxythio) -phenyl] -2-morpholinopropan-2-one and the like can be mentioned. These may be used alone or in admixture. Examples of the α-aminoalkylphenone compound available on the market include "IRGACURE 369" and "IRGACURE 907" manufactured by BASF.

Specific examples of the α-hydroxyquinone compound include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-phenylpropan-1-one, and 2-hydroxy-1- {4- [4- [4- [4-]. (2-Hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy2-methyl- 1-Propane 1-on and the like can be mentioned. These may be used alone or in admixture. Examples of the α-hydroxyquinone compound available on the market include "IRGACURE 184", "DAROCURE 1173", "IRGACURE 2959", and "IRGACURE 127".

Specific examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4. -Diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like can be mentioned. These may be used alone or in admixture. Examples of the thioxanthone compound available on the market include "MKAYACURE DETX-S" manufactured by Nippon Kayaku Co., Ltd. and "Chivacure ITX" manufactured by Double Bond Chemical Co., Ltd.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether.

Specific examples of the anthraquinone compound include 2-ethylanthraquinone, 2-t-butyl anthraquinone, 2-chloroanthraquinone, and 2-amyl anthraquinone.

Specific examples of the ketal compound include acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.] and a benzophenone compound having 13 to 21 carbon atoms [eg, benzophenone, 4-benzoyl-4'-methyldiphenyl sulfate, 4,4. '-Bismethylaminobenzophenone and the like can be mentioned.

The content of the component (E) is 1 to 15 parts by weight with respect to 100 parts by weight of the entire resin composition. When the content of the component (E) is in the above range, the curability of the composition for the model material becomes good, and the dimensional accuracy of the stereolithographic object is improved. The content of the component (E) is preferably 2 parts by weight or more, and preferably 13 parts by weight or less. When two or more kinds of the component (E) are contained, the content is defined as the total content of each component (E).

<Surface conditioner (F)>
The surface conditioner (F) is contained in order to adjust the surface tension of the resin composition to an appropriate range. By adjusting the surface tension of the resin composition to an appropriate range, it is possible to prevent the composition for the model material and the composition for the support material from being mixed at the interface. As a result, stereolithography with good dimensional accuracy can be obtained by using these resin compositions. In order to obtain this effect, the content of the component (F) is 0.005 to 3.0 parts by weight with respect to 100 parts by weight of the entire resin composition.

Examples of the component (F) include silicone compounds and the like. Examples of the silicone-based compound include a silicone-based compound having a polydimethylsiloxane structure. Specific examples thereof include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, and polyaralkyl-modified polydimethylsiloxane. As these, the trade names are BYK-300, BYK-302, BYK-306, BYK-307, BYK-310, BYK-315, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-344, BYK-370, BYK-375, BYK-377, BYK-UV3500, BYK-UV3510, BYK-UV3570 (all manufactured by Big Chemie), TEGO-Rad2100 , TEGO-Rad2200N, TEGO-Rad2250, TEGO-Rad2300, TEGO-Rad2500, TEGO-Rad2600, TEGO-Rad2700 (all manufactured by Degusa), Granol 100, Granol 115, Granol 400, Granol 410, Granol 435, Granol 440, Granol 450, B-1484, Polyflow ATF-2, KL-600, UCR-L72, UCR-L93 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like may be used. Further, other than silicone compounds (for example, fluorine-based surface conditioners and nonionic surface conditioners) can also be used. These may be used alone or in combination of two or more. When two or more kinds of the component (E) are contained, the content is defined as the total content of each component (E).

<Preservation stabilizer (G)>
The composition for a model material according to the present embodiment preferably further contains a storage stabilizer (G). The storage stabilizer (G) can enhance the storage stability of the resin composition. In addition, it is possible to prevent head clogging caused by polymerization of the polymerizable compound by thermal energy. In order to obtain these effects, the content of the component (G) is preferably 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the entire resin composition.

Examples of the component (G) include hindered amine compounds (HALS), phenolic antioxidants, phosphorus-based antioxidants, nitrosamine-based compounds and the like. Specifically, hydroquinone, methquinone, benzoquinone, p-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monobutyl ether, TEMPO, 4-hydroxy-TEMPO, TEMPOL, cuperon Al, IRGASTAB UV-10, IRGASTAB UV-22, FIRSTCURE ST- 1 (manufactured by ALBEMARLLE), t-butylcatechol, pyrogallol, TINUVIN 111 FDL manufactured by BASF, TINUVIN 144, TINUVIN 292, TINUVIN XP40, TINUVIN XP60, TINUVIN 400 and the like. These may be used alone or in combination of two or more. When two or more types of the (G) component are contained, the above content is defined as the total content of each (G) component.

The composition for the model material may contain other additives, if necessary, as long as the effects of the present invention are not impaired. Examples of other additives include antioxidants, colorants, ultraviolet absorbers, light stabilizers, polymerization inhibitors, chain transfer agents, fillers and the like.

The composition for a model material according to the present embodiment is not particularly limited, but for example, the above-mentioned components (A) to (F), and if necessary, the above-mentioned (G) component and other additives can be added. It can be produced by uniformly mixing using a mixing stirrer, a disperser, or the like.

The composition for a model material according to the present embodiment produced in this manner preferably has a viscosity at 25 ° C. of 150 mPa · s or less, preferably 120 mPa · s, from the viewpoint of improving the ejection property from the inkjet head. It is more preferably s or less, and further preferably 100 mPa · s or less. The viscosity of the composition for the model material can be measured by using an R100 type viscometer in accordance with JIS Z 8803.

The surface tension of the composition for a model material of the present invention is preferably 24 to 30 mN / m, more preferably 24.5 mN / m or more, still more preferably 25 mN / m or more, and more preferably 29. It is 5 mN / m or less, more preferably 29 mN / m or less. When the surface tension is within the above range, droplets ejected from the nozzle can be normally formed even when the material jet is ejected at high speed, ensuring an appropriate droplet amount and landing accuracy, and generating satellites. It is possible to suppress it, and it becomes easy to improve the molding accuracy. The surface tension of the composition for the model material can be controlled by adjusting the type and content of the surface conditioner. The surface tension of the composition for the model material can be measured according to the Du Nouey method or the Wilhelmy method based on JIS K2241.

<Material Jet Stereolithography Composition Set>
The composition for a model material of the present invention is used alone in a stereolithography method such as a liquid tank stereolithography method in which a tank or the like is filled and light irradiation is performed to cure the composition to produce a three-dimensional model. Although it is possible, in the material jet stereolithography method, it can be used in combination with a support material for supporting a model material during three-dimensional modeling in order to form a complicated shape or a precise shape with high accuracy. Therefore, the present invention also covers a material jet stereolithography composition set including the composition for a model material of the present invention and a composition for a support material for modeling a support material by the material jet stereolithography method. To do.

2. 2. Composition for support material <Composition for support material>
The composition for a support material is a photocurable composition for a support material that gives the support material by photocuring. After the model material is created, it can be removed from the model material by physically peeling the support material from the model material or by dissolving the support material in an organic solvent or water. The composition for a model material of the present invention can be used in combination with various conventionally known compositions as a composition for a support material, but the model material is not damaged when the support material is removed, and the environment It is preferable that the composition for the support material constituting the stereolithography composition set of the present invention is water-soluble because the support material can be removed cleanly and easily in detail.

In the present invention, the composition for a water-soluble support material contains at least one water-soluble monofunctional ethylenically unsaturated monomer (a), at least one polyalkylene glycol (b), and a photopolymerization initiator. Is preferable.

Examples of the water-soluble monofunctional ethylenically unsaturated monomer contained in the composition for a support material of the present invention include a hydroxyl group-containing (meth) acrylate having 5 to 15 carbon atoms [for example, hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc.], hydroxyl group-containing (meth) acrylate with a number average molecular weight (Mn) of 200 to 1,000 [for example, polyethylene glycol mono (meth) acrylate, monoalkoxy (carbon) Numbers 1 to 4) Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, monoalkoxy (carbon number 1 to 4) polypropylene glycol mono (meth) acrylate, PEG-PPG block polymer mono (meth) acrylate, etc. ], (Meta) acrylamide derivatives [eg (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N, N' -Dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide, etc.], (Meta) Acryloylmorpholin and the like can be mentioned. These may be used alone or in combination of two or more.

The content of the water-soluble monofunctional ethylenically unsaturated monomer (a) contained in the support material composition is preferably 19 to 80 parts by mass with respect to 100 parts by mass of the support material composition. , More preferably 22 parts by mass or more, further preferably 25 parts by mass or more, more preferably 76 parts by mass or less, still more preferably 73 parts by mass or less. When the content of the water-soluble monofunctional ethylenically unsaturated monomer (a) is within the above range, the removability of the support material by water can be improved without lowering the support force of the support material.

The polyalkylene glycol (b) that can be contained in the composition for the support material may be either a linear type or a multi-chain type. Further, as long as it is soluble in water, it may contain an alkyl group at the terminal, and for example, it may preferably contain an alkyl chain having 6 or less carbon atoms. Specific examples of such a polyalkylene glycol (b) include polyalkylene glycol containing an oxybutylene group. These may be used alone or in combination of two or more.

The structure of the alkylene portion of the polyalkylene glycol (b) that can be contained in the composition for a support material is not particularly limited, and for example, a polybutylene glycol having only an oxybutylene group (oxytetramethylene group) may be used alone. It may be a polybutylene polyoxyalkylene glycol having both an oxybutylene group and another oxyalkylene group (for example, polybutylene polyethylene glycol). For example, the polybutylene glycol is represented by the following chemical formula (1), and the polybutylene polyethylene glycol is represented by the following chemical formula (2).

In the above chemical formula (2), m is preferably an integer of 5 to 300, and n is preferably an integer of 2 to 150. More preferably, m is 6 to 200 and n is 3 to 100. Further, the oxybutylene group in the chemical formula (1) and the chemical formula (2) may be linear or branched.
When the composition for the support material contains the polyalkylene glycol (b), the removability by water can be further improved without lowering the support force of the support material. These may be used alone or in combination of two or more.

The number average molecular weight (M _n ) of the polyalkylene glycol (b) is preferably 100 to 5000. When the number average molecular weight of the polyalkylene glycol (b) is within the above range, it is likely to be compatible with the water-soluble monofunctional ethylenically unsaturated monomer (a) in the composition before curing, but after light irradiation. It becomes difficult to be compatible with the cured product of the water-soluble monofunctional ethylenically unsaturated monomer, and the support material can be easily removed with water or a water-soluble solvent.

The content of the polyalkylene glycol (b) in the support material composition is preferably 15 to 75 parts by mass, more preferably 17 parts by mass or more, based on 100 parts by mass of the support material composition. It is more preferably 20 parts by mass or more, more preferably 72 parts by mass or less, and further preferably 70 parts by mass or less. When the content of the polyalkylene glycol (b) is within the above range, the removability of the support material by water or a water-soluble solvent can be improved without lowering the support power of the support material.

The composition for the support material may contain a water-soluble organic solvent (c). The water-soluble organic solvent (c) is a component that improves the solubility of the support material obtained by photocuring the composition for the support material in water. It also has a function of adjusting the composition for a support material to a low viscosity.

As the water-soluble organic solvent (c), it is preferable to use a glycol-based solvent. Specifically, for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate. Glycolester solvents such as acetate, tripropylene glycol monoacetate, tetraethylene glycol monoacetate, tetrapropylene glycol monoacetate, ethylene glycol diacetate, propylene glycol diacetate; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, triethylene glycol monomethyl Ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, ethylene glycol monopropyl ether, propylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, tetrapropylene glycol monobutyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, Glycol ether solvents such as ethylene glycol diethyl ether, propylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dibutyl ether, diethylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, propylene glycol Monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monobutyl ether acetate Examples thereof include glycol monoether acetate-based solvents such as. These may be used alone or in combination of two or more.

Among them, triethylene glycol monomethyl ether and diethylene glycol diethyl are examples of the water-soluble organic solvent (c) because it is easy to prepare a low-viscosity support material composition and the support material obtained by curing has excellent water solubility. Ether and dipropylene glycol monomethyl ether acetate are preferred.

The content of the water-soluble organic solvent (c) in the composition for the support material is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, based on 100 parts by mass of the composition for the support material. More preferably, it is 25 parts by mass or less. When the content of the water-soluble organic solvent (c) is within the above range, the removability of the support material by water or a water-soluble solvent can be improved without lowering the support force of the support material.

As the photopolymerization initiator, the compound described above can be similarly used as the photopolymerization initiator that can be contained in the composition for the model material. The content of the photopolymerization initiator in the composition for the support material is preferably 1 to 20 parts by mass, and more preferably 2 to 18 parts by mass with respect to 100 parts by mass of the composition for the support material. When the content of the photopolymerization initiator is within the above range, it is easy to sufficiently reduce the unreacted polymerization component and sufficiently improve the curability of the support material.

In one preferred embodiment of the present invention, the support material composition is based on 100 parts by mass of the support material composition.
19-80 parts by mass of water-soluble monofunctional ethylenically unsaturated monomer (a),
15-75 parts by mass of polyalkylene glycol (b),
Water-soluble organic solvent (c) of 30 parts by mass or less, and
It contains 1 to 20 parts by mass of a photopolymerization initiator. By including each of the above components in the above range, a composition for a support material having excellent water solubility and support ability can be obtained. In particular, since it has excellent support power, there is no concern that the support power will be reduced by taking in moisture in the air during molding, and a stereolithographic product with good dimensional accuracy can be obtained.

The composition for the support material may contain other additives, if necessary. Examples of other additives include surface conditioners, antioxidants, colorants, pigment dispersants, storage stabilizers, ultraviolet absorbers, light stabilizers, polymerization inhibitors, chain transfer agents, fillers and the like. ..

By blending a surface conditioner with the composition for the support material, the surface tension of the composition for the support material can be controlled within an appropriate range, and the composition for the model material and the composition for the support material are mixed at the interface. It can be suppressed. As a result, a stereolithographic object with good dimensional accuracy can be obtained. As the surface conditioner that can be contained in the composition for the support material, the same one as that exemplified as the surface conditioner that can be used in the composition for the model material of the present invention can be used, and the content thereof is the support material composition. It is preferably 0.005 to 3 parts by mass with respect to 100 parts by mass of the product.

Further, the storage stability can be improved by adding a storage stabilizer to the composition for the support material. As the storage stabilizer that can be contained in the composition for the support material, the same one as that exemplified as the storage stabilizer that can be used in the composition for the model material of the present invention can be used, and the content thereof is the support material composition. It is preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the product.

In the present invention, the viscosity of the composition for a support material is preferably 30 to 200 mPa · s at 25 ° C., more preferably 35 mPa · s or more, and further, from the viewpoint of improving the discharge property from the material jet nozzle. It is preferably 40 mPa · s or more, more preferably 170 mPa · s or less, and further preferably 150 mPa · s or less. The viscosity can be measured using an R100 type viscometer in accordance with JIS Z 8803.

In the present invention, the surface tension of the support material composition is preferably 24 to 30 mN / m, more preferably 24.5 to 29.5 mN / m, and even more preferably 25 to 29 mN / m. When the surface tension is within the above range, the droplets ejected from the nozzle can be formed normally, the appropriate droplet amount and landing accuracy can be ensured, and the generation of satellites can be suppressed. It becomes easy to secure high molding accuracy. The surface tension of the support material composition can be measured according to the same method as the method for measuring the surface tension of the model material composition.

The method for producing the composition for a support material of the present invention is not particularly limited, and for example, it can be produced by uniformly mixing the components constituting the composition for a support material using a mixing stirrer, a disperser, or the like. it can.

3. 3. Material Jet Stereolithography Composition Set The material jet stereolithography composition set of the present invention is provided by combining the model material composition of the present invention and the support material composition of the present invention. The material jet stereolithography composition set of the present invention is used for producing an optical model by photocuring a model material composition by a material jet stereolithography method. In the material jet stereolithography composition set of the present invention, the model material has excellent modeling accuracy, and the support material has excellent independence and removability, so that the dimensional accuracy of the stereolithography is not impaired, so that the three-dimensional modeling is excellent in accuracy. It is something that can provide things.

4. Stereolithography and its manufacturing method The method for manufacturing a stereolithography of this embodiment is a method of manufacturing a stereolithography using the material jet stereolithography composition set described in the above-described embodiment, and is a material jet (inkjet). ) Method After discharging the composition for the model material and the composition for the support material using a printer, the composition for the model material is photo-cured to obtain the model material, and the composition for the water-soluble support material is photo-cured. It includes a step of obtaining a water-soluble support material and a step of removing the water-soluble support material by bringing it into contact with water.

Since the method for producing a stereolithography of the present embodiment uses the above-mentioned material jet stereolithography composition set, it is possible to form a stereolithography with excellent molding accuracy.

Hereinafter, the method for manufacturing the stereolithography of the present embodiment will be described with reference to the drawings. FIG. 1 is a schematic side view showing a state in which a composition for a support material and a composition for a model material are discharged and irradiated with energy rays by a material jet modeling method. In FIG. 1, the three-dimensional modeling apparatus 10 includes an inkjet head module 11 and a modeling table 12. Further, the inkjet head module 11 includes an ink unit 11a for stereolithography, a roller 11b, and a light source 11c. Further, the stereolithography ink unit 11a includes a model material inkjet head 11aM filled with the model material ink 13 and a support material inkjet head 11aS filled with the support material ink 14.

The model material composition 13 is discharged from the model material inkjet head 11aM, the support material composition 14 is discharged from the support material inkjet head 11aS, and the energy rays 15 are emitted from the light source 11c and discharged. The model material composition 13 and the support material composition 14 are cured to form the model material 13PM and the support material 14PS. FIG. 1 shows a state in which the model material 13PM and the support material 14PS of the first layer are formed.

Next, the method for manufacturing the stereolithography of the present embodiment will be described in more detail based on the drawings. In the method for manufacturing a stereolithographic object of the present embodiment, first, as shown in FIG. 2, the inkjet head module 11 is scanned in the X direction (right direction in FIG. 2) with respect to the modeling table 12, and the inkjet for the model material is used. The model material composition 13 is discharged from the head 11aM, and the support material composition 14 is discharged from the support material inkjet head 11aS. As a result, the layer made of the model material precursor 13M and the layer made of the support material precursor 14S are arranged adjacent to each other on the modeling table 12 so that their interfaces are in contact with each other.

Next, as shown in FIG. 3, the inkjet head module 11 is scanned in the reverse X direction (left direction in FIG. 3) with respect to the modeling table 12, and the model material precursor 13M and the support material precursor 14S are used by the roller 11b. After smoothing the surface of the layer made of, the energy ray 15 is irradiated from the light source 11c to cure the layer made of the model material precursor 13M and the support material precursor 14S, and the first layer model material 13PM and the support material 14PS are cured. Form a layer consisting of.

Subsequently, the modeling table 12 is lowered by one layer in the Z direction, and the same steps as described above are performed to form a second layer of the model material and the support material. After that, by repeating the above steps, as shown in FIG. 4, the stereolithography precursor 16 composed of the model material 13PM and the support material 14PS is formed.

Finally, the stereolithography precursor 16 shown in FIG. 4 is brought into contact with water, for example, by immersing it in water to dissolve and remove the support material 14PS, and the stereolithography product 17 as shown in FIG. 7 is formed. Will be done.

In the method for manufacturing a stereolithographic object of the present embodiment, for example, a high-pressure mercury lamp, a metal halide lamp, a UV-LED, or the like can be used as a light source. UV-LED is preferable from the viewpoint that the three-dimensional modeling apparatus 10 can be miniaturized and the power consumption is low. The amount of light is preferably ^{200 to 500 mJ / cm 2} from the viewpoint of hardness and dimensional accuracy of the modeled product. When a UV-LED is used as a light source, it is preferable to use a UV-LED having a center wavelength of 385 to 415 nm because the light can easily reach deep layers and the hardness and dimensional accuracy of the stereolithographic product can be improved. Further, as the energy ray 15 emitted from the light source 11c, ultraviolet rays, near ultraviolet rays, visible rays, infrared rays, far infrared rays, electron beams, α rays, γ rays, X-rays and the like can be used, but the curing work is easy. And from the viewpoint of efficiency, ultraviolet rays or near-ultraviolet rays are preferable.

In the manufacturing method of the present invention, for example, based on the three-dimensional CAD data of the object to be manufactured, the data of the composition for the model material which is laminated by the material jet method to form the three-dimensional model, and the three-dimensional modeling in the process of production. Data on the composition for the support material that supports the object is created, and slice data for ejecting each composition is created using a material jet type 3D printer. Based on the prepared slice data, each for the model material and the support material. After discharging the composition, the stereolithography treatment is repeated layer by layer to prepare a stereolithographic product composed of a cured product (model material) of the composition for the model material and a cured product (support material) of the composition for the support material. it can.

The thickness of each layer constituting the three-dimensional model is preferably thin from the viewpoint of modeling accuracy, but is preferably 5 to 30 μm from the viewpoint of the balance with the modeling speed.

The obtained stereolithography is a combination of a model material and a support material. The support material is removed from the stereolithographic object to obtain a stereolithographic article as a model material. The support material can be removed, for example, by immersing the stereolithographic object obtained in a removal solvent that dissolves the support material, making the support material flexible, and then removing the support material from the surface of the model material with a brush or the like. preferable. Water, a water-soluble solvent, for example, a glycol-based solvent, an alcohol-based solvent, or the like may be used as the solvent for removing the support material. These may be used alone or in combination of two or more.

The stereolithographic product suppresses water absorption and swelling when it comes into contact with water, and is less likely to cause damage or deformation of the microstructure portion. In addition, the stereolithographic product has excellent water and oil repellency and is not easily contaminated.

Hereinafter, examples in which the present embodiment is disclosed more specifically will be shown. The present invention is not limited to these examples.

The stereolithographic product obtained by the above steps has a relatively high surface hardness in certain embodiments. For example, the stereolithographic product has a surface hardness of 50 or more, preferably 60 or more, more preferably 70 or more in shore-D hardness. The stereolithography product has high dimensional accuracy because water absorption and swelling are suppressed because the time required for contact with water when removing the support material is short.

Hereinafter, examples in which the present embodiment is disclosed more specifically will be shown. The present invention is not limited to these examples.

<Composition for model material>
(Manufacturing of composition for model material)
The components shown in Tables 1 to 5 are uniformly mixed in a predetermined amount using a mixing and stirring device, and the pigment is dispersed by a bead mill or the like using zirconia beads as necessary. Compositions for model materials 1 to 9 were produced. Hereinafter, in the table, Examples may be displayed as “Actual” and Comparative Examples may be displayed as “Ratio”. The details of the ingredients used are as follows.

MA-8: Acidic carbon black pigment [MA-8 (trade name), manufactured by Mitsubishi Chemical Corporation]
Yellow 4G01: Condensation azo pigment [NOVOPERM YELLOW 4G01 (trade name), manufactured by Clariant AG]
RT355D: Quinacridone pigment [CINQUASIA Magenda RT-355D (trade name), manufactured by Ciba)
P-BFS: Copper phthalocyanine pigment [HOSTAPERM BLUE P-BFS (trade name), manufactured by Clariant AG]
JR-806: Titanium oxide (rutile type, alumina-silica surface modification) [JR806 (trade name), manufactured by TAYCA CORPORATION]
Sol. 32000: Dispersant (comb-shaped copolymer having a basic functional group) [Solspurs 32000 (trade name), manufactured by Abyssia)
IBOA: Isobornyl acrylate (ethylene double bond / 1 molecule: 1) [SR506D (trade name), manufactured by Arkema)
TMCHA: trimethylcyclohexanol acrylate (ethylene double bond / 1 molecule: 1) [SR420NS (trade name), manufactured by Arkema]
TMPFA: Trimethylolpropane Formal Acrylate (Ethylene Double Bond / 1 Molecule: 1) [SR531NS (trade name), manufactured by Arkema]
PEA: Phenoxyethyl acrylate (ethylene double bond / 1 molecule: 1) [SR339NS (trade name), manufactured by Arkema]
HEAA: Hydroxyethyl acrylamide (ethylene double bond / 1 molecule: 1) [HEAA (trade name), manufactured by KJ Chemicals]
ACMO: Acryloyl morpholine (ethylene double bond / 1 molecule: 1) [ACMO (trade name), manufactured by KJ Chemicals]
DMAA: Dimethylacrylamide (ethylene double bond / 1 molecule: 1) [DMAA (trade name), manufactured by KJ Chemicals Co., Ltd.]
NVC: N-vinylcaprolactam HDDA: Hexanediol diacrylate (ethylene double bond / 1 molecule: 2) [SR238NS (trade name), manufactured by Arkema]
TPGDA: Tripropylene glycol diacrylate (ethylene double bond / 1 molecule: 2) [SR306 (trade name), manufactured by Arkema]
TEGDA: Trierylene glycol diacrylate (ethylene double bond / 1 molecule: 2) [SR272 (trade name), manufactured by Arkema]
PE-3A: Pentaerythritol triacrylate (ethylene double bond / 1 molecule: 3) [Light acrylate PE-3A (trade name), manufactured by Kyoeisha Chemical Co., Ltd.]
EBECRYL7100: Monomer having a tertiary amino group [EBECRYL7100 (trade name), manufactured by Daicel Ornex]
CN371: Monomer having a tertiary amino group (ethylene double bond / 1 molecule: 2) [CN371 (trade name), manufactured by Arkema)
Laromer PO9103: Monomer having a tertiary amino group (ethylene double bond / 1 molecule: 2) [Laromer PO9103 (trade name), manufactured by BASF]
GC1100Z: Monomer having a tertiary amino group (ethylene double bond / 1 molecule: 2) [GC1100Z (trade name), manufactured by Qualipoly Chem)
EBECRYL8402: Urethane acrylate oligomer (ethylene double bond / 1 molecule: 2) [EBECRYL8402 (trade name), manufactured by Daicel Ornex]
CN9911: Urethane acrylate oligomer (ethylene double bond / 1 molecule: 2) [CN991 (trade name), manufactured by Arkema)
EBECRYL600: Epoxy acrylate oligomer (ethylene double bond / 1 molecule: 2) [EBECRYL600 (trade name), Daicel Ornex]
CN2203: Polyester acrylate oligomer (ethylene double bond / 1 molecule: 2) [CN2203 (trade name), manufactured by Arkema)
DAROCURE TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [DAROCURE TPO (trade name), manufactured by BASF Ltd.]
IRGACURE 819: [IRGACURE 819 (trade name), manufactured by BASF]
DAROCURE 1173: [DAROCURE 1173 (trade name), manufactured by BASF]
TEGO-Rad2100: Silicon acrylate having a polydimethylsiloxane structure [TEGO-Rad2100 (trade name), manufactured by Evonik Degussa Japan Co., Ltd.]
H-TEMPO: 4-Hydroxy-2,2,6,6-Tetramethylpiperidin-N-Oxyl [HYDROXY-TEMPO (trade name), manufactured by Evonik Degussa Japan]

Then, the following evaluations were carried out using these composition for model materials. The evaluation results are shown in Tables 1-5.

(Measurement of viscosity)
The viscosity of each model material composition was measured using an R100 type viscometer (manufactured by Toki Sangyo Co., Ltd.) under the conditions of 25 ° C. and a cone rotation speed of 5 rpm, and evaluated according to the following criteria.

◯: Viscosity ≤ 100 mPa · s
X: Viscosity> 100 mPa · s

(Evaluation of curability)
First, the composition for each model material is printed on a film made of polyethylene terephthalate (A4300, manufactured by Toyobo Co., Ltd., 100 mm × 150 mm × thickness 188 μm) with a bar coater (# 4), and a thickness of 3 μm is printed. A film was formed. An ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) was used as an irradiation means on this printing film, and the printing film was cured by irradiating it with ultraviolet rays so that ^{the total irradiation light amount was 500 mJ / cm 2.} The printed film cured in this manner was touched with a finger, and the presence or absence of ink adhesion to the finger was visually inspected, and the curability was evaluated according to the following criteria. The evaluation was performed by rubbing the image with a finger from the image portion to the non-printed portion.

◯: The surface was smooth and there was no feeling of adhesion to the fingers.
Δ: The surface was slightly moist, and the feeling of adhesion to the fingers was sticky.
X: The surface was sticky, and a part of the uncured ink adhered to the finger.

(Creation of test piece)
Spacers with a thickness of 1 mm were arranged on the four sides of the upper surface of a glass plate (trade name "GLASS PLATE", manufactured by AS ONE Corporation, 200 mm x 200 mm x thickness 5 mm) and partitioned into a square of 10 cm x 10 cm. After casting the composition for each model material into the square, another glass plate was placed on top of each other. Then, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) was used as an irradiation means, and ultraviolet rays were irradiated and cured so that ^{the total irradiation light amount was 500 mJ / cm 2.} Then, the cured product was released from the glass plate and cut into a shape having a width of 5 mm and a length of 50 mm with a cutter to obtain a test piece. The performance of the test piece was evaluated by the following method. In addition, the evaluation result shows the average result of the result obtained by evaluating 5 test pieces.

(Evaluation of curing shrinkage)
First, the test pieces obtained from the compositions for each model material were immersed in the prepared 28% aqueous potassium iodide solution. At that time, the test piece was floating in the aqueous solution. Next, pure water was added to the aqueous solution until the test piece floated in the middle layer in the water bath. The specific gravity of the potassium iodide aqueous solution at this time was calculated and used as the specific gravity of the test piece. The specific gravity of each model material composition was measured with a density hydrometer DA-130 (manufactured by Kyoto Electronics Industry Co., Ltd.). The curing shrinkage was determined by the following formula (i) and evaluated according to the following criteria.

◯: Curing shrinkage ≤ 10%
Δ: 10% <curing shrinkage <13%
×: Curing shrinkage ≧ 13%

Curing shrinkage rate (%) = (specific gravity of test piece-specific gravity of composition for model material) / specific gravity of test piece ... (i)

(Measurement of glass transition point Tg)
The glass transition point Tg of the test piece obtained from the composition for each model material was measured using a thermogravimetric analyzer (TG-DTA2000S Thermo Plus EvoII DSC8230, manufactured by Rigaku Co., Ltd.). The measurement was carried out at a temperature rise temperature: 10 ° C./min and a measurement temperature range: −60 ° C. to 200 ° C.

(Evaluation of breaking strength)
Using an autograph (manufactured by Shimadzu Corporation), the test pieces obtained from the composition for each model material were pulled at a test speed of 50 mm / min, and the tensile breaking strength was measured according to JIS K7113 to obtain the breaking strength. .. The breaking strength was evaluated according to the following criteria.

◯: Breaking strength ≧ 30 MPa
X: Breaking strength <30 MPa

As can be seen from the results in Tables 1 to 5, the composition for the model material of Examples 1 to 31 satisfying all the requirements of the present invention had good curability, curing shrinkage, breaking strength and viscosity. On the other hand, the compositions for model materials of Comparative Examples 1 to 9 were inferior in curability, curing shrinkage, breaking strength or viscosity.

<Composition for support material>
Table 6 summarizes the components used in the support material composition in the following Examples and Comparative Examples.

(Examples 1 to 10 and Comparative Examples 1 to 8)
First, the support material compositions of Examples 1 to 10 were prepared as follows. That is, the components (A) to (G) shown in Table 7 were measured in a plastic bottle in the blending amount (unit: parts by mass) shown in Table 7, and these were mixed to prepare each support material composition. ..

Next, with respect to the support material compositions of Examples 1 to 10, the low temperature stability of the support material composition and the high temperature and high humidity condition stability of the cured support material obtained by curing the support material composition ( Supporting power) and water removability were evaluated.

<Low temperature stability of support material composition>
The stability of the support material composition at low temperature was evaluated. Each support material composition was placed in a glass bottle, and the glass bottle containing the support material composition was stored for 24 hours in a constant temperature bath set at a temperature of 10 ° C. Then, the state of the support material composition after storage was visually confirmed, and the low temperature stability of the support material composition was evaluated according to the following criteria.

When the support material composition remains liquid: low temperature stability A (excellent)
When the support material composition is partially solidified (solidified): Low temperature stability B (good)
When the support material composition is solidified (solidified): Low temperature stability C (poor)

<Supporting power of cured material>
A frame is formed on a glass plate with a frame-shaped silicon rubber having a length of 30 mm, a width of 30 mm, and a thickness of 5 mm, each support material composition is poured into the frame, and an ultraviolet ray having an ^{integrated light amount of 500 mJ / cm 2 is used by a metal halide lamp.} Was irradiated to prepare a cured support material. Subsequently, the cured product was placed in a glass petri dish, and the petri dish containing the cured product was left in a constant temperature bath at a temperature of 40 ° C. and a relative humidity of 90% for 2 hours. Then, the state of the cured product after being left to stand was visually confirmed, and the supporting power of the cured support material was evaluated according to the following criteria.

When no liquid substance is generated on the surface of the cured product and no softening of the cured product is confirmed: Supporting power A (excellent)
When a small amount of liquid matter is generated on the surface of the cured product and some softening of the cured product is confirmed: Support force B (good)
When a liquid substance is generated on the surface of the cured product and softening of the cured product is confirmed: Support force C (defective)

<Water removability of cured support material>
A cured support material was produced in the same manner as in the case of evaluating the supporting force of the cured support material. Next, the cured product was placed in a beaker filled with 50 mL of ion-exchanged water, treated with an ultrasonic cleaner while maintaining the water temperature at 25 ° C., and the time until the cured product was dissolved was measured. The water removability of the cured support material was evaluated based on the criteria.

When it takes 30 minutes for the cured product to completely dissolve: Water removability A (excellent)
When it took 1 hour for the cured product to completely dissolve: Water removability B (good)
When it takes 2 hours for the cured product to completely dissolve: Water removability C (poor)

The above results are shown in Table 8.

It can be seen that the support material compositions of Examples 1 to 10 obtained satisfactory results in all the evaluation items.

<Material Jet Stereolithography Composition Set>
Examples 1 to 8 were prepared by combining the composition for the model material and the composition for the support material as shown in Table 9.

Spacers with a thickness of 1 mm were arranged on the four sides of the upper surface of a glass plate (trade name "GLASS PLATE", manufactured by AS ONE Corporation, 200 mm x 200 mm x thickness 5 mm) and partitioned into a square of 10 cm x 10 cm. After casting the composition for the support material into the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as an irradiation means, and ultraviolet rays are irradiated so that ^{the total irradiation light amount is 500 mJ / cm 2.} And cured to obtain a support material.

Next, spacers having a thickness of 1 mm were arranged on the four sides of the upper surface of the support material, and the support material was divided into squares of 10 cm × 10 cm. After casting the composition for the model material into the square, an ultraviolet LED (NCCU001E, manufactured by Nichia Corporation) is used as an irradiation means, and ultraviolet rays are irradiated so that ^{the total irradiation light amount is 500 mJ / cm 2.} And cured to obtain a model material.

(Evaluation of adhesion)
In this state, the mixture was left in a constant temperature bath at 30 ° C. for 12 hours, and the state of adhesion between the model material and the support material was visually confirmed and evaluated according to the following criteria. The results are shown in Table 9.
◯: The model material and the support material were in close contact with each other.
Δ: The model material and the support material were in close contact with each other, but the interface between the model material and the support material was scratched with a nail and peeled off.
X: Peeling occurred at the interface between the model material and the support material, and the model material was peeled off so as to warp due to curing shrinkage of the model material.

As can be seen from the results in Table 9, Examples 1 to 8 in which both the composition for the model material and the composition for the support material satisfy the requirements of the present invention did not cause peeling at the interface between the model material and the support material. The model material and the support material were in close contact with each other. If the model material and the support material are in close contact with each other in this way, a stereolithographic product with good dimensional accuracy can be obtained.
for

The composition for model material and the composition set for material jet stereolithography of the present invention can provide a three-dimensional model having excellent dimensional accuracy, surface hardness and abrasion resistance by photocuring. Therefore, these resin compositions can be suitably used for producing a three-dimensional model by the material jet stereolithography method.

10 Three-dimensional modeling equipment 11 Ink unit for stereolithography 11a Ink unit for stereolithography 11a Ink head for model material 11aS Ink head for support material 11b Roller 11c Light source 12 Modeling table 13 Ink for model material 13M Model material precursor 13PM Model material 14 Support material Ink for 14S Support material precursor 14PS Support material 15 Energy ray 16 Stereolithography precursor (Stereolithography)
17 Stereolithography

Claims (14)

Material A composition for model materials used to model a stereolithography by the jet stereolithography method.
For 100 parts by weight of the entire resin composition
With the monofunctional ethylenically unsaturated monomer (A),
With 15 to 50 parts by weight of a bifunctional or higher polyfunctional ethylenically unsaturated monomer (B),
With 2 to 40 parts by weight of the (meth) acrylated amine compound (C),
With 5 to 40 parts by weight of oligomer (D),
With 1 to 15 parts by weight of the photopolymerization initiator (E),
0.005 to 3.0 parts by weight of the surface conditioner (F)
Composition for model material to be contained. The model material according to claim 1, wherein the component (A) contains 19 to 49 parts by weight of a monofunctional ethylenically unsaturated monomer (A-2) with respect to 100 parts by weight of the entire resin composition. Composition. The composition for a model material according to claim 1 or 2, wherein the component (C) has a tertiary amino group in the molecule. The composition for a model material according to any one of claims 1 to 3, wherein the component (C) has the same number of hydroxyl groups as the tertiary amino group in the molecule. The composition for a model material according to any one of claims 1 to 4, wherein the content of the component (B) is 20 to 45 parts by weight with respect to 100 parts by weight of the entire resin composition. The composition for a model material according to any one of claims 1 to 5, wherein the content of the component (C) is 5 to 30 parts by weight with respect to 100 parts by weight of the entire resin composition. The composition for a model material according to any one of claims 1 to 6, wherein the content of the component (E) is 2 to 13 parts by weight with respect to 100 parts by weight of the entire resin composition. A material jet stereolithography composition set used in a material jet stereolithography method having the model material composition and the water-soluble support material composition according to any one of claims 1 to 7.
A material jet stereolithography composition set in which the composition for a water-soluble support material contains a polyalkylene glycol, a water-soluble monofunctional ethylenically unsaturated monomer, and a photopolymerization initiator. The material jet stereolithography composition set according to claim 8, wherein the polyalkylene glycol is a polyalkylene glycol having an oxybutylene group. The composition for the water-soluble support material
The material jet stereolithography according to claim 8 or 9, which contains the polyalkylene glycol containing the oxybutylene group in an amount of 15 parts by weight or more and 75 parts by weight or less with respect to 100 parts by weight of the entire composition for a support material. Composition set. The content of the water-soluble monofunctional ethylenically unsaturated monomer is 19 parts by weight or more and 80 parts by weight or less with respect to 100 parts by weight of the entire composition for the water-soluble support material, and the content of the photopolymerization initiator is contained. The material jet stereolithography composition set according to any one of claims 8 to 10, wherein the amount is 1 part by weight or more and 20 parts by weight or less. The composition for the water-soluble support material
Further contains a water-soluble organic solvent,
The material jet stereolithography according to any one of claims 8 to 11, wherein the content of the water-soluble organic solvent is 30 parts by weight or less with respect to 100 parts by weight of the entire composition for the water-soluble support material. Composition set. A photo-modeled product containing a model material obtained by photo-curing the composition for a model material according to any one of claims 1 to 7 by a material jet stereolithography method. The method for producing a stereolithography according to claim 13 by the material jet stereolithography method.
The composition for model material according to any one of claims 1 to 7 is photocured to obtain a model material, and the material jet stereolithography composition set according to any one of claims 8 to 12 is obtained. Step (I) of obtaining a water-soluble support material by photo-curing the composition for the water-soluble support material of
Step (II) of removing the water-soluble support material by contacting it with water, and
A method for manufacturing a stereolithography product.

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