PHOTOCURABLE COMPOSITION FOR SUPPORT MATERIALS FOR INKJET 3D PRINTERS, INK, CARTRIDGE, METHOD FOR PRODUCING SUPPORT MATERIAL, AND METHOD FOR PRODUCING OPTICALLY SHAPED ARTICLE

Abstract

In the present invention, a photocurable composition for a support material for an inkjet 3D printer comprises a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion, and a water content is not more than 10 mass % in 100 mass % of the photocurable composition for a support material. It is preferably that the photocurable composition for a support material for an inkjet 3D printer further comprises a photopolymerization initiator.

Claims

1. A photocurable composition for a support material for an inkjet 3D printer comprising a water-soluble ethylenically unsaturated monomer containing an ionic group and a counter ion, wherein a water content is not more than 10 mass % in 100 mass % of said photocurable composition for a support material.

2. The photocurable composition for a support material for an inkjet 3D printer of claim 1, further comprising a photopolymerization initiator.

3. An ink for an inkjet 3D printer, the ink comprising the photocurable composition for a support material for an inkjet 3D printer of claim 1.

4. A cartridge for an inkjet 3D printer, the cartridge filled with the ink for an inkjet 3D printer of claim 3.

5. A method for producing a support material, wherein said support material is formed by using the photocurable composition for a support material for an inkjet 3D printer of claim 1.

6. A method for producing an optically shaped article by using the photocurable composition for a support material for an inkjet 3D printer of claim 1, the method comprising: a step for forming a support material by using said photocurable composition for a support material for an inkjet 3D printer or said ink for an inkjet 3D printer; a step for forming a model material; and a step for removing said support material.

7. A method for producing a support material, wherein said support material is formed by using the photocurable composition for a support material for an inkjet 3D printer of claim 2.

8. A method for producing a support material, wherein said support material is formed by using the ink for an inkjet 3D printer of claim 3.

9. A method for producing an optically shaped article by using the photocurable composition for a support material for an inkjet 3D printer of claim 2, the method comprising: a step for forming a support material by using said photocurable composition for a support material for an inkjet 3D printer or said ink for an inkjet 3D printer; a step for forming a model material; and a step for removing said support material.

10. A method for producing an optically shaped article by using the ink for an inkjet 3D printer of claim 3, the method comprising: a step for forming a support material by using said photocurable composition for a support material for an inkjet 3D printer or said ink for an inkjet 3D printer; a step for forming a model material; and a step for removing said support material.

Description

EXAMPLES

[0107] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples, and of course, it can be changed within a range that can conform to the gist of the foregoing and the following. All of them are included in the technical scope of the present invention.

Example 1

[0108] To 7 parts by mass of water and 23 parts by mass of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.), 35 parts by mass of potassium acrylate (manufactured by Nippon Shokubai Co., Ltd.) as the water-soluble ethylenically unsaturated monomer, 10 parts by mass of lactic acid (manufactured by Wako Pure Chemical Industries, Ltd.), 25 parts by mass of polyethylene glycol (PEG200, manufactured by Wako Pure Chemical Industries, Ltd.), and 0.3 parts by mass of Irgacure 2959 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator were added and mixed by stirring, to obtain a composition for a support material.

Examples 2 to 16 and Comparative Examples 1 to 4

[0109] In each of Examples 2 to 16 and Comparative Examples 1 to 4, a composition for a support material was obtained in the same manner of Example 1 except that the compounds and quantities (parts by mass) were changed as shown in the following Tables 1 and 2. In Tables 1 and 2, sodium acrylate, zinc acrylate and calcium acrylate manufactured by Nippon Shokubai Co., Ltd., DMAPAA-Q (dimethylaminopropylacrylamide methyl chloride quaternary salt) manufactured by KJ Chemicals Co., Ltd. , ACMO (acryloylmorpholine) manufactured by Tokyo Chemical Industry Co., Ltd., HEAA (hydroxyethyl acrylamide) manufactured by Tokyo Chemical Industry Co., Ltd., AA (acrylic acid) manufactured by Nippon Shokubai Co., Ltd., SFT70 (C12-C14 straight chain EO 7 mole adduct to secondary alcohol) manufactured by Nippon Shokubai Co., Ltd., diethylene glycol, triethylene glycol and propylene glycol manufactured by Nippon Shokubai Co., Ltd., ethylene glycol monomethyl ether manufactured by Wako Pure Chemical Industries, Ltd., dipropylene glycol manufactured by Wako Pure Chemical Industries, Ltd., glycerol manufactured by Wako Pure Chemical Industries, Ltd., PPG400 manufactured by Wako Pure Chemical Industries, Ltd., PEG600 (polyethylene glycol) manufactured by Wako Pure Chemical Industries, Ltd., Irgacure 184 manufactured by BASF Japan Ltd., and Lucirin TPO manufactured by BASF Japan Ltd. were used as commercially available products.

[0110] The compositions for support materials obtained in Examples 1 to 16 and Comparative Examples 1 to 4 were evaluated by the following evaluation methods.

[0111] (i) Appearance Evaluation

[0112] The compositions for support materials obtained in Examples 1 to 16 and Comparative Examples 1 to 4 were respectively placed in a transparent glass container having a diameter of 20 mm, and the appearance was visually evaluated. The evaluation criteria were as follows. The results are shown in Tables 1 and 2.

[0113] A: Uniform and Transparent

[0114] B: Uniform

[0115] C: Separation

[0116] (ii) Odor Evaluation

[0117] Odor of the compositions for support materials obtained in Examples 1 to 16 and Comparative Examples 1 to 4 were evaluated. The evaluation criteria were as follows. The results are shown in Tables 1 and 2.

[0118] A: No irritating odor by monomers was observed.

[0119] B: Slightly irritating odor by monomers was observed.

[0120] C: Strong irritating odor by monomers was observed.

[0121] (iii) Curability Evaluation

[0122] The compositions for support materials obtained in Examples 1 to 16 and Comparative Examples 1 to 4 were irradiated with a light of 250 mJ/cm.sup.2, 500 mJ/cm.sup.2 or 1000 mJ/cm.sup.2 to evaluate curability. The evaluation criteria were as follows. The results are shown in Tables 1 and 2.

[0123] A: The composition was cured with a light of 250 mJ/cm.sup.2.

[0124] B: The composition was cured with a light of 500 mJ/cm.sup.2.

[0125] C: The composition was cured with a light of 1000 mJ/cm.sup.2.

[0126] D: The composition was not cured with a light of 1000 mJ/cm.sup.2, and remained in a liquid state.

[0127] (iv) Solubility Evaluation

[0128] A piece (110.5 cm) of the cured product, which was cured in (iii) Curability Evaluation, of each of the compositions for support materials of Examples 1 to 16 and Comparative Examples 1, 2 and 4 was placed on a wire net, and placed in water having a water temperature of 25 C. and volume of 100 mL to evaluate solubility. The evaluation criteria were as follows. The results are shown in Tables 1 and 2.

[0129] A: The composition was dissolved in the water within 1 hour.

[0130] B: The composition was dissolved in the water within 1 hour and a half.

[0131] C: The composition was dissolved within 2 hours.

[0132] D: The composition was not dissolved within 2 hours.

[0133] (v) Supportability Evaluation

[0134] Hardness of the cured product, which was cured in (iii) Curability Evaluation, of each of the compositions for support materials (when the UV irradiation amount was 500 mJ/cm.sup.2) of Examples 1 to 16 and Comparative Examples 1, 2 and 4 was measured with Durometer E type (manufactured by Kobunshi Keiki Co., Ltd.) and evaluated. The evaluation criteria were as follows. The results are shown in Tables 1 and 2.

[0135] A: not less than 40

[0136] B: not less than 30 and less than 40

[0137] C: not less than 20 and less than 30

[0138] D: not less than 10 and less than 20

[0139] E: less than 10 (unmeasurable)

TABLE-US-00001 TABLE 1 Examples 1 2 3 4 5 6 7 8 9 10 Ionic potassium acrylate 35 25 31 25 15 12 15 10 15 17 Monomers sodium acrylate 5 zinc acrylate 5 5 4 8 5 calcium acrylate 3 DMAPAA-Q Non-Ionic ACMO Monomers HEAA AA Others lactic acid 10 10 10 10 6 SFT70 5 Solvents water 7 7 1 3 9 8 ethylene glycol 23 38 13 14 diethylene glycol 38 47 80 75 40 60 60 triethylene glycol 3 propylene glycol 75 ethylene glycol 35 monomethyl ether dipropylene glycol glycerol 5 PEG200 25 20 15 10 PPG400 PEG600 photopolymer- Irgacure 184 0.3 0.5 ization LucirinTPO 0.3 0.3 0.3 0.5 initiators Irgacure2959 0.3 0.3 0.3 0.3 Appearance A A A A A A A A B A Odor of Ink A A A A A A A A A A Curability A A A B A A A A B A Solubility A A A A A A B C B A Supportability C A A A A B B A B D

TABLE-US-00002 TABLE 2 Examples Comparative Examples 11 12 13 14 15 16 1 2 3 4 Ionic potassium acrylate 31 15 12 13 12 15 35 25 Monomers sodium acrylate zinc acrylate 5 7 5 6 8 calcium acrylate DMAPAA-Q 15 Non-Ionic ACMO 40 40 Monomers HEAA 10 AA 10 Others lactic acid 10 10 10 SFT70 Solvents water 10 5 9 15 13 ethylene glycol 39 15 30 diethylene glycol 71 47 28 38 triethylene glycol propylene glycol 75 ethylene glycol monomethyl ether dipropylene glycol 77 glycerol 5 40 PEG200 20 25 14 20 15 PPG400 35 PEG600 20 photopolymer- Irgacure 184 0.8 0.05 ization LucirinTPO 0.4 0.3 0.3 1 initiators Irgacure2959 0.3 0.3 0.3 0.5 Appearance A A A A A A A A A A Odor of Ink B A A A A A A A C C Curability A A B B A B C C D C Solubility B B A B C A A A C Supportability B B A A A A E E D

[0140] In all of the compositions for support materials of Examples 1 to16, a content of the water was not more than 10 mass % with Karl Fischer titration measurement. As shown in Tables 1 and 2, the compositions for support materials, having the water content of not more than 10 mass %, had excellent curability and sufficient hardness of the cured product, and had excellent solubility in the solvent after curing.

INDUSTRIAL APPLICABILITY

[0141] According to the present invention, the photocurable composition for support materials for inkjet 3D printers, having excellent curability and sufficient hardness of the cured product, and having excellent solubility in the solvent after curing, the ink and cartridge containing thereof, the method for producing the support materials, and the method for producing optically shaped articles using the support materials, can be provided.