# US 11,111,401 B2 · Light curing molding ink set, and method for manufacturing light cured article

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- Number: US 11,111,401 B2
- Document ID: US11111401B2
- Status: Granted
- Kind: B2
- Application number: 15/759,796
- Filed: 2016-09-15
- Published: 2018-09-20
- Granted: 2021-09-07
- Earliest claimed: 2015-09-15
- Assignees: Maxell Holdings, Ltd.; Mimaki Engineering Co., Ltd.
- Applicants: Maxell Holdings, Ltd.; Mimaki Engineering Co., Ltd.
- Inventors: Katsuyuki Kitou; Taeko Izumo; Masakatsu Okawa; Kenta Hongo
- Web page: https://patentgrep.com/patent/US11111401B2

## CPC

- C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
- B29C 64/112: using individual droplets, e.g. from jetting heads
- B29C 64/40: Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
- B29C 67/00: Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B33Y 10/00: Processes of additive manufacturing
- B33Y 70/00: Materials specially adapted for additive manufacturing
- B41M 5/00: Duplicating or marking methods; Sheet materials for use therein (by using light-sensitive materials G03; electrography, magnetography G03G {; repeatedly usable boards or tablets for writing or drawing B43L1/00})
- C09D 11/107: from unsaturated acids or derivatives thereof
- C09D 11/30: Inkjet printing inks
- C09D 11/322: Pigment inks
- C09D 11/38: characterised by non-macromolecular additives other than solvents, pigments or dyes
- C09D 11/40: Ink-sets specially adapted for multi-colour inkjet printing
- B29K 2033/08: {Polymers of acrylic acid esters, e.g. PMA, i.e. polymethylacrylate}
- B29K 2071/02: {Polyalkylene oxides, e.g. PEO, i.e. polyethylene oxide, or derivatives thereof}
- B29K 2071/12: {PPO, i.e. polyphenylene oxide; PPE, i.e. polyphenylene ether}
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B41M: PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING, (correction of typographical errors B41J; processes for applying transfer pictures or the like B44C1/16; fluid media for correction of typographical errors by coating C09D10/00; printing textiles D06P)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

There is provided a light curing molding ink set used for a manufacturing method for light curing molding using an ink-jet scheme, comprising a combination of a resin composition for a modeling material used for shaping the modeling material and a resin composition for a supporting material used for shaping the supporting material, wherein surface tension Mt (mN/m) of the resin composition for a modeling material is greater than surface tension St (mN/m) of the resin composition for a supporting material, and the surface tension Mt and the surface tension St satisfy the [0<Mt −St<5] expression, and this light curing molding ink set can afford a light cured article having the good dimensional accuracy.

## Claims

### Claim 1

A light curing molding ink set used for a manufacturing method for light curing molding using an ink-jet scheme, comprising a combination of a resin composition for a modeling material used for shaping the modeling material and a resin composition for a supporting material used for shaping the supporting material,
wherein surface tension Mt (mN/m) of the resin composition for a modeling material is greater than surface tension St (mN/m) of the resin composition for a supporting material, and the surface tension Mt and the surface tension St satisfy the following (i) expression:
0<Mt−St<5 (i).

### Claim 2 (depends on 1)

The light curing molding ink set according to claim 1, wherein the surface tension Mt is 26.0 to 33.3 mN/m.

### Claim 3 (depends on 1)

The light curing molding ink set according to claim 1, wherein the resin composition for a modeling material contains a water-insoluble monofunctional ethylenic unsaturated monomer (A), a di- or more-functional polyfunctional ethylenic unsaturated monomer (B), a photopolymerization initiator (C), and a surface adjusting agent (D).

### Claim 4 (depends on 3)

The light curing molding ink set according to claim 3, wherein a content of the water-insoluble monofunctional ethylenic unsaturated monomer (A) is 19 to 49 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material.

### Claim 5 (depends on 3)

The light curing molding ink set according to claim 3, wherein a content of the di- or more-functional polyfunctional ethylenic unsaturated monomer (B) is 15 to 60 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material.

### Claim 6 (depends on 3)

The light curing molding ink set according to claim 3, wherein a content of the water-insoluble monofunctional ethylenic unsaturated monomer (A) is 19 to 49 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material, and a content of the di- or more-functional polyfunctional ethylenic unsaturated monomer (B) is 15 to 60 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material.

### Claim 7 (depends on 3)

The light curing molding ink set according to claim 3, wherein the resin composition for a modeling material further contains an oligomer.

### Claim 8 (depends on 7)

The light curing molding ink set according to claim 7, wherein a content of the oligomer is 10 to 45 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material.

### Claim 9 (depends on 1)

The light curing molding ink set according to claim 1, wherein the surface tension St is 24.0 to 33.0 mN/m.

### Claim 10 (depends on 1)

The light curing molding ink set according to claim 1, wherein the resin composition for a supporting material contains a water-soluble monofunctional ethylenic unsaturated monomer (E), polyalkylene glycol comprising an oxyethylene group and/or an oxypropylene group (F), a photopolymerization initiator (C), and a surface adjusting agent (D).

### Claim 11 (depends on 10)

The light curing molding ink set according to claim 10, wherein a content of the water-soluble monofunctional ethylenic unsaturated monomer (E) is 20 to 50 parts by weight, based on 100 parts by weight of the whole resin composition for a supporting material.

### Claim 12 (depends on 10)

The light curing molding ink set according to claim 10, wherein a content of the oxyethylene group and/or an oxypropylene group (F) is 20 to 49 parts by weight, based on 100 parts by weight of the whole resin composition for a supporting material.

### Claim 13 (depends on 10)

The light curing molding ink set according to claim 10, wherein a content of the water-soluble monofunctional ethylenic unsaturated monomer (E) is 20 to 50 parts by weight, based on 100 parts by weight of the whole resin composition for a supporting material, and a content of the oxyethylene group and/or an oxypropylene group (F) is 20 to 49 parts by weight, based on 100 parts by weight of the whole resin composition for a supporting material.

### Claim 14 (depends on 10)

The light curing molding ink set according to claim 10, wherein a number average molecular weight Mn of the oxyethylene group and/or an oxypropylene group (F) is 100 to 5,000.

### Claim 15 (depends on 1)

A method for manufacturing a light cured article using the light curing molding ink set as defined in claim 1 by a manufacturing method for light curing molding using an ink-jet scheme, comprising:
a step (I) of discharging a resin composition for a modeling material and a resin composition for a supporting material from an ink-jet head, so that a resin composition layer in which a layer composed of the resin composition for a modeling material and a layer composed of the resin composition for a supporting material are arranged contiguously,
a step (II) of photocuring the resin composition for a modeling material and the resin composition for a supporting material constituting the resin composition layer, respectively, thereby, obtaining a modeling material and a supporting material, and
a step (III) of removing the supporting material, thereby, obtaining a light cured article.