# US 7,611,817 B2 · Aromatic sulfonium salt compound, photo-acid generator comprising the same and photopolymerizable composition containing the same, resin composition for optical three-dimensional shaping, and method of optically forming three-dimensional shape

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- Number: US 7,611,817 B2
- Document ID: US7611817B2
- Status: Granted
- Kind: B2
- Application number: 10/529,015
- Filed: 2003-09-25
- Published: 2006-03-16
- Granted: 2009-11-03
- Earliest claimed: 2002-09-25
- Assignees: Adeka Corporation
- Inventors: Tetsuyuki Nakayashiki; Hiroyuki Tachikawa
- Web page: https://patentgrep.com/patent/US7611817B2

## CPC

- B41C 1/003: {the relief or intaglio pattern being obtained by imagewise deposition of a liquid, e.g. by an ink jet}
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C07D 333/76: Dibenzothiophenes
- C08G 59/687: {containing sulfur}
- 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
- G03F 7/0037: {Production of three-dimensional images}
- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/029: Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021)
- B41M 3/16: Braille printing (typewriters or selective printing mechanisms for Braille printing B41J3/32)
- B41M 5/0023: {Digital printing methods characterised by the inks used (inks per se C09D11/00)}
- C08K 5/378: containing heterocyclic rings
- Y10S 430/106: Binder containing
- Y10S 430/114: Initiator containing
- Y10S 430/115: Cationic or anionic
- B41C: PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES (photomechanical processes for producing printing surfaces G03F; photoelectrical processes for producing printing surfaces G03G)
- 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
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- 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)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

Novel aromatic sulfonium salt compounds of general formula (I), photo-acid generators comprising the same, and photo-polymerizable compositions containing the same, capable of providing stereolithographic resin compositions which do not suffer from the hindrance to curing by oxygen, can easily give shaped articles having desired sizes by virtue of the high accuracy thereof in curing, can attain a satisfactory curing depth owing to the high sensitivity thereof for radiant energy and can be employed for wide usage, such as photoresist and ink for foods-packing medium, since the release of benzene is suppressed; and a stereolithographic process, using said stereolithographic resin composition.

## Claims

### Claim 1

An aromatic sulfonium salt compound expressed by a general formula (I),
wherein, R1 to R17 are identical or different and are a group selected from the group consisting of hydrogen, halogen, nitro, hydroxyl, alkyl, alkoxy, acyl, phenoxy, ester, aryl, thioether, thiocarbonyl, sulfinyl, sulfonyl, amino, amide, imide, nitrile, phosphino, phospho, phosphoryl and fluoroalkyl groups of 1-8 carbon atoms,
wherein the moieties other than the functional groups of these groups can be saturated aliphatic hydrocarbon, unsaturated aliphatic hydrocarbon, alicyclic hydrocarbon, carbocyclic aromatic hydrocarbon or heterocyclic aromatic hydrocarbon of 1-12 carbon atoms, and R5 and R6 can be condensed together with to form a covalent bond, provided that R1 to R5 are not all hydrogen at the same time, and that R6 to R10 are not all hydrogen at the same time, X is the same described above, and
wherein at least one of R1 to R17 is acyl group having of the formula R—CO— or Ar—CO—, where
Ar is
and R is straight or branched alkyl group, or alicyclic hydrocarbon group, and R18 to R63 are identical or different, respectively hydrogen. halogen, hydroxyl, alkyl or alkoxy.

### Claim 2 (depends on 1)

A photo-acid generator comprising an aromatic sulfonium salt compound of claim 1.

### Claim 3 (depends on 2)

A photo-polymerizable composition comprising (1) cationically polymerizing organic substances and (2) of claim 2 as an energy beam sensitive cationically polymerizing initiator, as essential components.

### Claim 4 (depends on 1)

An ultraviolet curing ink composition which comprises the photo-polymerizable composition of claim 1.

### Claim 5 (depends on 1)

An ultraviolet curing ink composition for wrapping material of foods which comprises the photo-polymerizable composition of claim 1.

### Claim 6 (depends on 1)

An wrapping material of foods printed by the ultraviolet curing ink composition or the ultraviolet curing ink composition for wrapping material of foods of claim 1.

### Claim 7 (depends on 3)

The photo-polymerizable composition of claim 3, which additionally comprises (3) radically polymerizing organic substance and (4) energy beam sensitive radical polymerizing initiator, as essential components.

### Claim 8 (depends on 3)

The photo-polymerizable composition of claim 3, wherein at least one among the (1) cationically polymerizing organic substance is an organic compound having one or more epoxy group in a molecule.

### Claim 9 (depends on 3)

The photo-polymerizable composition of claim 3, which comprises a compound having a cyclohexenoxide structure in a molecule at the content of 30% by weight or more based on the (1) cationically polymerizing organic substance.

### Claim 10 (depends on 7)

The photo-polymerizable composition of claim 7, which comprises a compound having (meth)acrylic group in a molecule at the content of 50% by weight or more based on the (3) radically polymerizing organic substance.