US20190233670A1 - Ultraviolet curable silicone composition and cured product of same - Google Patents

Ultraviolet curable silicone composition and cured product of same Download PDF

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US20190233670A1
US20190233670A1 US16/311,209 US201716311209A US2019233670A1 US 20190233670 A1 US20190233670 A1 US 20190233670A1 US 201716311209 A US201716311209 A US 201716311209A US 2019233670 A1 US2019233670 A1 US 2019233670A1
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ultraviolet curable
curable silicone
silicone composition
component
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Nobuaki Matsumoto
Taichi KITAGAWA
Atsushi Yaginuma
Masaaki Shirota
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Shin Etsu Chemical Co Ltd
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Assigned to SHIN-ETSU CHEMICAL CO., LTD. reassignment SHIN-ETSU CHEMICAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KITAGAWA, Taichi, MATSUMOTO, NOBUAKI, SHIROTA, MASAAKI, YAGINUMA, ATSUSHI
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • 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
    • B29C64/00—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
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/14—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers obtained by ring-opening polymerisation of carbocyclic compounds having one or more carbon-to-carbon double bonds in the carbocyclic ring, i.e. polyalkeneamers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

  • the present invention relates to an ultraviolet curable silicone composition capable of being ejected via inkjet ejection; and a cured product thereof.
  • Ultraviolet curable ink-jet inks in the field of industrial inkjet printer are about to become mainstream, due to the fact that they are quick-drying and low-volatile, and can even be printed on a non-absorbable material.
  • Patent documents 1, 2 and 3 where silicone is contained by a small amount in such ultraviolet curable ink-jet ink, as a defoaming agent, a surfactant and/or a wear resistance improving agent
  • silicone is used as a main component in such ink jet ink. This is mainly because silicone has a significantly low surface tension; and if contained in the ink by a large amount, the ink cannot be ejected via inkjet ejection.
  • silicone can be used as a main component, not only a favorable rubber property can be imparted, but the weather resistance of the ink itself can be improved as well, which broadens the range of the industrial purposes of silicone.
  • Patent document 4 materials for use in an ink-jet 3D printer are being actively developed, these materials are often resins that are extremely hard.
  • Patent document 5 silicone material for use in a 3D printer
  • Patent document 5 silicone material capable of being ejected via inkjet ejection.
  • strongly desired is the development of a material capable of being ejected via inkjet ejection and exhibiting favorable rubber properties after curing.
  • an object of the present invention to provide an ultraviolet curable silicone composition capable of being ejected via inkjet ejection, and forming a cured product having favorable rubber properties.
  • an ultraviolet curable silicone composition capable of being ejected via inkjet ejection and a cured product thereof, by employing a particular ultraviolet curable organopolysiloxane component; and a monofunctional ethylene group-containing compound having no siloxane structure and/or a multifunctional ethylene group-containing compound having no siloxane structure.
  • the present invention is to provide the following ultraviolet curable silicone composition.
  • An ultraviolet curable silicone composition containing:
  • each R 1 independently represents a group selected from a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyl group, a methacryloyl group, an alkyl acrylate group and an alkyl methacrylate group, while the component (A) has per molecule at least two groups selected from an acryloyl group, a methacryloyl group, an alkyl acrylate group and an alkyl methacrylate group; n represents a number satisfying 10 ⁇ n ⁇ 1,000;
  • component (C) a multifunctional (meth)acrylate compound having no siloxane structure, the component (B) and/or the component (C) being in an amount of 1 to 500 parts by mass per 100 parts by mass of the component (A);
  • each R 2 independently represents a group selected from a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyl group, a methacryloyl group, an alkyl acrylate group and an alkyl methacrylate group, while the component (E) has per molecule one group selected from an acryloyl group, a methacryloyl group, an alkyl acrylate group and an alkyl methacrylate group; m represents a number satisfying 10 ⁇ m ⁇ 1,000.
  • a cured product of the ultraviolet curable silicone composition as set forth in any one of [1] to [3].
  • An ink composition for 3D printer containing the ultraviolet curable silicone composition as set forth in any one of [1] to [3].
  • the ultraviolet curable silicone composition of the present invention has a favorable viscosity, surface tension and curability, and can be ejected via inkjet ejection. Further, the cured product of this composition has favorable rubber properties (hardness, tensile strength and elongation at break). In this way, the ultraviolet curable silicone composition of the invention is useful as an ink-jet ink material, particularly as a silicone material for use in an ink-jet 3D printer.
  • FIG. 1 is a picture showing how a composition prepared in a working example 1 is ejected via inkjet ejection.
  • FIG. 2 is a picture showing how a composition prepared in a working example 4 is ejected via inkjet ejection.
  • a component (A) is an organopolysiloxane represented by the following general formula (1).
  • each R 1 independently represents a group selected from a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyl group, a methacryloyl group, an alkyl acrylate group, and an alkyl methacrylate group.
  • a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms is preferred as such monovalent aliphatic hydrocarbon group, examples of which include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group. More preferred is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms; particularly, it is preferred, in terms of ease of synthesis and cost, that 80% or more of all the R 1 s be methyl groups.
  • At least two of the R 1 s in the above formula (1) are selected from an acryloyl group, a methacryloyl group, an alkyl acrylate group and an alkyl methacrylate group.
  • alkyl acrylate groups include an acrylic acid butyl group and an acrylic acid propyl group; and examples of such alkyl methacrylate groups include a methacrylic acid butyl group and a methacrylic acid propyl group.
  • n represents a number satisfying 10 ⁇ n ⁇ 1,000, preferably 20 ⁇ n ⁇ 500, more preferably 30 ⁇ n ⁇ 300.
  • n is smaller than 10
  • the composition will easily volatilize; when n is larger than 1,000, the viscosity of the composition will increase such that inkjet ejection will be difficult.
  • the value of n can be calculated as an average value via 29 Si-NMR measurement.
  • the organopolysiloxane represented by the formula (1) be that having a methacrylic acid propyl group or acrylic acid propyl group at each of the two ends of the molecule.
  • organopolysiloxane examples include the following compounds.
  • each R 1 independently represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, specific examples of which include groups similar to those listed as the examples of R 1 in the general formula (1).
  • the organopolysiloxane as the component (A) be contained in the composition by an amount of 10 to 95% by mass, more preferably 15 to 80% by mass.
  • a component (B) is a monofunctional (meth)acrylate compound having no siloxane structure.
  • monofunctional (meth)acrylate compound having no siloxane structure include isoamylacrylate, lauryl acrylate, stearyl acrylate, ethoxy-diethylene glycol acrylate, methoxy-triethylene glycol acrylate, 2-ethylhexyl-diglycol acrylate, phenoxy ethyl acrylate, phenoxydiethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, and mixtures thereof, among which isobornyl acrylate is preferred.
  • a component (C) is a multifunctional (meth)acrylate compound having no siloxane structure.
  • multifunctional (meth)acrylate compound having no siloxane structure include triethylene glycol diacrylate, polytetramethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, dimethylol-tricyclodecane diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and mixtures thereof, among which dimethylol-tricyclodecane diacrylate is preferred.
  • any one or both of the (meth)acrylate compounds as the components (B) and (C) is/are added in a total amount of 1 to 500 parts by mass, preferably 10 to 400 parts by mass, per 100 parts by mass of the component (A).
  • the total amount of the components (B) and/or (C) added is smaller than 1 part by mass per 100 parts by mass of the component (A)
  • the composition will exhibit an insufficient curability, and inkjet ejection will be difficult as the surface tension weakens.
  • the viscosity of the composition as a whole can be adjusted to a desired range suitable for performing inkjet ejection, by increasing the total amount of the components (B) and/or (C) added.
  • the cured product will exhibit a hardness higher than necessary in a way such that a desired rubber property cannot be achieved.
  • a component (D) is a photopolymerization initiator.
  • photopolymerization initiator examples include 2,2-diethoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651 by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 by BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Irgacure 1173 by BASF), 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl ⁇ -2-methyl-propane-1-one (Irgacure 127 by BASF), phenylglyoxylic acid methyl ester (Irgacure MBF by BASF), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (Irgacure 907 by BASF), 2-benzyl-2-
  • the photopolymerization initiator is added in an amount of 0.1 to 20 parts by mass per 100 parts by mass of the component (A). If such amount added is smaller than 0.1 parts by mass per 100 parts by mass of the component (A), the composition will exhibit an insufficient curability; if such amount added is greater than 20 parts by mass per 100 parts by mass of the component (A), a depth-curability of the composition will be impaired.
  • the ultraviolet curable silicone composition of the present invention may further contain, as a component (E), an organopolysiloxane represented by the following general formula (2), if necessary.
  • a component (E) an organopolysiloxane represented by the following general formula (2), if necessary.
  • Each R 2 in the above formula (2) independently represents a group selected from a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyl group, a methacryloyl group, an alkyl acrylate group and an alkyl methacrylate group.
  • a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms is preferred, examples of which include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group. More preferred is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms; particularly, it is preferred, in terms of ease of synthesis and cost, that 80% or more of all the R 2 s be methyl groups.
  • one of the R 2 s in the above formula (2) is an acryloyl group, a methacryloyl group, an alkyl acrylate group or an alkyl methacrylate group.
  • alkyl acrylate group include an acrylic acid butyl group and an acrylic acid propyl group
  • alkyl methacrylate group include a methacrylic acid butyl group and a methacrylic acid propyl group.
  • the aforementioned one R 2 be a methacrylic acid propyl group or an acrylic acid propyl group in terms of ease of synthesis.
  • m represents a number satisfying 10 ⁇ m ⁇ 1,000, preferably 20 ⁇ m ⁇ 500, more preferably 30 ⁇ m ⁇ 300.
  • m is smaller than 10
  • the composition will easily volatilize; when m is larger than 1,000, the viscosity of the composition will increase such that inkjet ejection will be difficult.
  • the value of m can be calculated as an average value via 29 Si-NMR measurement.
  • the organopolysiloxane represented by the formula (2) be that having a methacrylic acid propyl group or acrylic acid propyl group at one end of the molecule.
  • organopolysiloxane examples include the following compounds.
  • each R 2 independently represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, specific examples of which include groups similar to those listed as the examples of R 2 in the above general formula (2).
  • the component (E) be added in an amount of 0.1 to 1,000 parts by mass, more preferably 1 to 100 parts by mass, per 100 parts by mass of the component (A). If the component (E) is added in an amount of 0.1 to 1,000 parts by mass per 100 parts by mass of the component (A), the cured product of the composition is expected to exhibit an improved elongation at break.
  • Additives such as a color material (pigment or dye), a silane coupling agent, an adhesion aid, a polymerization inhibitor, an antioxidant, an ultraviolet absorber and a light stabilizer can be added to the composition of the invention without impairing the effects of the invention. Further, the composition of the invention may also be appropriately mixed with an other resin composition(s) before use.
  • the ultraviolet curable silicone composition of the invention can be produced by, for example, stirring and mixing the components (A), (B), (C) and (D); as well as the component (E) and other components, if necessary.
  • a device used to perform stirring or the like there may be used, for example, a kneader, triple roll mill, a ball mill and a planetary mixer. Further, these devices may also be appropriately used in combination.
  • the viscosity of the ultraviolet curable silicone composition of the invention at 23° C. be not higher than 2,000 mPa ⁇ s, more preferably not higher than 1,000 mPa ⁇ s. Further, it is preferred that the surface tension of the composition be not smaller than 21 mN/m, and not larger than 36 mN/m. If the viscosity and surface tension of the composition are within these ranges, inkjet ejection can be performed in a stable manner.
  • the ultraviolet curable silicone composition of the invention can be rapidly cured when irradiated by an ultraviolet light.
  • a light source of the ultraviolet light with which the ultraviolet curable silicone composition of the invention is irradiated include a UVLED lamp, a high-pressure mercury lamp, a super-high pressure mercury lamp, a metal halide lamp, a carbon-arc lamp and a xenon lamp.
  • the irradiance level (cumulative light intensity) of the ultraviolet light be 1 to 5,000 mJ/cm 2 , more preferably 10 to 4,000 mJ/cm 2 , with respect to a sheet formed of the composition of the invention and having a thickness of about 2.0 mm. That is, when using an ultraviolet light of an intensity of 100 mW/cm 2 , an ultraviolet irradiation for about 0.01 to 50 seconds will suffice.
  • a hardness measured after curing be not lower than 10 (Type A), more preferably not lower than 20 (Type A).
  • a tensile strength is preferably not lower than 0.5 MPa, more preferably not lower than 0.8 MPa.
  • An elongation at break is preferably not lower than 10%, more preferably not lower than 20%.
  • the hardness after curing can be adjusted by increasing or reducing the amount of any one or both of the components (B) and (C) added.
  • the tensile strength and elongation at break after curing can be adjusted in a similar manner.
  • compositions in working examples 1 to 6; and comparative examples 1 and 2 were prepared at the composition ratios shown in Table 1, and then evaluated by the following methods.
  • a viscosity of the composition refers to a value measured by a rotary viscometer at 23° C.
  • a surface tension refers to a value measured by a CBVP-Z type automatic surface tensiometer manufactured by Kyowa Interface Science Co., Ltd.
  • an inkjet ejection property was evaluated as follows. Specifically, there was used a droplet observation device IJK-2005 (glass-made 1-nozzle inkjet head IJHE-1000) manufactured by MICROJET Corporation, and an ejection status was shot with camera for evaluation under ejection conditions of: drive voltage 80V; head temperature 80° C.; and nozzle diameter 80 ⁇ m. There, “ ⁇ ” was given when a droplet of 100 pl/droplet or more had been ejected; whereas “x” was given when such status was not met.
  • IJK-2005 glass-made 1-nozzle inkjet head IJHE-1000 manufactured by MICROJET Corporation
  • FIGS. 1 and 2 show how inkjet ejection takes place with regard to the compositions prepared in the working examples 1 and 4.
  • a hardness, elongation at break and tensile strength of the cued product was measured in accordance with JIS-K6249.
  • the cured product was obtained by performing an ultraviolet irradiation of an intensity of 4,000 mJ/cm 2 under a nitrogen atmosphere, using a lamp H (M) 06-L-61 manufactured by EYE GRAPHICS Co., Ltd. Further, the sheet of the cured product was formed to a thickness of 2.0 mm.
  • D-1 2-hydroxy-2-methyl-1-phenyl-propane-1-one (Irgacure 1173 by BASF)
  • D-2 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO by BASF)
  • Hexamethylcyclotrisiloxane of 100 g and toluene of 100 g were mixed together in a glass-made reactor equipped with a cooling tube, a thermometer, a dropping funnel and a stirrer, followed by performing azeotropic dehydration for an hour. Later, the reaction solution was cooled to 10° C., followed by delivering thereinto by drops 8.2 g of n-butyllithium (15% by mass hexane solution), and then raising the temperature to 25° C. to perform stirring for an hour. Next, 2 g of dimethylformamide was added to perform a polymerization reaction at 25° C.
  • organopolysiloxane A-5 was obtained in a similar manner as the synthesis example 4, except that the amount of octamethylcyclotetrasiloxane used was 8,300 g.
  • the structure of A-5 (number of repeating units of dimethylsiloxy groups) was calculated via 29 Si-NMR.
  • the ultraviolet curable silicone composition of the present invention has a favorable inkjet ejection property and curability, and exhibits superior rubber properties after curing.
  • the composition of the invention is useful as an ink-jet ink material, particularly as a silicone material for use in an ink-jet 3D printer.
  • inkjet ejection was not possible due to an increased viscosity
  • in the comparative example 2 where the component (B) was not used the inkjet property deteriorated due to an insufficient surface tension, and an insufficient curability was observed.

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  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
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  • Macromonomer-Based Addition Polymer (AREA)
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JP7074641B2 (ja) 2018-10-29 2022-05-24 信越化学工業株式会社 （メタ）アクリロイル基含有オルガノシロキサン
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WO2020210143A1 (en) * 2019-04-08 2020-10-15 Henkel IP & Holding GmbH Uv and/or heat curable silicone based materials and formulations
FR3096606A1 (fr) * 2019-05-29 2020-12-04 Elkem Silicones France Sas Méthode de fabrication additive pour produire un article en élastomère silicone
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JP7290115B2 (ja) * 2020-01-10 2023-06-13 信越化学工業株式会社 （メタ）アクリル官能性オルガノポリシロキサンの製造方法、硬化性組成物およびインクジェット用インク
WO2021140862A1 (ja) 2020-01-10 2021-07-15 信越化学工業株式会社 硬化性組成物およびインクジェット用インク
KR20230071164A (ko) 2020-09-23 2023-05-23 신에쓰 가가꾸 고교 가부시끼가이샤 자외선 경화성 실리콘 조성물 및 경화물
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WO2018003381A1 (ja) 2018-01-04
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CN109415472A (zh) 2019-03-01

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