WO2020080011A1 - Uv-curable silicone composition and cured product thereof - Google Patents

Uv-curable silicone composition and cured product thereof Download PDF

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Publication number
WO2020080011A1
WO2020080011A1 PCT/JP2019/036159 JP2019036159W WO2020080011A1 WO 2020080011 A1 WO2020080011 A1 WO 2020080011A1 JP 2019036159 W JP2019036159 W JP 2019036159W WO 2020080011 A1 WO2020080011 A1 WO 2020080011A1
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group
formula
curable silicone
silicone composition
carbon atoms
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PCT/JP2019/036159
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French (fr)
Japanese (ja)
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展明 松本
太一 北川
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信越化学工業株式会社
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Priority to JP2020552972A priority Critical patent/JPWO2020080011A1/en
Publication of WO2020080011A1 publication Critical patent/WO2020080011A1/en

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Classifications

    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/08—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polysiloxanes
    • 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
    • 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
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

  • the present invention relates to an ultraviolet curable silicone composition and a cured product thereof.
  • Patent Document 1 An acrylate photocurable resin composition or a urethane acrylate photocurable resin composition, but cured products of these compositions cannot be bent very hard. It is becoming more and more necessary to use a soft rubber-like material depending on the application, and a material suitable for the molding method has already been developed.
  • Patent Document 2 a composition containing an alkenyl group-containing organopolysiloxane, a mercapto group-containing organopolysiloxane and an MQ resin has already been disclosed (Patent Document 2). Also disclosed is a silicone mixture containing a platinum catalyst that is activated by ultraviolet rays for dispensing technology (Patent Document 3).
  • the viscosity of the modeling material needs to be low, and the above-mentioned materials cannot be used as they are.
  • the present invention has been made in view of the above circumstances, has a viscosity that can be used even in a molding method such as a lifting method, has a low odor, and its cured product is an ultraviolet curable silicone composition that can be used as a soft rubber-like 3D printer molding material.
  • the object is to provide a cured product and a cured product thereof.
  • the present inventors have conducted extensive studies in order to achieve the above object, and as a result, by using a specific long-chain UV-curable organopolysiloxane component and short-chain UV-curable organopolysiloxane component, a low viscosity before curing is obtained.
  • they have found that it is possible to provide an ultraviolet-curable silicone composition having low odor and good rubber physical properties after curing, and completed the present invention.
  • the present invention provides the following ultraviolet curable silicone composition and its cured product.
  • (A) Organopolysiloxane represented by the following formula (1): 100 parts by mass, [In the formula (1), n is a number satisfying 80 ⁇ n ⁇ 1,000, R 1 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is the following formula (2). Is a group represented by. [In the formula (2), p is a number satisfying 0 ⁇ p ⁇ 10, a is a number satisfying 1 ⁇ a ⁇ 3, and R 1's are independently of each other a monovalent hydrocarbon having 1 to 20 carbon atoms.
  • R 2 is an oxygen atom or an alkylene group
  • R 3 is an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group.
  • (B) Organopolysiloxane represented by the following formula (3): 5 to 100 parts by mass
  • R 4 is independently a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group and a methacryloyloxyalkyloxy group.
  • m is a number that satisfies 5 ⁇ m ⁇ 50.
  • C a photopolymerization initiator: 0.1 to 20 parts by mass, which is an ultraviolet-curable silicone composition.
  • an ultraviolet-curable silicone composition in which a molded article cured by ultraviolet rays exhibits good rubber physical properties and has low viscosity and low odor.
  • the component (A) is an organopolysiloxane represented by the following formula (1).
  • N in the formula (1) is 80 ⁇ n ⁇ 1,000, preferably 90 ⁇ n ⁇ 800, and more preferably 95 ⁇ n ⁇ 700. If n is less than 80, the cured product will be a brittle material, and if n is more than 1,000, the viscosity of the composition will be high and handleability will be poor.
  • a in the formula (1) is a group represented by the following formula (2).
  • R 1's each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms excluding an aliphatic unsaturated group, More preferably, it represents a monovalent hydrocarbon group of 1 to 8.
  • the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl and n.
  • -Alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl groups; vinyl, allyl (2-propenyl), 1-propenyl , Alkenyl groups such as isopropenyl and butenyl groups; aryl groups such as phenyl, tolyl, xylyl and naphthyl groups; aralkyl groups such as benzyl, phenylethyl and phenylpropyl groups.
  • some or all of the hydrogen atoms bonded to the carbon atoms of these monovalent hydrocarbon groups may be substituted with other substituents, and specific examples thereof include chloromethyl, bromoethyl, trifluoropropyl, Examples thereof include halogen-substituted hydrocarbon groups such as cyanoethyl group and cyano-substituted hydrocarbon groups.
  • R 1 an alkyl group having 1 to 5 carbon atoms and a phenyl group are preferable, and a methyl group, an ethyl group and a phenyl group are more preferable.
  • R 2 represents an oxygen atom or an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 and more preferably 1 to 5.
  • the alkylene group having 1 to 20 carbon atoms represented by R 2 may be linear, branched or cyclic, and specific examples thereof include methylene, ethylene, propylene, trimethylene, tetramethylene, isobutylene, Examples include pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decylene group and the like.
  • R 2 is preferably an oxygen atom, methylene, ethylene or trimethylene group, more preferably an oxygen atom or ethylene group.
  • R 3's each independently represent an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group.
  • the carbon number of the alkyl (alkylene) group in the acryloyloxyalkyl group, methacryloyloxyalkyloxy group, acryloyloxyalkyloxy group, or methacryloyloxyalkyloxy group of R 3 is not particularly limited. However, 1 to 10 is preferable, and 1 to 5 is more preferable. Specific examples of these alkyl groups include those having 1 to 10 carbon atoms among the groups exemplified for R 1 .
  • R 3 examples include, but include those represented by the following formula, but is not limited thereto. (In the formula, b represents a number satisfying 1 ⁇ b ⁇ 4, and R 5 represents an alkylene group having 1 to 10 carbon atoms.)
  • p represents a number satisfying 0 ⁇ p ⁇ 10, preferably 0 or 1
  • a represents a number satisfying 1 ⁇ a ⁇ 3, and preferably 1 or 2.
  • organopolysiloxane represented by the above formula (1) examples include the following compounds. (In the formula, R 1 , R 2 , R 5 , n, and b have the same meanings as described above.)
  • Such an organopolysiloxane can be produced by a known method.
  • the organopolysiloxane represented by the above formula (4) is, for example, a dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends, a diphenylpolysiloxane capped with dimethylvinylsiloxy groups with both ends or a dimethylsiloxane-diphenylsiloxane blocked with dimethylvinylsiloxy groups at both ends.
  • the organopolysiloxane represented by the above formula (5) is, for example, a dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends, a diphenylpolysiloxane capped with dimethylvinylsiloxy groups at both ends or a dimethylsiloxane-diphenylsiloxane capped with dimethylvinylsiloxy groups at both ends. It can be obtained by reacting 2-hydroxyethyl acrylate with a hydrosilylation reaction product of a diorganopolysiloxane blocked with dimethylvinylsiloxy groups at both ends such as a copolymer and dichloromethylsilane.
  • the component (A) is preferably contained in the composition of the present invention in an amount of 40 to 95% by mass, more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass.
  • the component (B) is an organopolysiloxane represented by the following formula (3).
  • R 4 in the above formula (3) is independently a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group or a methacryloyloxyalkyloxy group. It is the group of choice.
  • the monovalent aliphatic hydrocarbon group is preferably a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group.
  • alkyl groups such as More preferably, it is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and among them, from the viewpoint of ease of synthesis and cost, 80% or more of the total number of R 4 are methyl groups.
  • Two of R 4 in the above formula (3) are a polymerizable group selected from an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group and a methacryloyloxyalkyloxy group.
  • the polymerizable groups may be the same or different, and specific examples thereof include the same ones as those mentioned above as R 3 .
  • the polymerizable group may be present at either the end of the molecular chain of the organopolysiloxane or in the middle thereof, but it is preferable that one is present at each end of the molecule in terms of ease of synthesis and cost.
  • M in the formula (3) is a number satisfying 5 ⁇ m ⁇ 50, preferably 8 ⁇ m ⁇ 50, and more preferably 10 ⁇ m ⁇ 30.
  • m is less than 5, the odor becomes strong, and when m is more than 50, the reactivity of the composition becomes poor and the material after curing becomes brittle.
  • the value of m can be calculated as an average value by, for example, 29 Si-NMR measurement.
  • organopolysiloxanes examples include the following compounds. (In the formula, Me represents a methyl group, and m represents the same meaning as the above.)
  • the amount of the component (B) added is in the range of 5 to 100 parts by mass, preferably 10 to 70 parts by mass, relative to 100 parts by mass of the component (A).
  • the added amount of the component (B) is less than 5 parts by mass relative to 100 parts by mass of the component (A)
  • the curability of the composition is insufficient and the cured product becomes brittle.
  • the viscosity of the entire composition can be adjusted to a desired range suitable for the lifting method by increasing the addition amount of the component (B), and the reactivity can be enhanced.
  • the addition amount of the component (B) exceeds 100 parts by mass with respect to 100 parts by mass of the component (A)
  • the hardness of the cured product becomes unnecessarily high, and desired rubber physical properties cannot be obtained.
  • C Photopolymerization Initiator
  • known compounds can be used, and examples thereof include 2,2-diethoxyacetophenone and 2,2-dimethoxy-1,2-diphenyl.
  • Ethan-1-one (Irgacure 651 from BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 from BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure 1173 from BASF) ), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one (BASF Irgacure 127), phenylgly Oxic acid methyl ester (Irgacure MBF manufactured by BASF), 2- Tyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacur
  • component (C) preferred from the viewpoint of compatibility with the component (A) are 2,2-diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF).
  • BASF 2-hydroxy-2-methyl-1-phenyl-propan-1-one
  • Irgacure 1173 2,2-diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one
  • Irgacure 819 manufactured by BASF
  • IIrgacure TPO 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
  • the addition amount of the photopolymerization initiator is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A). If the addition amount of the component (C) is less than 0.1 parts by mass relative to 100 parts by mass of the component (A), the curability is insufficient, and if it is added in an amount exceeding 20 parts by mass, the deep part curability is deteriorated. .
  • the composition of the present invention further contains a coloring material (pigment or dye), a silane coupling agent, an adhesion aid, a polymerization inhibitor, an antioxidant, and a light resistance stabilizer as long as the effects of the present invention are not impaired. Additives such as an ultraviolet absorber and a light stabilizer can be blended. Further, the composition of the present invention can be used by appropriately mixing it with another resin composition.
  • the ultraviolet curable silicone composition of the present invention is obtained by stirring and mixing the above-mentioned component (A), component (B) and component (C) and, if necessary, other components.
  • the device used for operations such as stirring is not particularly limited, but a crusher, three rolls, ball mill, planetary mixer or the like can be used. Further, these devices may be combined appropriately.
  • the viscosity of the composition is preferably 10 to 5,000 mPa ⁇ s, and more preferably 100 to 2,000 mPa ⁇ s, as a standard for forming by the lifting method. Is more preferable.
  • the viscosity is a value measured at 25 ° C using a rotational viscometer. When the viscosity of the composition is within such a range, it is possible to suppress the flow at the portion irradiated with ultraviolet rays during molding.
  • the viscosity of the composition can be adjusted by changing the chain length of the component (A) or increasing or decreasing the addition amount of the component (B).
  • the ultraviolet curable silicone composition of the present invention cures rapidly when irradiated with ultraviolet rays.
  • the light source of the ultraviolet light with which the ultraviolet curable silicone composition of the present invention is irradiated include UV LED lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, carbon arc lamps, and xenon lamps.
  • the irradiation amount of ultraviolet rays is, for example, preferably 1 to 5,000 mJ / cm 2 , and more preferably 10 to 5,000 for a sheet formed by molding the composition of the present invention to a thickness of about 2.0 mm. It is 4,000 mJ / cm 2 . That is, when using ultraviolet light having an illuminance of 100 mW / cm 2 at 365 nm, the ultraviolet light may be irradiated for about 0.01 to 50 seconds.
  • the hardness after curing is in the range of 5 to 80 (TypeA), preferably 10 to 70 (TypeA).
  • the tensile strength after curing is preferably 0.5 MPa or more, more preferably 0.8 MPa or more. If the tensile strength is less than 0.5 MPa, the shaped article may become brittle.
  • the elongation at break after curing is preferably 50% or more, more preferably 80% or more. If the elongation at break is less than 50%, the molded article cannot follow when folded and is easily cracked. Note that these values are values measured according to JIS-K6249.
  • the rubber physical properties of the cured product can be adjusted by changing the chain length of the component (A) or by increasing or decreasing the addition amount of the component (B).
  • Examples 1 to 3 and Comparative Examples 1 to 4 The following components were mixed at the composition ratio shown in Table 1 (numerical values represent parts by mass) to obtain an ultraviolet curable silicone composition.
  • the viscosity of the composition obtained in each example is a value measured at 25 ° C. using a rotational viscometer.
  • each composition was poured into a frame and cured under a nitrogen atmosphere under an ultraviolet irradiation condition of 2,000 mJ / cm 2 using a lamp H (M) 06-L-61 manufactured by Eye Graphics Co., Ltd. A 2.0 mm thick cured sheet was obtained.
  • the hardness, tensile strength and elongation at break of the obtained cured sheet were measured according to JIS-K6249.
  • those having a strong odor were marked with X, and those having a weak odor were marked with ⁇ .
  • the results obtained are shown in Table 1.
  • Component (A-1) organopolysiloxane represented by the following formula (6) produced by the above-mentioned method
  • Component (B-1) organopolysiloxane represented by the following formula (8)
  • Component (C-1) 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF's Irgacure 1173)
  • C-2) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO manufactured by BASF)
  • the ultraviolet-curable silicone composition of the present invention has a sufficiently low viscosity, exhibits excellent rubber physical properties after curing, and has a low odor. Therefore, it is particularly suitable for a 3D printer using a molding method such as a surface exposure method or a lifting method. It is useful as a silicone material.
  • Comparative Example 1 containing no component (B) curing did not occur, and in Comparative Examples 2 to 4 in which the polymerizable component outside the scope of the present invention was used in place of the component (B), the composition had a strong odor. It had (Comparative Examples 2 and 4) or had insufficient tensile strength (Comparative Example 3).

Abstract

Provided are a low-odor UV-curable silicone composition having a viscosity that enables use even in modeling methods, e.g., pull-up methods, and a cured product thereof. The UV-curable silicone composition comprises: (A) an organopolysiloxane represented by formula (1), wherein in formula (1), n is 80 ≤ n ≤ 1,000, R1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is a group represented by formula (2), wherein in formula (2), p is 0 ≤ p ≤ 10, a is 1 ≤ a ≤ 3, R1 is a monovalent hydrocarbon group having 1 to 20 carbon atoms, R2 is an oxygen atom or an alkylene group, and R3 is an acryloyloxyalkyl group and so forth; (B) an organopolysiloxane represented by formula (3), wherein in formula (3), R4 is a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or an acryloyloxyalkyl group and so forth, and m is a number that satisfies 5 ≤ m ≤ 50; and (C) a photopolymerization initiator.

Description

紫外線硬化性シリコーン組成物及びその硬化物Ultraviolet curable silicone composition and cured product thereof
　本発明は、紫外線硬化性シリコーン組成物及びその硬化物に関する。 The present invention relates to an ultraviolet curable silicone composition and a cured product thereof.
　近年３Ｄプリンタで用いられる造形材料の開発が盛んになってきており、造形材料の種類は金属から樹脂まで様々なものが存在している。樹脂分野での主流はアクリレート系光硬化性樹脂組成物やウレタンアクリレート系光硬化性樹脂組成物であるが、これらの組成物の硬化物は非常に硬く曲げることは出来ない（特許文献１）。
　用途に応じて柔らかいゴムライクな材料が必要になることも多くなってきており、造形方式に合せた材料が既に開発されている。例えば、光造形方式（ＳＬＡ）向けの材料として、アルケニル基含有オルガノポリシロキサン、メルカプト基含有オルガノポリシロキサン及びＭＱレジンを含有した組成物が既に開示されている（特許文献２）。また、ディスペンス技術向けに紫外線によって活性化される白金触媒を含有したシリコーン混合物も開示されている（特許文献３）。
　しかしながら、近年普及し始めている吊り上げ方式の場合は、造形材料の粘度が低い必要が有り、上述した材料をそのまま使用することは出来ない。また、インクジェット方式を用いる３Ｄプリンタ向けに光硬化性の低粘度シリコーン材料が開示されている（特許文献４）が、材料の反応性を高める為の紫外線反応性成分に由来する臭気が問題となっていた。 In recent years, the development of modeling materials used in 3D printers has been brisk, and there are various types of modeling materials from metals to resins. The mainstream in the resin field is an acrylate photocurable resin composition or a urethane acrylate photocurable resin composition, but cured products of these compositions cannot be bent very hard (Patent Document 1).
It is becoming more and more necessary to use a soft rubber-like material depending on the application, and a material suitable for the molding method has already been developed. For example, as a material for stereolithography (SLA), a composition containing an alkenyl group-containing organopolysiloxane, a mercapto group-containing organopolysiloxane and an MQ resin has already been disclosed (Patent Document 2). Also disclosed is a silicone mixture containing a platinum catalyst that is activated by ultraviolet rays for dispensing technology (Patent Document 3).
However, in the case of the hoisting method, which has become popular in recent years, the viscosity of the modeling material needs to be low, and the above-mentioned materials cannot be used as they are. In addition, a photocurable low-viscosity silicone material has been disclosed for a 3D printer using an inkjet method (Patent Document 4), but an odor derived from an ultraviolet reactive component for increasing the reactivity of the material becomes a problem. Was there.
特開２０１２－１１１２２６号公報JP, 2012-111226, A 特許第４７８８８６３号公報Japanese Patent No. 4788863 特許第５３８４６５６号公報Japanese Patent No. 5384656 国際公開第２０１８／００３３８１号公報International Publication No. 2018/003381
　本発明は、上記事情に鑑みなされたもので、吊り上げ方式等の造形方式でも使用可能な粘度で、低臭気であり、その硬化物は柔らかいゴムライクな３Ｄプリンタ造形材料として使用出来る紫外線硬化性シリコーン組成物及びその硬化物を提供することを目的とする。 The present invention has been made in view of the above circumstances, has a viscosity that can be used even in a molding method such as a lifting method, has a low odor, and its cured product is an ultraviolet curable silicone composition that can be used as a soft rubber-like 3D printer molding material. The object is to provide a cured product and a cured product thereof.
　本発明者らは上記目的を達成するために鋭意研究を重ねた結果、特定の長鎖紫外線硬化性オルガノポリシロキサン成分及び短鎖紫外線硬化性オルガノポリシロキサン成分を用いることで、硬化前は低粘度且つ低臭気であり、硬化後は良好なゴム物性を示す紫外線硬化性シリコーン組成物を提供出来ることを見出し、本発明を完成した。 The present inventors have conducted extensive studies in order to achieve the above object, and as a result, by using a specific long-chain UV-curable organopolysiloxane component and short-chain UV-curable organopolysiloxane component, a low viscosity before curing is obtained. In addition, they have found that it is possible to provide an ultraviolet-curable silicone composition having low odor and good rubber physical properties after curing, and completed the present invention.
　本発明は、下記の紫外線硬化性シリコーン組成物及びその硬化物を提供する。
［１］
（Ａ）下記式（１）で示されるオルガノポリシロキサン：１００質量部、
Figure JPOXMLDOC01-appb-C000004
 ［式（１）中、ｎは８０≦ｎ≦１，０００を満たす数であり、Ｒ1は互いに独立に炭素原子数１～２０の一価炭化水素基であり、Ａは下記式（２）で示される基である。
Figure JPOXMLDOC01-appb-C000005
 ［式（２）中、ｐは０≦ｐ≦１０を満たす数であり、ａは１≦ａ≦３を満たす数であり、Ｒ1は互いに独立に炭素原子数１～２０の一価炭化水素基であり、Ｒ2は酸素原子又はアルキレン基であり、Ｒ3はアクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基、またはメタクリロイルオキシアルキルオキシ基である。］］
（Ｂ）下記式（３）で示されるオルガノポリシロキサン：５～１００質量部
Figure JPOXMLDOC01-appb-C000006
 ［式（３）中、Ｒ4は、夫々独立に炭素原子数１～１０の一価脂肪族炭化水素基、アクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基及びメタクリロイルオキシアルキルオキシ基より選ばれる基であり、１分子中にアクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基及びメタクリロイルオキシアルキルオキシ基から選ばれる基を２個有する。ｍは５≦ｍ≦５０を満たす数である。］
及び
（Ｃ）光重合開始剤：０．１～２０質量部
を含有することを特徴とする紫外線硬化性シリコーン組成物。 The present invention provides the following ultraviolet curable silicone composition and its cured product.
[1]
(A) Organopolysiloxane represented by the following formula (1): 100 parts by mass,
Figure JPOXMLDOC01-appb-C000004
 [In the formula (1), n is a number satisfying 80 ≦ n ≦ 1,000, R 1 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is the following formula (2). Is a group represented by.
Figure JPOXMLDOC01-appb-C000005
 [In the formula (2), p is a number satisfying 0 ≦ p ≦ 10, a is a number satisfying 1 ≦ a ≦ 3, and R 1's are independently of each other a monovalent hydrocarbon having 1 to 20 carbon atoms. R 2 is an oxygen atom or an alkylene group, and R 3 is an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group. ]]
(B) Organopolysiloxane represented by the following formula (3): 5 to 100 parts by mass
Figure JPOXMLDOC01-appb-C000006
 [In the formula (3), R 4 is independently a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group and a methacryloyloxyalkyloxy group. A group selected from the group consisting of acryloyloxyalkyl group, methacryloyloxyalkyl group, acryloyloxyalkyloxy group and methacryloyloxyalkyloxy group in one molecule. m is a number that satisfies 5 ≦ m ≦ 50. ]
And (C) a photopolymerization initiator: 0.1 to 20 parts by mass, which is an ultraviolet-curable silicone composition.
［２］
　２５℃での粘度が１０～５，０００ｍＰａ・ｓであることを特徴とする［１］に記載の紫外線硬化性シリコーン組成物。 [2]
The ultraviolet-curable silicone composition according to [1], which has a viscosity at 25 ° C. of 10 to 5,000 mPa · s.
［３］
　［１］又は［２］に記載の紫外線硬化性シリコーン組成物の硬化物。 [3]
A cured product of the ultraviolet curable silicone composition according to [1] or [2].
［４］
　３Ｄプリンタインク用である［１］又は［２］に記載の紫外線硬化性シリコーン組成物。 [4]
The ultraviolet-curable silicone composition according to [1] or [2], which is for a 3D printer ink.
　本発明によれば、紫外線にて硬化した造形物が、良好なゴム物性を示し、低粘度且つ低臭気な紫外線硬化性シリコーン組成物を提供することが出来る。 According to the present invention, it is possible to provide an ultraviolet-curable silicone composition in which a molded article cured by ultraviolet rays exhibits good rubber physical properties and has low viscosity and low odor.
以下、本発明をより詳細に説明する。
［（Ａ）成分］
　（Ａ）成分は、下記式（１）で示されるオルガノポリシロキサンである。
Figure JPOXMLDOC01-appb-C000007
 Hereinafter, the present invention will be described in more detail.
[(A) component]
The component (A) is an organopolysiloxane represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000007
　式（１）中のｎは８０≦ｎ≦１，０００であり、好ましくは９０≦ｎ≦８００、より好ましくは９５≦ｎ≦７００である。ｎが８０より小さいと硬化物が脆い材料になり、ｎが１，０００より大きいと組成物の粘度が高くなり、取り扱い性に劣る。 N in the formula (1) is 80 ≦ n ≦ 1,000, preferably 90 ≦ n ≦ 800, and more preferably 95 ≦ n ≦ 700. If n is less than 80, the cured product will be a brittle material, and if n is more than 1,000, the viscosity of the composition will be high and handleability will be poor.
　式（１）中のＡは下記式（２）で示される基である。
Figure JPOXMLDOC01-appb-C000008
 A in the formula (1) is a group represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000008
　式（１）および式（２）において、Ｒ1は、互いに独立して炭素原子数１～２０の一価炭化水素基、好ましくは、脂肪族不飽和基を除く、炭素原子数１～１０、より好ましくは１～８の一価炭化水素基を表す。 In formulas (1) and (2), R 1's each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms excluding an aliphatic unsaturated group, More preferably, it represents a monovalent hydrocarbon group of 1 to 8.
　式（１）及び式（２）において、Ｒ1の炭素原子数１～２０の一価炭化水素基は、直鎖、分岐、環状のいずれでもよく、その具体例としては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔｅｒｔ－ブチル、ｎ－ヘキシル、シクロヘキシル、ｎ－オクチル、２－エチルヘキシル、ｎ－デシル基等のアルキル基；ビニル、アリル（２－プロペニル）、１－プロペニル、イソプロペニル、ブテニル基等のアルケニル基；フェニル、トリル、キシリル、ナフチル基等のアリール基；ベンジル、フェニルエチル、フェニルプロピル基等のアラルキル基などが挙げられる。
　また、これら一価炭化水素基の炭素原子に結合した水素原子の一部または全部は、その他の置換基で置換されていてもよく、その具体例としては、クロロメチル、ブロモエチル、トリフルオロプロピル、シアノエチル基等のハロゲン置換炭化水素基や、シアノ置換炭化水素基などが挙げられる。
　これらの中でも、Ｒ1としては、炭素原子数１～５のアルキル基及びフェニル基が好ましく、メチル基、エチル基及びフェニル基がより好ましい。 In the formulas (1) and (2), the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 1 may be linear, branched or cyclic, and specific examples thereof include methyl, ethyl and n. -Alkyl groups such as propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl groups; vinyl, allyl (2-propenyl), 1-propenyl , Alkenyl groups such as isopropenyl and butenyl groups; aryl groups such as phenyl, tolyl, xylyl and naphthyl groups; aralkyl groups such as benzyl, phenylethyl and phenylpropyl groups.
Further, some or all of the hydrogen atoms bonded to the carbon atoms of these monovalent hydrocarbon groups may be substituted with other substituents, and specific examples thereof include chloromethyl, bromoethyl, trifluoropropyl, Examples thereof include halogen-substituted hydrocarbon groups such as cyanoethyl group and cyano-substituted hydrocarbon groups.
Among these, as R 1 , an alkyl group having 1 to 5 carbon atoms and a phenyl group are preferable, and a methyl group, an ethyl group and a phenyl group are more preferable.
　また、式（２）において、Ｒ2は、酸素原子または炭素原子数１～２０、好ましくは１～１０、より好ましくは１～５のアルキレン基を表す。 Further, in the formula (2), R 2 represents an oxygen atom or an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 and more preferably 1 to 5.
　式（２）において、Ｒ2の炭素原子数１～２０のアルキレン基は、直鎖、分岐、環状のいずれでもよく、その具体例としては、メチレン、エチレン、プロピレン、トリメチレン、テトラメチレン、イソブチレン、ペンタメチレン、ヘキサメチレン、ヘプタメチレン、オクタメチレン、ノナメチレン、デシレン基等が挙げられる。 In the formula (2), the alkylene group having 1 to 20 carbon atoms represented by R 2 may be linear, branched or cyclic, and specific examples thereof include methylene, ethylene, propylene, trimethylene, tetramethylene, isobutylene, Examples include pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decylene group and the like.
　これらの中でも、Ｒ2としては、酸素原子、メチレン、エチレン及びトリメチレン基が好ましく、酸素原子またはエチレン基がより好ましい。 Of these, R 2 is preferably an oxygen atom, methylene, ethylene or trimethylene group, more preferably an oxygen atom or ethylene group.
　さらに、式（２）において、Ｒ3は、互いに独立して、アクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基、またはメタクリロイルオキシアルキルオキシ基を表す。 Further, in the formula (2), R 3's each independently represent an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group.
　式（２）において、Ｒ3のアクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基、またはメタクリロイルオキシアルキルオキシ基におけるアルキル（アルキレン）基の炭素数としては、特に限定されるものではないが、１～１０が好ましく、１～５がより好ましい。これらアルキル基の具体例としては、上記Ｒ1で例示した基のうち、炭素原子数１～１０のものが挙げられる。 In formula (2), the carbon number of the alkyl (alkylene) group in the acryloyloxyalkyl group, methacryloyloxyalkyloxy group, acryloyloxyalkyloxy group, or methacryloyloxyalkyloxy group of R 3 is not particularly limited. However, 1 to 10 is preferable, and 1 to 5 is more preferable. Specific examples of these alkyl groups include those having 1 to 10 carbon atoms among the groups exemplified for R 1 .
　Ｒ3の具体例としては、下記式で示されるものが挙げられるが、これらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000009
 （式中、ｂは、１≦ｂ≦４を満たす数を表し、Ｒ5は、炭素原子数１～１０のアルキレン基を表す。） Specific examples of R 3 include, but include those represented by the following formula, but is not limited thereto.
Figure JPOXMLDOC01-appb-C000009
 (In the formula, b represents a number satisfying 1 ≦ b ≦ 4, and R 5 represents an alkylene group having 1 to 10 carbon atoms.)
　上記式（２）中のｐは、０≦ｐ≦１０を満たす数を表すが、０または１が好ましく、ａは、１≦ａ≦３を満たす数を表すが、１または２が好ましい。 In the above formula (2), p represents a number satisfying 0 ≦ p ≦ 10, preferably 0 or 1, and a represents a number satisfying 1 ≦ a ≦ 3, and preferably 1 or 2.
　上記式（１）で表されるオルガノポリシロキサンの例としては、例えば下記の化合物を挙げることができる。
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ1、Ｒ2、Ｒ5、ｎ、およびｂは、上記と同じ意味を表す。） Examples of the organopolysiloxane represented by the above formula (1) include the following compounds.
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R 1 , R 2 , R 5 , n, and b have the same meanings as described above.)
　このようなオルガノポリシロキサンは公知の方法で製造することができる。上記式（４）で表されるオルガノポリシロキサンは、例えば、両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、両末端ジメチルビニルシロキシ基封鎖ジフェニルポリシロキサン又は両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体等の両末端ジメチルビニルシロキシ基封鎖ジオルガノポリシロキサンと３－（１，１，３，３－テトラメチルジシロキサニル）プロピルメタクリラート（ＣＡＳ　Ｎｏ．９６４７４－１２－３）とのヒドロシリル化反応物として得られる。
　上記式（５）で表されるオルガノポリシロキサンは、例えば、両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン、両末端ジメチルビニルシロキシ基封鎖ジフェニルポリシロキサン又は両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体等の両末端ジメチルビニルシロキシ基封鎖ジオルガノポリシロキサンとジクロロメチルシランとのヒドロシリル化反応物に２－ヒドロキシエチルアクリレートを反応させて得ることができる。
　（Ａ）成分は、本発明組成物中４０～９５質量％含有することが好ましく、更に４０～９０質量％含有することが好ましく、特に５０～９０質量％含有することが好ましい。 Such an organopolysiloxane can be produced by a known method. The organopolysiloxane represented by the above formula (4) is, for example, a dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends, a diphenylpolysiloxane capped with dimethylvinylsiloxy groups with both ends or a dimethylsiloxane-diphenylsiloxane blocked with dimethylvinylsiloxy groups at both ends. Of a diorganopolysiloxane having dimethylvinylsiloxy groups blocked at both ends such as a copolymer and 3- (1,1,3,3-tetramethyldisiloxanyl) propyl methacrylate (CAS No. 96474-12-3) Obtained as a hydrosilylation reaction product.
The organopolysiloxane represented by the above formula (5) is, for example, a dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends, a diphenylpolysiloxane capped with dimethylvinylsiloxy groups at both ends or a dimethylsiloxane-diphenylsiloxane capped with dimethylvinylsiloxy groups at both ends. It can be obtained by reacting 2-hydroxyethyl acrylate with a hydrosilylation reaction product of a diorganopolysiloxane blocked with dimethylvinylsiloxy groups at both ends such as a copolymer and dichloromethylsilane.
The component (A) is preferably contained in the composition of the present invention in an amount of 40 to 95% by mass, more preferably 40 to 90% by mass, and particularly preferably 50 to 90% by mass.
［（Ｂ）成分］
　（Ｂ）成分は、下記式（３）で示されるオルガノポリシロキサンである。
Figure JPOXMLDOC01-appb-C000011
 [(B) component]
The component (B) is an organopolysiloxane represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000011
　上記式（３）におけるＲ4は、夫々独立に炭素原子数１～１０の一価脂肪族炭化水素基、アクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基及びメタクリロイルオキシアルキルオキシ基より選ばれる基である。該一価脂肪族炭化水素基としては、炭素原子数１～８の一価脂肪族炭化水素基が好ましく、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、オクチル基などのアルキル基が挙げられる。さらに好ましくは炭素原子数１～６の一価脂肪族炭化水素基であり、中でも、合成のし易さ、コストの面からＲ4の全数のうち８０％以上がメチル基であるものが好ましい。 R 4 in the above formula (3) is independently a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group or a methacryloyloxyalkyloxy group. It is the group of choice. The monovalent aliphatic hydrocarbon group is preferably a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group. And alkyl groups such as More preferably, it is a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and among them, from the viewpoint of ease of synthesis and cost, 80% or more of the total number of R 4 are methyl groups.
　また、上記式（３）中のＲ4のうち２個は、アクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基及びメタクリロイルオキシアルキルオキシ基より選ばれる重合性基であり、これら２個の重合性基は同一であっても異なっていてもよく、具体的には上記Ｒ3として挙げられたものと同様のものが挙げられる。該重合性基はオルガノポリシロキサンの分子鎖の末端、途中の何れに存在してもよいが、合成のし易さ、コストの面から１分子の両末端に１個ずつ存在するものが好ましい Two of R 4 in the above formula (3) are a polymerizable group selected from an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group and a methacryloyloxyalkyloxy group. The polymerizable groups may be the same or different, and specific examples thereof include the same ones as those mentioned above as R 3 . The polymerizable group may be present at either the end of the molecular chain of the organopolysiloxane or in the middle thereof, but it is preferable that one is present at each end of the molecule in terms of ease of synthesis and cost.
　式（３）中のｍは５≦ｍ≦５０を満たす数であり、好ましくは８≦ｍ≦５０、より好ましくは１０≦ｍ≦３０である。ｍが５より小さいと臭いが強くなり、ｍが５０より大きいと組成物の反応性が劣り、硬化後の材料も脆くなる。ｍの値は、例えば29Ｓｉ－ＮＭＲ測定などにより平均値として算出できる。 M in the formula (3) is a number satisfying 5 ≦ m ≦ 50, preferably 8 ≦ m ≦ 50, and more preferably 10 ≦ m ≦ 30. When m is less than 5, the odor becomes strong, and when m is more than 50, the reactivity of the composition becomes poor and the material after curing becomes brittle. The value of m can be calculated as an average value by, for example, 29 Si-NMR measurement.
　このようなオルガノポリシロキサンの例としては、例えば下記の化合物を挙げることができる。
Figure JPOXMLDOC01-appb-C000012
 （式中、Ｍｅはメチル基を表し、ｍは上記と同じ意味を表す。） Examples of such organopolysiloxanes include the following compounds.
Figure JPOXMLDOC01-appb-C000012
 (In the formula, Me represents a methyl group, and m represents the same meaning as the above.)
　（Ｂ）成分の添加量は、（Ａ）成分１００質量部に対して、５～１００質量部の範囲であり、好ましくは１０～７０質量部である。（Ｂ）成分の添加量が（Ａ）成分１００質量部に対して５質量部未満の場合は、組成物の硬化性が不足し、硬化物も脆くなってしまう。高粘度の（Ａ）成分と組み合わせる場合、（Ｂ）成分の添加量を増やすことにより組成物全体の粘度を吊り上げ方式に適した所望の範囲に調整することができ、反応性を高めることができるが、（Ｂ）成分の添加量が（Ａ）成分１００質量部に対して１００質量部を超えると、硬化物の硬度が必要以上に高くなり、所望のゴム物性が得られなくなる。 The amount of the component (B) added is in the range of 5 to 100 parts by mass, preferably 10 to 70 parts by mass, relative to 100 parts by mass of the component (A). When the added amount of the component (B) is less than 5 parts by mass relative to 100 parts by mass of the component (A), the curability of the composition is insufficient and the cured product becomes brittle. When combined with a high-viscosity component (A), the viscosity of the entire composition can be adjusted to a desired range suitable for the lifting method by increasing the addition amount of the component (B), and the reactivity can be enhanced. However, if the addition amount of the component (B) exceeds 100 parts by mass with respect to 100 parts by mass of the component (A), the hardness of the cured product becomes unnecessarily high, and desired rubber physical properties cannot be obtained.
（Ｃ）光重合開始剤
　光重合開始剤（Ｃ）としては、公知のものを用いることができ、これには例えば、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　６５１）、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　１８４）、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　１１７３）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチループロピオニル）－ベンジル］－フェニル｝－２－メチル－プロパン－１－オン（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　１２７）、フェニルグリオキシリックアシッドメチルエステル（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　ＭＢＦ）、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　９０７）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－１－ブタノン（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　３６９）、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　８１９）、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　ＴＰＯ）及びこれらの混合物等が挙げられる。 (C) Photopolymerization Initiator As the photopolymerization initiator (C), known compounds can be used, and examples thereof include 2,2-diethoxyacetophenone and 2,2-dimethoxy-1,2-diphenyl. Ethan-1-one (Irgacure 651 from BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (Irgacure 184 from BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure 1173 from BASF) ), 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (BASF Irgacure 127), phenylgly Oxic acid methyl ester (Irgacure MBF manufactured by BASF), 2- Tyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907 manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- Butanone (Irgacure 369 from BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819 from BASF), 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO from BASF) ) And mixtures thereof.
　上記（Ｃ）成分のうち、（Ａ）成分との相溶性の観点から好ましいものは、２，２－ジエトキシアセトフェノン、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　１１７３）、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　８１９）、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド（ＢＡＳＦ製Ｉｒｇａｃｕｒｅ　ＴＰＯ）である。 Among the above-mentioned component (C), preferred from the viewpoint of compatibility with the component (A) are 2,2-diethoxyacetophenone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF). Manufactured by Irgacure 1173), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Irgacure 819 manufactured by BASF), and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO manufactured by BASF). .
　光重合開始剤の添加量は（Ａ）１００質量部に対して、０．１～２０質量部である。（Ｃ）成分の添加量が（Ａ）成分１００質量部に対して０．１質量部未満であると硬化性が不足し、２０質量部を超える量で添加した場合は深部硬化性が悪化する。 The addition amount of the photopolymerization initiator is 0.1 to 20 parts by mass with respect to 100 parts by mass of (A). If the addition amount of the component (C) is less than 0.1 parts by mass relative to 100 parts by mass of the component (A), the curability is insufficient, and if it is added in an amount exceeding 20 parts by mass, the deep part curability is deteriorated. .
　本発明の組成物には、更に本発明の効果を損なわない範囲で、色材（顔料或いは染料）、シランカップリング剤、接着助剤、重合禁止剤、酸化防止剤、耐光性安定剤である紫外線吸収剤、光安定化剤等の添加剤を配合することができる。また、本発明の組成物は他の樹脂組成物と適宜混合して使用する事もできる。 The composition of the present invention further contains a coloring material (pigment or dye), a silane coupling agent, an adhesion aid, a polymerization inhibitor, an antioxidant, and a light resistance stabilizer as long as the effects of the present invention are not impaired. Additives such as an ultraviolet absorber and a light stabilizer can be blended. Further, the composition of the present invention can be used by appropriately mixing it with another resin composition.
シリコーン組成物の調製方法
　本発明の紫外線硬化性シリコーン組成物は、上記（Ａ）成分、（Ｂ）成分及び（Ｃ）成分、並びに必要に応じてその他の成分を攪拌及び混合等することにより得られる。攪拌等の操作に用いる装置は特に限定されないが、擂潰機、３本ロール、ボールミル、プラネタリーミキサー等を用いることができる。また、これら装置を適宜組み合わせてもよい。 Method for Preparing Silicone Composition The ultraviolet curable silicone composition of the present invention is obtained by stirring and mixing the above-mentioned component (A), component (B) and component (C) and, if necessary, other components. To be The device used for operations such as stirring is not particularly limited, but a crusher, three rolls, ball mill, planetary mixer or the like can be used. Further, these devices may be combined appropriately.
　本発明の紫外線硬化性シリコーン組成物において、吊り上げ方式による造形が可能な目安としては、組成物の粘度は１０～５，０００ｍＰａ・ｓであることが好ましく、１００～２，０００ｍＰａ・ｓであることがより好ましい。なお、粘度は、回転粘度計を用いて２５℃で測定した値である。組成物の粘度がこのような範囲であれば、造形中に紫外線を照射した箇所の流動を抑制することができる。組成物の粘度は、（Ａ）成分の鎖長を変更したり、（Ｂ）成分の添加量を増減することによって調整できる。 In the ultraviolet curable silicone composition of the present invention, the viscosity of the composition is preferably 10 to 5,000 mPa · s, and more preferably 100 to 2,000 mPa · s, as a standard for forming by the lifting method. Is more preferable. The viscosity is a value measured at 25 ° C using a rotational viscometer. When the viscosity of the composition is within such a range, it is possible to suppress the flow at the portion irradiated with ultraviolet rays during molding. The viscosity of the composition can be adjusted by changing the chain length of the component (A) or increasing or decreasing the addition amount of the component (B).
　本発明の紫外線硬化性シリコーン組成物は、紫外線を照射することにより速やかに硬化する。本発明の紫外線硬化性シリコーン組成物に照射する紫外線の光源としては、例えば、ＵＶＬＥＤランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアークランプ、及びキセノンランプ等が挙げられる。紫外線の照射量（積算光量）は、例えば、本発明の組成物を２．０ｍｍ程度の厚みに成形したシートに対して、好ましくは１～５，０００ｍＪ／ｃｍ2であり、より好ましくは１０～４，０００ｍＪ／ｃｍ2である。つまり、３６５ｎｍにて照度１００ｍＷ／ｃｍ2の紫外線を用いた場合、０．０１～５０秒程度紫外線を照射すればよい。 The ultraviolet curable silicone composition of the present invention cures rapidly when irradiated with ultraviolet rays. Examples of the light source of the ultraviolet light with which the ultraviolet curable silicone composition of the present invention is irradiated include UV LED lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, carbon arc lamps, and xenon lamps. The irradiation amount of ultraviolet rays (integrated light amount) is, for example, preferably 1 to 5,000 mJ / cm 2 , and more preferably 10 to 5,000 for a sheet formed by molding the composition of the present invention to a thickness of about 2.0 mm. It is 4,000 mJ / cm 2 . That is, when using ultraviolet light having an illuminance of 100 mW / cm 2 at 365 nm, the ultraviolet light may be irradiated for about 0.01 to 50 seconds.
　また、本発明の紫外線硬化性シリコーン組成物からなる硬化物が優れたゴム物性を示す為には、硬化後の硬度は５～８０（ＴｙｐｅＡ）の範囲であり、好ましくは１０～７０（ＴｙｐｅＡ）である。硬化後の引張強さは０．５ＭＰａ以上であることが好ましく、０．８ＭＰａ以上であることがより好ましい。引張強さが０．５ＭＰａ未満であると造形物が脆くなる場合がある。硬化後の切断時伸びは５０％以上であることが好ましく、８０％以上であることがより好ましい。切断時伸びが５０％未満になると造形物を折り曲げた際に追随出来ずに割れ易くなる。なお、これらの値は、ＪＩＳ－Ｋ６２４９に準じて測定したときの値である。硬化物のゴム物性は、（Ａ）成分の鎖長を変更したり、（Ｂ）成分の添加量を増減することによって調整できる。 In order for the cured product of the ultraviolet-curable silicone composition of the present invention to exhibit excellent rubber physical properties, the hardness after curing is in the range of 5 to 80 (TypeA), preferably 10 to 70 (TypeA). Is. The tensile strength after curing is preferably 0.5 MPa or more, more preferably 0.8 MPa or more. If the tensile strength is less than 0.5 MPa, the shaped article may become brittle. The elongation at break after curing is preferably 50% or more, more preferably 80% or more. If the elongation at break is less than 50%, the molded article cannot follow when folded and is easily cracked. Note that these values are values measured according to JIS-K6249. The rubber physical properties of the cured product can be adjusted by changing the chain length of the component (A) or by increasing or decreasing the addition amount of the component (B).
　以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.
［実施例１～３、比較例１～４］
　下記の各成分を表１に示す組成比（数値は質量部を表す）で混合して紫外線硬化性シリコーン組成物を得た。
なお、各例で得られた組成物の粘度は、回転粘度計を用いて２５℃で測定した値である。
　また、各組成物を枠に流し、アイグラフィックス株式会社製のランプＨ（Ｍ）０６－Ｌ－６１を用いて、窒素雰囲気下、２，０００ｍＪ／ｃｍ2の紫外線照射条件で硬化させ、厚さ２．０ｍｍの硬化シートを得た。得られた硬化シートについて、硬度、引張強さ及び切断時伸びをＪＩＳ－Ｋ６２４９に準じて測定した。また、硬化前の各組成物について臭気の強いものは×とし、弱いものは〇とした。得られた結果を表１に示す。 [Examples 1 to 3 and Comparative Examples 1 to 4]
The following components were mixed at the composition ratio shown in Table 1 (numerical values represent parts by mass) to obtain an ultraviolet curable silicone composition.
The viscosity of the composition obtained in each example is a value measured at 25 ° C. using a rotational viscometer.
In addition, each composition was poured into a frame and cured under a nitrogen atmosphere under an ultraviolet irradiation condition of 2,000 mJ / cm 2 using a lamp H (M) 06-L-61 manufactured by Eye Graphics Co., Ltd. A 2.0 mm thick cured sheet was obtained. The hardness, tensile strength and elongation at break of the obtained cured sheet were measured according to JIS-K6249. In addition, regarding each composition before curing, those having a strong odor were marked with X, and those having a weak odor were marked with ◯. The results obtained are shown in Table 1.
・（Ａ）成分
（Ａ－１）：上述した方法により製造した下記式（６）で表されるオルガノポリシロキサン
Figure JPOXMLDOC01-appb-C000013
 Component (A-1): organopolysiloxane represented by the following formula (6) produced by the above-mentioned method
Figure JPOXMLDOC01-appb-C000013
（Ａ－２）：上述した方法により製造した下記式（７）で表されるオルガノポリシロキサン
Figure JPOXMLDOC01-appb-C000014
 (A-2): Organopolysiloxane represented by the following formula (7) produced by the above method
Figure JPOXMLDOC01-appb-C000014
・（Ｂ）成分
（Ｂ－１）：下記式（８）で表されるオルガノポリシロキサン
Figure JPOXMLDOC01-appb-C000015
 Component (B-1): organopolysiloxane represented by the following formula (8)
Figure JPOXMLDOC01-appb-C000015
（Ｂ－２）：下記式（９）で表されるオルガノポリシロキサン
Figure JPOXMLDOC01-appb-C000016
 (B-2): Organopolysiloxane represented by the following formula (9)
Figure JPOXMLDOC01-appb-C000016
・（比較成分）
（Ｂ－３）：下記式（１０）で表されるオルガノジシロキサン
Figure JPOXMLDOC01-appb-C000017
 ・ (Comparative ingredients)
(B-3): an organodisiloxane represented by the following formula (10)
Figure JPOXMLDOC01-appb-C000017
（Ｂ－４）：下記式（１１）で表されるオルガノポリシロキサン
Figure JPOXMLDOC01-appb-C000018
 (B-4): Organopolysiloxane represented by the following formula (11)
Figure JPOXMLDOC01-appb-C000018
（Ｂ－５）：イソボルニルアクリレート（共栄社化学（株）製ライトアクリレートＩＢ－ＸＡ） (B-5): Isobornyl acrylate (light acrylate IB-XA manufactured by Kyoeisha Chemical Co., Ltd.)
・（Ｃ）成分
（Ｃ－１）：２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（ＢＡＳＦ社製Ｉｒｇａｃｕｒｅ　１１７３）
（Ｃ－２）：２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド（ＢＡＳＦ社製Ｉｒｇａｃｕｒｅ　ＴＰＯ） Component (C-1): 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF's Irgacure 1173)
(C-2): 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (Irgacure TPO manufactured by BASF)
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
　本発明の紫外線硬化性シリコーン組成物は充分に低粘度であり、硬化後は優れたゴム物性を示し、低臭気であるため、特に面露光方式や吊し上げ方式等の造形方式を用いる３Ｄプリンタ向けのシリコーン材料として有用である。一方、（Ｂ）成分を含まない比較例１では硬化が起こらず、（Ｂ）成分に代えて本発明の範囲外の重合性成分を使用した比較例２～４では、組成物が強い臭気を有したり（比較例２、４）、引張強さが不十分なものとなった（比較例３）。 The ultraviolet-curable silicone composition of the present invention has a sufficiently low viscosity, exhibits excellent rubber physical properties after curing, and has a low odor. Therefore, it is particularly suitable for a 3D printer using a molding method such as a surface exposure method or a lifting method. It is useful as a silicone material. On the other hand, in Comparative Example 1 containing no component (B), curing did not occur, and in Comparative Examples 2 to 4 in which the polymerizable component outside the scope of the present invention was used in place of the component (B), the composition had a strong odor. It had (Comparative Examples 2 and 4) or had insufficient tensile strength (Comparative Example 3).

Claims (4)

  1. （Ａ）下記式（１）で示されるオルガノポリシロキサン：１００質量部、
    Figure JPOXMLDOC01-appb-C000001
     ［式（１）中、ｎは８０≦ｎ≦１，０００を満たす数であり、Ｒ1は互いに独立に炭素原子数１～２０の一価炭化水素基であり、Ａは下記式（２）で示される基である。
    Figure JPOXMLDOC01-appb-C000002
     ［式（２）中、ｐは０≦ｐ≦１０を満たす数であり、ａは１≦ａ≦３を満たす数であり、Ｒ1は互いに独立に炭素原子数１～２０の一価炭化水素基であり、Ｒ2は酸素原子又はアルキレン基であり、Ｒ3はアクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基、またはメタクリロイルオキシアルキルオキシ基である。］］
    （Ｂ）下記式（３）で示されるオルガノポリシロキサン：５～１００質量部
    Figure JPOXMLDOC01-appb-C000003
     ［式（３）中、Ｒ4は、夫々独立に炭素原子数１～１０の一価脂肪族炭化水素基、アクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基及びメタクリロイルオキシアルキルオキシ基より選ばれる基であり、１分子中にアクリロイルオキシアルキル基、メタクリロイルオキシアルキル基、アクリロイルオキシアルキルオキシ基及びメタクリロイルオキシアルキルオキシ基から選ばれる基を２個有する。ｍは５≦ｍ≦５０を満たす数である。］
    及び
    （Ｃ）光重合開始剤：０．１～２０質量部
    を含有することを特徴とする紫外線硬化性シリコーン組成物。     (A) Organopolysiloxane represented by the following formula (1): 100 parts by mass,
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (1), n is a number satisfying 80 ≦ n ≦ 1,000, R 1 is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is the following formula (2). Is a group represented by.
    Figure JPOXMLDOC01-appb-C000002
     [In the formula (2), p is a number satisfying 0 ≦ p ≦ 10, a is a number satisfying 1 ≦ a ≦ 3, and R 1's are independently of each other a monovalent hydrocarbon having 1 to 20 carbon atoms. R 2 is an oxygen atom or an alkylene group, and R 3 is an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group, or a methacryloyloxyalkyloxy group. ]]
    (B) Organopolysiloxane represented by the following formula (3): 5 to 100 parts by mass
    Figure JPOXMLDOC01-appb-C000003
     [In the formula (3), R 4 are each independently a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, an acryloyloxyalkyl group, a methacryloyloxyalkyl group, an acryloyloxyalkyloxy group and a methacryloyloxyalkyloxy group. A group selected from the group consisting of acryloyloxyalkyl group, methacryloyloxyalkyl group, acryloyloxyalkyloxy group and methacryloyloxyalkyloxy group in one molecule. m is a number that satisfies 5 ≦ m ≦ 50. ]
    And (C) a photopolymerization initiator: 0.1 to 20 parts by mass, which is an ultraviolet-curable silicone composition.
  2. 　２５℃での粘度が１０～５，０００ｍＰａ・ｓである請求項１に記載の紫外線硬化性シリコーン組成物。 The ultraviolet curable silicone composition according to claim 1, which has a viscosity at 25 ° C of 10 to 5,000 mPa · s.
  3. 　請求項１又は２に記載の紫外線硬化性シリコーン組成物の硬化物。 A cured product of the ultraviolet curable silicone composition according to claim 1 or 2.
  4. 　３Ｄプリンタインク用である請求項１又は２に記載の紫外線硬化性シリコーン組成物。 The ultraviolet curable silicone composition according to claim 1 or 2 for a 3D printer ink.
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