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WO2015194378A1 - Composition pour former un objet moulé tridimensionnel, procédé de production d'un objet moulé tridimensionnel à l'aide de celui-ci et objet moulé tridimensionnel - Google Patents

Composition pour former un objet moulé tridimensionnel, procédé de production d'un objet moulé tridimensionnel à l'aide de celui-ci et objet moulé tridimensionnel Download PDF

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Publication number
WO2015194378A1
WO2015194378A1 PCT/JP2015/066060 JP2015066060W WO2015194378A1 WO 2015194378 A1 WO2015194378 A1 WO 2015194378A1 JP 2015066060 W JP2015066060 W JP 2015066060W WO 2015194378 A1 WO2015194378 A1 WO 2015194378A1
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Prior art keywords
molding
composition
dimensional
elastomers
dimensional structure
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English (en)
Japanese (ja)
Inventor
大造 林田
阿部　慈
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JSR Corp
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JSR Corp
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    • 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
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

  • the present invention relates to a composition for molding a three-dimensional model, a method for manufacturing a three-dimensional model using the composition, and a three-dimensional model.
  • a method for obtaining a three-dimensional (three-dimensional) shaped molded article generally, a cast molding method using a thermosetting resin or a photocurable resin, or a layered molding method using a thermoplastic resin or a photocurable resin.
  • An injection molding method using a thermoplastic resin is known.
  • a cast molding method using a thermosetting and soft polyurethane elastomer or silicone elastomer is often used.
  • Patent Document 1 a living body model used for medical students' education and practice, and practice by a doctor is known using a soft elastomer such as a silicone elastomer or a polyurethane elastomer.
  • the conventional three-dimensional molded object molding composition is not sufficient for molding a three-dimensional molded article having excellent moldability, flexibility and mechanical strength due to the characteristics of the resin material used.
  • the object of the present invention has been made in view of the above-mentioned problems of the prior art, and is a composition for molding a three-dimensional structure that is excellent in moldability, flexibility, and mechanical properties, and the same. It is providing the manufacturing method of a three-dimensional molded item, and a three-dimensional molded item.
  • the present inventors have obtained a three-dimensional structure molding composition.
  • a product when a polymer and a polar group-containing organic compound having a molecular weight of 1,000 or less are contained and are solid at least at 25 ° C., than a conventional three-dimensionally shaped article molding composition The inventors have found that excellent moldability, flexibility and mechanical properties can be obtained, and completed the present invention.
  • compositions for molding a three-dimensional model which contains a polymer and a polar group-containing organic compound having a molecular weight of 1,000 or less and is solid at least at 25 ° C.
  • the polar group-containing organic compound comprises an aliphatic carboxylic acid compound, an aliphatic carboxylic acid ester compound, an aliphatic ether compound, an aliphatic ketone compound, an aliphatic alcohol compound, an aliphatic amine compound, or a silyl ether compound.
  • DSC method differential scanning calorimetry
  • Three-dimensional molded object molding composition [4] The composition for molding a three-dimensional structure according to any one of [1] to [3], wherein the polymer includes an elastomer.
  • the elastomer is conjugated diene elastomer (excluding hydrogenated conjugated diene elastomer), hydrogenated conjugated diene elastomer, olefin elastomer, vinyl chloride elastomer, urethane elastomer, silicone elastomer, ester elastomer,
  • the composition for molding a three-dimensional structure according to any one of the above [1] to [4], which contains at least one selected from amide-based elastomers.
  • the elastomer contains at least one selected from conjugated diene elastomers (excluding hydrogenated conjugated diene elastomers), hydrogenated conjugated diene elastomers, and olefin elastomers.
  • a composition for molding a three-dimensional structure according to crab. [7] The composition for molding a three-dimensional structure according to any one of [1] to [4], wherein the elastomer includes a crystalline polyolefin.
  • the content ratio of the polymer and the polar group-containing organic compound is 100 parts by mass or more and 2,000 parts by mass or less with respect to 100 parts by mass of the polymer.
  • composition for three-dimensional molded item shaping molding in any one.
  • a method for producing a three-dimensional structure comprising a step of forming a three-dimensional structure using the composition for forming a three-dimensional structure according to any one of [1] to [9].
  • the step of forming the three-dimensional structure is a method in which the three-dimensional structure molding composition is fluidized by heating and then cooled and solidified.
  • the manufacturing method of a three-dimensional molded item which has the process of shape
  • the present invention it is possible to provide a composition in which the resulting three-dimensional model has a very high flexibility, a high strength, a little deterioration in performance during long-term storage, and a simple three-dimensional model.
  • the composition for molding a three-dimensional structure according to the present invention includes (A) a polymer (hereinafter also referred to as “polymer (A)”) and (B) a polar group-containing organic compound having a molecular weight of 1,000 or less. Hereinafter, it is also referred to as “polar group-containing organic compound (B)”) and is solid at least at 25 ° C.
  • thermoplastic elastomer As the polymer (A) used in the present invention, an elastomer is preferably used, and among them, a thermoplastic elastomer is more preferably used.
  • the elastomer has rubber elasticity and serves as a binder component that favorably includes the polar group-containing organic compound (B). Therefore, it is possible to prevent leakage of the polar group-containing organic compound (B) when the three-dimensional model is formed.
  • the thermoplastic elastomer is preferable because the molding process can be repeatedly performed at the time of manufacturing the three-dimensional model.
  • elastomer examples include conjugated diene elastomers (excluding hydrogenated conjugated diene elastomers), hydrogenated conjugated diene elastomers, olefin elastomers, vinyl chloride elastomers, urethane elastomers, ester elastomers, amide elastomers, and the like. Mention may be made of elastomers. These may be used alone or in combination of two or more.
  • conjugated diene-based elastomers (excluding hydrogenated conjugated diene-based elastomers), hydrogenated conjugated diene-based elastomers, and olefin-based elastomers are more preferable from the viewpoints of compatibility and excellent moldability, flexibility, and mechanical strength. preferable.
  • conjugated diene elastomers examples include natural rubber, and also include butadiene rubber (BR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), and isoprene. Synthetic rubbers such as rubber (IR) and butyl rubber (IIR) can also be mentioned.
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • NBR nitrile rubber
  • IIR butyl rubber
  • hydrogenated conjugated diene elastomers examples include styrene-ethylene / butylene-styrene block (co) polymer (SEBS), styrene-ethylene / propylene-styrene block (co) polymer (SEPS), and styrene-ethylene / butylene. Examples thereof include alkenyl aromatic compounds such as block (co) polymer (SEB) and styrene-ethylene / propylene block (co) polymer (SEP), and hydrogenated products of block (co) polymers of conjugated diene compounds.
  • SEBS styrene-ethylene / butylene-styrene block (co) polymer
  • SEPS styrene-ethylene / propylene-styrene block
  • SEP styrene-ethylene / butylene.
  • hydrogenated conjugated diene elastomers include alkenyl aromatic compounds such as styrene-ethylene / butylene-olefin crystal block (co) polymer (SEBC), olefin crystal block (co) polymers, and olefin crystals. Examples also include olefin crystal block (co) polymers such as ethylene / butylene-olefin crystal block (co) polymer (CEBC).
  • SEBC styrene-ethylene / butylene-olefin crystal block
  • CEBC olefin crystal block
  • a terminal-modified hydrogenated conjugated diene elastomer in which a functional group containing a polar group such as a carboxy group, a hydroxy group, or an amino group is bonded to the polymer terminal can also be used.
  • a functional group containing a polar group such as a carboxy group, a hydroxy group, or an amino group is bonded to the polymer terminal
  • an aliphatic carboxylic acid compound an aliphatic carboxylic acid ester compound, an aliphatic ether compound, an aliphatic ketone compound, an aliphatic alcohol compound, or an aliphatic amine compound as the polar group-containing organic compound described later.
  • an olefin crystal block (co) polymer such as olefin crystal-ethylene / butylene-olefin crystal block (co) polymer (CEBC).
  • olefin elastomer examples include ethylene / ⁇ -olefin copolymer rubber.
  • examples of the ethylene / ⁇ -olefin copolymer rubber include a binary copolymer rubber of ethylene and ⁇ -olefin (eg, ethylene / propylene copolymer rubber (EPM)), non-conjugated with ethylene and ⁇ -olefin.
  • terpolymer rubber with diene eg, ethylene / propylene / diene copolymer rubber (EPDM)).
  • Examples of the ⁇ -olefin include ⁇ -olefins having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms, such as propylene and 1-octene.
  • the ⁇ -olefin may be used alone or in combination of two or more.
  • Examples of the non-conjugated diene include ethylidene-2-norbornene.
  • a nonconjugated diene may be used individually by 1 type, and may use 2 or more types together.
  • urethane elastomer examples include, for example, a polyester urethane elastomer having a main chain generated by a reaction between a polyester diol and an isocyanate, and a polyether urethane elastomer having a main chain generated by a reaction between a polyether diol and an isocyanate. Can be mentioned.
  • ester elastomer examples include a copolymer rubber having a polyester segment and a polyether segment. Specific examples of the copolymer rubber having a polyester segment and a polyether segment include polybutylene terephthalate-based polyester-polytetramethylene glycol copolymer rubber.
  • amide elastomer examples include a copolymer rubber having a polyamide segment and a polyether segment.
  • examples of the polyamide segment include nylon 6, nylon 66, nylon 11 and nylon 12, and examples of the polyether segment include polyethylene glycol and polypropylene glycol.
  • the elastomer preferably has a polystyrene equivalent weight average molecular weight (hereinafter also referred to as “Mw”) of 10,000 to 700,000, more preferably 100,000 to 500,000, and more preferably 200,000 to 500,000. It is particularly preferred that In order to obtain the required mechanical properties, it is preferable that Mw is 10,000 or more, and in order to ensure fluidity for molding a three-dimensional shaped object molding composition, Mw is 700,000 or less. Preferably there is.
  • Mw polystyrene equivalent weight average molecular weight
  • the elastomer preferably has a melting point of 70 ° C. or higher and 140 ° C. or lower as measured by a differential scanning calorimetry (DSC method). It is more preferable that the temperature is not lower than 120 ° C and not higher than 120 ° C.
  • the melting point of the polymer (A) in this specification corresponds to Tim when measured according to JIS K-7121.
  • MFR melt flow rate
  • a polymer (A) is the value measured by 230 degreeC and the load of 21.2N based on JISK7210.
  • molding contains further polymers other than an elastomer from a viewpoint of improving the mechanical strength of the three-dimensional molded article obtained besides containing an elastomer. can do.
  • polystyrene examples include crystalline polyolefin, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polyamide, polyacetal, polycarbonate, polyphenylene ether, and polyester.
  • conjugated diene elastomers excluding hydrogenated conjugated diene elastomers
  • hydrogenated conjugated diene elastomers hydrogenated conjugated diene elastomers
  • olefin elastomers examples include crystalline polyolefin, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polyamide, polyacetal, polycarbonate, polyphenylene ether, and polyester.
  • the polymer (A) contains a crystalline polyolefin resin, the mechanical strength of the three-dimensional structure can be easily improved.
  • the crystalline polyolefin has a melting point equal to or higher than the melting point of the polar group-containing organic compound (B) when measured by a differential scanning calorimetry (DSC) method from the viewpoint of shape retention of a three-dimensional structure and suppression of bleeding in a high temperature region. It is preferable to have a melting point higher by 20 ° C. or more than the melting point of the polar group-containing organic compound (B). From the same viewpoint, the crystalline polyolefin preferably has a melting point higher than that of the thermoplastic elastomer.
  • the melting point of the crystalline polyolefin in this specification corresponds to Tim when measured according to JIS K-7121.
  • the weight average molecular weight (hereinafter also referred to as “Mw”) of the crystalline polyolefin in terms of polystyrene is preferably 1,000 to 10,000,000, and more preferably 10,000 to 5,000,000. It is preferably 10,000 to 1,000,000.
  • polyolefin means a polymer obtained by polymerizing at least one olefin selected from ethylene and ⁇ -olefin.
  • the polymerization method is not particularly limited, and for example, a polyolefin can be produced using a conventionally known polymerization method (eg, high pressure method, low pressure method).
  • Examples of the ⁇ -olefin include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene and 3-ethyl- Examples thereof include ⁇ -olefins having 3 to 12 carbon atoms such as 1-pentene, 1-octene, 1-decene and 1-undecene.
  • crystalline polyolefin examples include crystalline polyethylene, crystalline polypropylene, crystalline polybutene, and crystalline polymethylpentene. From the viewpoint of versatility, it is preferable to use crystalline polyethylene and crystalline polypropylene. It is particularly preferable to use polyethylene.
  • crystalline polyethylene examples include low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), linear low density polyethylene (LLDPE), ethylene / propylene copolymer, and ethylene / octene copolymer. It is done.
  • these crystalline polyethylenes may be biopolyethylenes made from ethylene made from renewable (plant) resources.
  • Examples of crystalline polypropylene include propylene / ⁇ -olefin copolymers, propylene / ethylene copolymers, propylene / butene copolymers, and propylene / ethylene / butene copolymers.
  • the crystalline polypropylene may be either a homopolymer or a copolymer.
  • the melting point of crystalline polyethylene measured by the differential scanning calorimetry (DSC) method is preferably 80 to 140 ° C., more preferably 90 to 140 ° C. Furthermore, as crystalline polyethylene, it is preferable to use what has melting
  • the melting point of crystalline polypropylene measured by a differential scanning calorimetry (DSC) method is preferably 100 to 170 ° C., more preferably 120 to 170 ° C. Furthermore, it is preferable to use what has melting
  • the melt flow rate (MFR) of crystalline polyethylene according to JIS K7210 at a temperature of 190 ° C. and a load of 2.16 kg is preferably 0.01 to 100 g / 10 min, more preferably 0.1 to 80 g / 10. Minutes.
  • the melt flow rate (MFR) of crystalline polypropylene according to JIS K7210 at a temperature of 230 ° C. and a load of 2.16 kg is preferably 0.01 to 100 g / 10 minutes, more preferably 0.1 to 80 g / 10. Minutes.
  • the MFR of crystalline polyethylene and crystalline polypropylene is 0.01 g / 10 min or more, the moldability and the like are further improved.
  • these MFRs are 100 g / 10 min or less, the suppression of bleeding of the polar group-containing organic compound (B) is further improved.
  • the content of the polymer other than the elastomer is preferably 0.1 parts by mass or more and 100 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the elastomer. More preferably, it is at least 30 parts by mass.
  • the content of the polymer other than the elastomer is within the above range, it is preferable from the viewpoint of increasing the compatibility and suppressing bleeding of the polar group-containing organic compound (B).
  • polymers other than an elastomer may be used individually by 1 type, and may use 2 or more types together.
  • the content of the polymer (A) in the composition for molding a three-dimensional structure is preferably 0.5% by mass or more and 50% by mass or less from the viewpoint of moldability, flexibility, and mechanical strength.
  • the content is more preferably no less than 40% by mass and no greater than 40% by mass, and still more preferably no less than 5% by mass and no greater than 30% by mass.
  • (B) Polar group-containing organic compound having a molecular weight of 1,000 or less
  • the molecular weight of the polar group-containing organic compound (B) is 1 from the viewpoint of obtaining excellent moldability, flexibility and mechanical strength of the three-dimensional structure. Is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. Moreover, it is preferable that the molecular weight of a polar group containing organic compound (B) is 50 or more from a viewpoint of obtaining the moldability, the softness
  • Examples of the polar group include a carboxy group, —C ( ⁇ O) —O— (ester bond), —O— (ether bond), carbonyl group, hydroxy group, amino group, sulfo group, amide group, and the like. . From the viewpoint of obtaining excellent moldability, flexibility and mechanical strength of a three-dimensional model, a carboxy group, —C ( ⁇ O) —O— (ester bond), —O— (ether bond), carbonyl group, hydroxy A group or an amino group is preferably used, and a carboxy group or an ester bond is more preferably used.
  • the polar group-containing organic compound (B) include aliphatic carboxylic acid compounds, aliphatic carboxylic acid ester compounds, aliphatic ether compounds, aliphatic ketone compounds, aliphatic alcohol compounds, aliphatic amines. And at least one selected from the group consisting of compounds and silyl ether compounds.
  • the number in the parenthesis of the compound illustrated below shows melting
  • aliphatic carboxylic acid compound for example, an aliphatic carboxylic acid having 5 to 30 carbon atoms can be used. Aliphatic carboxylic acid compounds are roughly classified into saturated aliphatic carboxylic acids and unsaturated aliphatic carboxylic acids. The saturated aliphatic carboxylic acid and unsaturated aliphatic carboxylic acid may be either linear or branched.
  • saturated aliphatic carboxylic acids examples include hexanoic acid ( ⁇ 3 ° C.), heptanoic acid ( ⁇ 7.5 ° C.), octanoic acid (17 ° C.), pelargonic acid (11 to 13 ° C.), and decanoic acid (16 ° C.).
  • linear saturated aliphatic carboxylic acids having 6 to 18 carbon atoms are preferably used from the viewpoint of availability.
  • Examples of the unsaturated aliphatic carboxylic acid include oleic acid (16 ° C.), palmitoleic acid ( ⁇ 0.1 ° C.), arachidonic acid ( ⁇ 49 ° C.), linoleic acid ( ⁇ 5 ° C.), ⁇ -linolenic acid ( ⁇ 11 ° C.) and docosahexaenoic acid ( ⁇ 44 ° C.).
  • oleic acid (16 ° C.), palmitoleic acid ( ⁇ 0.1 ° C.), arachidonic acid ( ⁇ 49 ° C.), linoleic acid ( ⁇ 5 ° C.), ⁇ -linolenic acid ( ⁇ 11 ° C.) and docosahexaenoic acid ( ⁇ 44 ° C.).
  • a straight chain unsaturated aliphatic acid having 6 to 20 carbon atoms is preferably used from the viewpoint of availability.
  • ester compound of the aliphatic carboxylic acid for example, a long-chain aliphatic carboxylic acid ester having 5 to 30 carbon atoms can be used. Specifically, methyl oleate ( ⁇ 20 ° C.), vinyl stearate (28 ° C), dimethyl sebacate (21 ° C), butyl stearate (19 ° C), isopropyl stearate (16 ° C), isopropyl palmitate (11 ° C), propyl palmitate (10 ° C).
  • aliphatic carboxylic acid ester compounds methyl, ethyl, propyl and butyl esters of straight-chain saturated aliphatic carboxylic acids having 6 to 18 carbon atoms are preferably used from the viewpoint of availability.
  • an aliphatic ether compound for example, an aliphatic ether having 14 to 60 carbon atoms can be used, and specific examples include heptyl ether ( ⁇ 24 ° C.) and octyl ether ( ⁇ 7 ° C.).
  • an ether compound (symmetric type) having a single oxygen atom and a symmetric structure from the viewpoint that the excellent moldability, flexibility and mechanical strength of the three-dimensional structure can be obtained and synthesis is easy.
  • Ether compounds are preferably used.
  • an aliphatic ketone compound for example, an aliphatic ketone having 6 to 30 carbon atoms can be used, and specific examples include 2-nonanone (-9 ° C.) and the like. Among these, an aliphatic ketone having one oxygen atom is preferably used from the viewpoint that excellent moldability, flexibility and mechanical strength of the three-dimensional structure can be obtained and synthesis is easy.
  • aliphatic alcohol compound for example, an aliphatic alcohol having 6 to 30 carbon atoms can be used. Specifically, 1-octanol ( ⁇ 16 ° C.), 1-dodecanol (24 ° C.), 2-dodecanol ( 19 ° C.). Among these, from the viewpoint of obtaining excellent moldability, flexibility and mechanical strength of the three-dimensional structure, an alcohol compound having a hydroxyl group at the molecular end (terminal alcohol compound) is preferably used.
  • aliphatic amine compounds for example, an aliphatic amine having 5 to 30 carbon atoms can be used. Aliphatic amine compounds are roughly classified into saturated aliphatic amines and unsaturated aliphatic amines. The amines are roughly classified into primary amines, secondary amines, and tertiary amines. Examples of saturated aliphatic primary amines include octylamine ( ⁇ 18 ° C.) and dodecylamine (24 to 29 ° C.). Examples of unsaturated aliphatic primary amines include oleylamine (8 to 18 ° C.).
  • saturated aliphatic tertiary amine examples include dimethyldodecylamine ( ⁇ 20 to 10 ° C.), dimethylhexadecylamine (3 to 8 ° C.), dimethyloctadecylamine (22 to 26 ° C.) and the like.
  • unsaturated aliphatic tertiary amine examples include dimethyloleylamine (less than 0 ° C.).
  • silyl ether compound for example, silyl ethers having 5 to 30 carbon atoms can be used. Specific examples include hexyltrimethoxysilane (less than 0 ° C.), decyltrimethoxysilane ( ⁇ 37 ° C.), and the like. It is done.
  • the melting point of the polar group-containing organic compound (B) measured by the differential scanning calorimetry (DSC method) is from ⁇ 50 ° C. to 30 ° C. from the viewpoint of excellent formability, flexibility and mechanical strength of the three-dimensional structure. It is preferably in the range of ⁇ 40 ° C. to 25 ° C., more preferably in the range of ⁇ 30 ° C. to 20 ° C.
  • a polar group containing organic compound (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content of the polar group-containing organic compound (B) is preferably 50 parts by mass or more with respect to 100 parts by mass of the polymer (A) from the viewpoint of obtaining the excellent flexibility of the three-dimensional structure. More preferably, it is more than 150 mass parts, More preferably, it is 200 mass parts or more. Further, the content of the polar group-containing organic compound (B) is preferably 3,000 parts by mass or less and 2,000 parts by mass or less from the viewpoint of obtaining the excellent mechanical strength of the three-dimensional model. More preferably, it is more preferably 1,500 parts by mass or less, and particularly preferably 1,000 parts by mass or less.
  • the content of the polar group-containing organic compound (B) is preferably 20% by mass or more with respect to the entire three-dimensional structure molding composition from the viewpoint of obtaining excellent flexibility of the three-dimensional structure.
  • the content is more preferably at least mass%, more preferably at least 60 mass%, particularly preferably at least 70 mass%.
  • the content of the polar group-containing organic compound (B) is preferably 99.5% by mass or less and 97% by mass or less from the viewpoint of obtaining excellent mechanical strength of the three-dimensional model. More preferably, it is more preferably 95% by mass or less.
  • the polar group-containing organic compound (B) has a melting point higher than 30 ° C. measured by the differential scanning calorimetry (DSC method) from the viewpoint of obtaining a three-dimensional shaped article having further excellent mechanical strength. Can also be used.
  • Examples of the compound having a melting point higher than 30 ° C. include the above-mentioned aliphatic carboxylic acid compounds, aliphatic carboxylic acid ester compounds, aliphatic ether compounds, aliphatic ketone compounds, aliphatic alcohol compounds, aliphatic amine compounds, silyl ether compounds. Among them, a compound having a melting point higher than 30 ° C. can be suitably used. In addition, the number in the parenthesis of the compound illustrated below shows melting
  • Examples of the aliphatic carboxylic acid compound include monocarboxylic acids such as dodecanoic acid (44 ° C.), tetradecanoic acid (58 ° C.), hexadecanoic acid (64 ° C.), and octadecanoic acid (69 ° C.), or octane diacid (141 to 144 ° C.), decanedioic acid (131-134.5 ° C.), dodecanedioic acid (127-129 ° C.), heptanedioic acid (103-105 ° C.), hexanedioic acid (152 ° C.), and the like. Can be mentioned. Among these compounds, it is preferable to use a dicarboxylic acid compound from the viewpoint of obtaining a three-dimensionally shaped product particularly excellent in mechanical strength.
  • ester compound of the aliphatic carboxylic acid examples include methyl laurate (44 to 46 ° C.) and methyl stearate (37 to 41 ° C.).
  • Examples of the aliphatic ether compound include tetradecyl ether (45 ° C.) and hexadecyl ether (55 ° C.).
  • Examples of the aliphatic ketone compound include 2-pentadecanone (40 ° C.), 3-hexadecanone (43 ° C.), 8-pentadecanone (43 ° C.), 4,4-bicyclohexanone (118 ° C.), and the like.
  • aliphatic alcohol compounds examples include 1-tetradecanol (39 ° C.), 7-tetradecanol (42 ° C.), 1-octadecanol (59 ° C.), 1-eicosanol (65 ° C.), 1,10-decane. Diol (73 degreeC) etc. are mentioned.
  • Examples of the aliphatic amine compound include octadecylamine (49 to 56 ° C.).
  • the content of the polar group-containing organic compound (B) having a melting point higher than 30 ° C. is preferably 0.1% by mass or more and 30% by mass or less of the entire polar group-containing organic compound (B), and 0.5% by mass. It is more preferably 20% by mass or less, and further preferably 1% by mass or more and 15% by mass or less.
  • the composition for molding a three-dimensional structure according to the present invention is a colorant, a filler, a plasticizer, a stabilizer, an anti-aging agent, an oxidation, in a range not impairing the effects of the present invention, for the purpose of imparting a function according to the use.
  • the composition for molding a three-dimensional structure of the present invention is used for a living organ model
  • the composition for forming a three-dimensional structure is colored with a colorant in a desired color in order to approximate the three-dimensional structure to the living organ model. It is preferable that
  • the content of the additive varies depending on the type in order to impart the desired function. From the viewpoint of maintaining the productivity at the time of molding of a three-dimensional molded article by the three-dimensional molded article molding composition, the content of the additive can maintain fluidity at a temperature equal to or higher than the melting point of the elastomer. The amount is desirable.
  • the content of the additive is preferably 0.01% by mass or more and 50% by mass or less, and 0.1% by mass or more and 40% by mass or less with respect to 100% by mass of the three-dimensional molded object molding composition. Is more preferable, and 1% by mass or more and 30% by mass or less is particularly preferable. From the viewpoint of imparting a desired function to the three-dimensional molded object molding composition, the content of the additive is particularly preferably 1% by mass or more, and the fluidity and molding of the three-dimensional molded article molding composition. From the viewpoint of maintaining the properties, it is particularly preferably 30% by mass or less.
  • molding has a property which is a solid state in 25 degreeC and 1.01325 * 10 ⁇ 5 > Pa.
  • the solid state means that the deformation or volume change is smaller than that of a liquid or gas, and a gel state is particularly preferable.
  • the composition for molding a three-dimensional structure has a property of being at least solid at 25 ° C. as a standard for general indoor temperature.
  • the temperature at which the composition for molding a three-dimensional structure is solid depends on the composition and is equal to or lower than a predetermined temperature.
  • the solid shape as a fixed shape cannot be maintained at a temperature higher than a predetermined temperature.
  • molding is thermoplastic from a viewpoint of obtaining the outstanding moldability.
  • the flow start temperature (pour point) of the three-dimensional molded object molding composition is 30 ° C. or higher and 200 ° C. or lower.
  • the flow start temperature refers to the lowest temperature at which the solid shape of the three-dimensional molded object molding composition is not maintained.
  • the composition for molding a three-dimensional structure has fluidity at 30 ° C. or higher and may have a property that the solid state cannot be maintained.
  • the flow start temperature is in accordance with “10. Flow test” of JIS K7311.
  • a tester CFT-500 (manufactured by Shimadzu Corporation)
  • the rate of temperature increase 3 ° C./min
  • start temperature 25 ° C.
  • test load 98 N
  • use die can be measured under conditions of a diameter of 1 mm and a length of 1 mm.
  • a temperature is started at the same time as a test load is applied by a die, and the temperature at which flow begins to flow out of the die is determined as the flow start temperature of the three-dimensional object molding composition (processing) Temperature).
  • the method of manufacturing the three-dimensional modeled object which consists of a composition for the above-mentioned three-dimensional modeled object is not limited in particular, after fluidizing the composition for three-dimensional modeled object by heating, It is preferable to have the process of cooling and shape
  • the composition for molding a three-dimensional model is fluidized by heating and injected into a mold having an inner surface shape corresponding to the shape of the target three-dimensional model, the three-dimensional model that is cooled and solidified is used.
  • a desired three-dimensional model can be obtained by molding and then removing the obtained three-dimensional model from the mold.
  • the material of the mold is not particularly limited, and may be either resin or metal.
  • the mold can also be shaped using rapid prototyping techniques such as stereolithography, powder sintering, ink jet, sheet lamination, and extrusion.
  • a three-dimensional molded item can also be shape
  • the composition for molding a three-dimensional structure that has been fluidized by heating is discharged from the dispense head onto a forming stage, and the three-dimensional object having a desired shape is obtained by moving the dispense head three-dimensionally according to the forming pattern. You can also.
  • the composition for molding a three-dimensional structure used in the method for manufacturing a three-dimensional structure is preferably a filament or a pellet.
  • Three-dimensional modeled object has excellent flexibility and mechanical strength, and is used for medical simulations such as human and animal biological tissues, medical device parts such as mouse inhalation pads and joint fixing devices, and rooms and automobiles. It can be suitably used as a flexible part for interior.
  • medical simulations such as human and animal biological tissues, medical device parts such as mouse inhalation pads and joint fixing devices, and rooms and automobiles. It can be suitably used as a flexible part for interior.
  • biological tissues such as stomach, small intestine, large intestine, liver and pancreas, circulatory organs such as heart and blood vessels, reproductive organs such as prostate, and urinary organs such as kidneys, and these living organs A living tissue.
  • the three-dimensional modeled object may be a laminate in which two or more types of three-dimensional modeled molding compositions are stacked from the viewpoint of increasing mechanical strength or approximating a living organ.
  • a three-dimensional molded item can also be made into a laminated body using the composition for three-dimensional molded item shaping
  • the hardness of the three-dimensional modeled object is not particularly limited, and for example, the hardness according to Duro-00 can be 0 or more and 80 or less. This hardness is measured by the measuring method shown in the following examples.
  • the breaking strength of the three-dimensional structure is not particularly limited, and can be, for example, 0.01 MPa or more and 20.0 MPa or less. In addition, this breaking strength is measured by the measuring method shown in the following Example.
  • the elongation at break of the three-dimensional structure is not particularly limited, and can be, for example, 10% or more and 2,000% or less.
  • this breaking elongation is measured by the measuring method shown in the following Example.
  • Example 1 15 parts by mass of the hydrogenated conjugated diene copolymer obtained in the above synthesis example as a polymer component, 80 parts by mass of oleic acid (melting point: 16 ° C.) and 5 parts by mass of dotecandioic acid as a polar group-containing organic compound, A thermoplastic three-dimensional molded object molding composition was manufactured by heating to 100 ° C. in a glass flask, mixing for 1 hour, and cooling to room temperature. And the obtained composition for three-dimensional molded object shaping
  • the produced sample piece had a hardness (Duro-00) of 18, a breaking strength of 0.06 MPa, a breaking elongation of 350%, and long-term storage stability was also acceptable (good).
  • Examples 2 and 3 In Examples 2 and 3, the three-dimensional object molding composition and the sample piece (three-dimensional object) are the same as Example 1 except that the distribution composition is changed from Example 1 as described in Table 1. Manufactured.
  • Example 4 to 7 in addition to the hydrogenated conjugated diene copolymer obtained in the above synthesis example, YF30 (melting point: 108 ° C.) manufactured by Nippon Polychem Co., Ltd. as a low density polyethylene was used as the polymer.
  • a composition for forming a three-dimensional object and a sample piece (three-dimensional object) were manufactured in the same manner as in Example 1 except that the distribution composition was changed from Example 1 as described in Table 1.
  • Comparative Example 1 In Comparative Example 1, no polymer was used, and a composition containing only 95 parts by mass of oleic acid (melting point: 16 ° C.) and 5 parts by mass of dotecanic acid as a polar group-containing organic compound was used. In this case, since it was liquid at room temperature (25 ° C.), a sample piece (three-dimensional model) could not be produced.
  • Comparative Example 2 In Comparative Example 2, the composition for molding a three-dimensional structure and the sample piece were the same as Example 1 except that tetradecane (melting point: 20 ° C.) as a nonpolar organic compound was used instead of the polar group-containing organic compound. (3D object) was manufactured.
  • the hardness of the prepared sample piece (Duro-00) was sufficiently soft as 15, but the breaking strength was so low that it could not be measured, the breaking elongation was as small as 80%, and the long-term storage stability was also unacceptable. It was.
  • the molded sample piece (three-dimensional model) was measured with a durometer (Duro-00 type) manufactured by Teclock. (Strength measurement / elastic modulus measurement)
  • a sample piece of a molded three-dimensional model was punched into a dumbbell shape (No. 6 size), and then a tensile strength test was performed using a Shimadzu Material Strength Tester (EZ Graph). (Long-term storage stability) The molded sample piece is allowed to stand at room temperature for 1 week or longer.
  • the above strength change does not decrease by 5% or more, and there is no change in the growth of bacteria such as mold or strange odor. In cases where there was a decrease of 5% or more, and there were changes in the growth of bacteria such as mold and changes in off-flavor, etc., it was judged as “failed”.
  • the flexibility is very high, and the mechanical strength of the breaking strength and elongation at break is also high, resulting in a decrease in performance in long-term storage. It turned out that few three-dimensional molded objects are obtained.
  • the composition for three-dimensional structure molding of the present invention is thermoplastic. Therefore, according to the composition for molding a three-dimensional object, it is possible to form the three-dimensional object by simple steps of heating and cooling, and it is also possible to repeatedly form the three-dimensional object.
  • the composition for molding a three-dimensional object according to the present invention is applied to the formation of a three-dimensional object such as cast molding or additive manufacturing.
  • the resulting three-dimensional model is excellent in flexibility and mechanical strength, used for medical simulation as a living organ model of humans and animals such as liver and kidney, and manufacturing medical equipment parts such as mouse inhalation pads and joint fixing devices, Furthermore, it can be expected to be used in various fields such as the production of flexible parts for interiors of rooms and automobiles.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Instructional Devices (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Abstract

　La présente invention concerne une composition visant à former un objet moulé tridimensionnel, ladite composition étant solide à une température de 25 °C et comprenant un polymère et un composé organique contenant un groupe polaire ayant un poids moléculaire de 1 000 ou moins. Le composé organique contenant un groupe polaire est au moins une substance choisie dans le groupe constitué de composés d'acides carboxyliques aliphatiques, d'esters d'acides carboxyliques aliphatiques, de composés d'éthers aliphatiques, de composés de cétones aliphatiques, de composés d'alcools aliphatiques, de composés d'amines aliphatiques et de composés d'éthers de silyle. Le polymère est au moins une substance choisie dans le groupe constitué d'élastomères diéniques conjugués (à l'exclusion des élastomères diéniques conjugués hydrogénés), d'élastomères diéniques conjugués hydrogénés, d'élastomères oléfiniques, d'élastomères de chlorure de vinyle, d'élastomères d'uréthane, d'élastomères d'ester et d'élastomères d'amide.
PCT/JP2015/066060 2014-06-16 2015-06-03 Composition pour former un objet moulé tridimensionnel, procédé de production d'un objet moulé tridimensionnel à l'aide de celui-ci et objet moulé tridimensionnel Ceased WO2015194378A1 (fr)

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WO2017030145A1 (fr) * 2015-08-19 2017-02-23 デンカ株式会社 Composition de résine pour modèles d'organes
WO2020217822A1 (fr) * 2019-04-26 2020-10-29 株式会社ｍｉｃｒｏ－ＡＭＳ Procédé de moulage de résine
JP2020183109A (ja) * 2019-04-26 2020-11-12 株式会社ｍｉｃｒｏ−ＡＭＳ 樹脂成形方法
JP2020183110A (ja) * 2019-04-26 2020-11-12 株式会社ｍｉｃｒｏ−ＡＭＳ 樹脂成形方法
CN116036366A (zh) * 2020-01-16 2023-05-02 四川大学 一种人工心脏瓣膜

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CN116036366A (zh) * 2020-01-16 2023-05-02 四川大学 一种人工心脏瓣膜

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