TWI607065B - Resin composition for three-dimensional printing - Google Patents

Description

Three-dimensional printing resin composition

The present invention relates to a resin composition, and more particularly to a resin composition for three-dimensional printing.

Compared to two-dimensional (2D) printing technology - that is, printing an image on a flat paper or object surface, three-dimensional (3D) printing refers to a method of forming a three-dimensional object. 3D printing is mainly used to shorten the time and expense required to prepare a prototype, and therefore, 3D printing can be used in various fields such as personal products, medical products, automobile parts, architectural articles, or the like.

One of the common 3D printing methods is fused deposition modeling (FDM), in which a thermoplastic resin is extruded through a nozzle to extrude a linear material, and the layers are stacked to produce a three-dimensional workpiece. Among them, raw materials which are often used in the FDM process may include, for example, acrylonitrile butadiene styrene (ABS), polylactic acid (PLA) or the like.

As a main material, ABS is an engineering plastic with good mechanical properties and can be applied to different 3D printing categories. However, ABS has problems such as easy deformation of the shape during processing (for example, printing failure due to severe warpage caused by thermal expansion and contraction) and significant odor during processing. Therefore, it is not suitable for operation in an office or studio.

The present invention provides a resin composition for three-dimensional printing which has improved warpage resistance and low processing odor, improves three-dimensional printing yield, and can meet the requirements of indoor space operation.

The resin composition for three-dimensional printing of the present invention comprises more than 70% by weight to 95% by weight of the rubber-modified styrene-based resin copolymer and 5% by weight to less than 30% by weight of the (meth) acrylate-styrene system Copolymer. The rubber-modified styrenic resin copolymer includes a dispersed phase formed by 1% by weight to 25% by weight of rubber particles and a continuous phase formed by 75% by weight to 99% by weight of the styrene-based resin copolymer. The rubber particles are formed of a rubbery polymer. The styrene resin copolymer includes a first styrene monomer unit and a first (meth) acrylate monomer unit, wherein the first styrene resin copolymer content is 100 parts by weight, the first The content of the styrene monomer unit ranges from 25 parts by weight to 65 parts by weight and the content of the first (meth) acrylate monomer unit ranges from 35 parts by weight to 75 parts by weight. The (meth) acrylate-styrene copolymer includes 40% by weight to 80% by weight of the second (meth) acrylate monomer unit and 20% by weight to 60% by weight of the second styrene monomer unit.

In an embodiment of the invention, the styrene resin copolymer may further include an acrylonitrile-based monomer unit, and the first styrene is 100 parts by weight of the styrene resin copolymer content. The content of the monomer unit ranges from 25 parts by weight to 64 parts by weight, and the content of the first (meth) acrylate monomer unit ranges from 35 parts by weight to 74 parts by weight, the acrylonitrile monomer unit The content ranges from 1 part by weight to 20 parts by weight.

In an embodiment of the invention, the styrene resin copolymer may further include an acrylonitrile-based monomer unit, and the first styrene is 100 parts by weight of the styrene resin copolymer content. The content of the monomer unit ranges from 27 parts by weight to 50 parts by weight, and the content of the first (meth) acrylate monomer unit ranges from 40 parts by weight to 70 parts by weight, the acrylonitrile monomer unit The content ranges from 2 parts by weight to 16 parts by weight.

In an embodiment of the invention, the rubbery polymer may comprise a polydiene rubber.

In an embodiment of the invention, the polydiene rubber is selected from the group consisting of butadiene rubber, isoprene rubber, chloroprene rubber, styrene-diene rubber, and acrylonitrile rubber. Group of.

In an embodiment of the invention, the rubbery polymer may include 92% by weight to 99% by weight of the styrene-diene block copolymer and 1% by weight to 8% by weight of the polydiene rubber .

In an embodiment of the present invention, the rubbery polymer may further include 93% by weight to 99% by weight of the styrene-diene block copolymer and 1% by weight to 7% by weight of the polydiene system. rubber.

In an embodiment of the present invention, the rubbery polymer may further include 94% by weight to 99% by weight of the styrene-diene block copolymer and 1% by weight to 6% by weight of the polydiene system. rubber.

In an embodiment of the invention, the (meth) acrylate-styrene copolymer may further include 40% by weight or less of copolymerizable monomer units.

In an embodiment of the invention, the (meth) acrylate-styrene copolymer may have a softening point temperature of from 100 ° C to 110 ° C.

Based on the above, the resin composition for three-dimensional printing according to the present invention is not easily warped due to heat expansion and contraction during processing, and can reduce the odor generated during processing, and contributes to the improvement of three-dimensional printing yield. Meet the needs of indoor space operations.

The above described features and advantages of the invention will be apparent from the following description.

Hereinafter, embodiments of the invention will be described in detail. However, these embodiments are illustrative, and the disclosure of the present invention is not limited thereto.

In an embodiment of the invention, the resin composition for three-dimensional printing comprises 70% by weight to 95% by weight of a rubber-modified styrene-based resin copolymer and 5% by weight to 30% by weight of a (meth) acrylate system. - a styrene copolymer. Among them, the rubber-modified styrene-based resin copolymer may include a dispersed phase formed by 1% by weight to 25% by weight of rubber particles and a continuous phase formed by 75% by weight to 99% by weight of the styrene-based resin copolymer. The rubber particles may be formed of a rubbery polymer. The styrene resin copolymer may contain 25 parts by weight to 65 parts by weight of the first styrene monomer unit and 35 parts by weight to 75 parts by weight of the first (meth) acrylate monomer unit. The (meth) acrylate-styrene copolymer may include 40% by weight to 80% by weight of the second (meth) acrylate monomer unit and 20% by weight to 60% by weight of the second styrene system. Monomer unit. The ingredients mentioned are explained in detail below.

< Rubber particles >

The rubber particles of the present invention have a weight average particle diameter of, for example, 0.15 μm to 1.5 μm, preferably 0.2 μm to 1.0 μm, and most preferably 0.25 μm to 0.7 μm. In detail, when the weight average particle diameter of the rubber particles is less than 0.15 μm, the impact strength and elongation of the resin composition are both lowered; and when the weight average particle diameter of the rubber particles is more than 1.5 μm, the transparency of the resin composition is poor. Specifically, the weight average particle diameter of the rubber particles is measured by a photograph taken by an ultrathin sectioning method in a transmission electron microscope, and more than 300 rubber particles are required in the photograph. In addition, the weight average particle diameter of the rubber particles may be adjusted by one or more of the following methods: rubber type selection, such as viscosity, molecular weight, cis/trans/vinyl (cis/trans/vinyl) Microstructure, etc.; type of polymerization reactor and stirring speed; reaction temperature; conversion ratio of polymerized monomer; type and amount of solvent.

< Rubbery polymer >

The rubbery polymer of the present invention may form rubber particles, the rubbery polymer may include a polydiene rubber, or may include 92% by weight to 99% by weight of a styrene-diene block copolymer and 1 weight. % to 8% by weight of the polydiene rubber, but is not limited thereto. The weight ratio of the styrene-diene block copolymer to the polydiene rubber is preferably from 93% by weight to 99% by weight/1% by weight to 7% by weight, most preferably from 94% by weight to 99% by weight/ 1% by weight to 6% by weight. In more detail, when the weight ratio of the polydiene rubber is less than 1% by weight, the impact resistance of the resin composition is poor and the elongation is lowered, and when the weight ratio of the polydiene rubber is more than 8% by weight At the time, the transparency of the resin composition is not good.

< Polydiene rubber >

Polydiene rubbers include, but are not limited to, butadiene rubber, isoprene rubber, chloroprene rubber, styrene-diene rubber, or acrylonitrile rubber.

The polydiene rubber is, for example, a homopolymer obtained by polymerizing a diene monomer. Specifically, the method for forming the polydiene rubber includes, but is not limited to, an organic lithium compound as an initiator in the presence of an organic solvent, and a polymerization reaction using a diene monomer and an appropriate amount of a solvent. The structure of the polydiene rubber is either a star type or a linear type, but is not limited thereto. From another point of view, the polydiene rubber may be a low-cis polydiene rubber, and its typical weight composition range of cis/vinyl is, for example, 30%. ~40%/5%~40%

The organolithium compound used for forming the polydiene rubber is a compound containing one or more lithium atoms in the molecule, and examples thereof may be, for example, ethyllithium, n-pentyllithium, isopropyllithium, n-butyllithium, or the like. Butyl butyl, hexyl lithium, cyclohexyl lithium, phenyl lithium, benzyl lithium, naphthyl lithium, tert-butyl lithium, trimethylene dilithium, tetramethylene dilithium, butadiene dilithium Or isoprene double lithium and the like. The above-exemplified compounds may be used alone or in combination of two or more.

Examples of the diene monomer used to form the polydiene rubber may be, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1, 3-butadiene, 1,3-pentadiene or 1,3-hexadiene, etc., of which 1,3-butadiene or 2-methyl-1,3-butadiene is preferred. The above-exemplified compounds may be used alone or in combination of two or more.

Further, in the polydiene rubber solution having a concentration of 5% by weight of styrene as a solvent, the solution viscosity of the polydiene rubber is, for example, 30 cps to 250 cps, preferably 60 cps to 230 cps, more preferably 70 cps. To 210cps. In detail, when the solution viscosity of the polydiene rubber is less than 30 cps, the impact resistance of the resin composition is deteriorated and the elongation is lowered. When the solution viscosity of the polydiene rubber is higher than 250 cps, the transparency of the resin composition is deteriorated. Further, the polydiene rubber has a weight average molecular weight of, for example, 300,000 to 800,000, preferably 350,000 to 700,000. Specifically, within the above range, the resin composition has a good balance of physical properties between transparency, impact resistance and elongation.

< Styrene - Diene block copolymer >

The styrenic-diene block copolymer of the present invention is, for example but not limited to, a block copolymer or a disordered copolymer, of which a block copolymer is preferred. The block structure of the styrene-diene block copolymer may be a homopolymer block structure, a partial random block structure, or a tapered block (taper-block). A configuration in which a block structure having an increasing composition is preferred. Further, the styrene-diene block copolymer of the present invention has a weight average molecular weight of, for example, 100,000 to 200,000, preferably 100,000 to 180,000. Specifically, in the above range, the balance of physical properties such as transparency, impact resistance, and elongation of the resin composition is preferable.

Further, a method of forming a styrene-diene block copolymer includes, but is not limited to, using an organolithium compound as a starter in the presence of an organic solvent, and a styrene monomer or a diene monomer. And an appropriate amount of solvent for anionic polymerization. Examples of the organolithium compound and the diene monomer used to form the styrene-diene block copolymer are the same as those described above for the organolithium compound and the diene monomer used for forming the polydiene rubber. This will not be repeated here.

Examples of the styrene-based monomer used to form the styrene-diene block copolymer may be, for example, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, ortho -methylstyrene, ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, α-methyl-p-methylstyrene, chloro-styrene or bromine-benzene Ethylene and the like. The above styrene monomers may be used singly or in combination of several kinds. Further, in the styrene-diene block copolymer of the present invention, the content of the styrene monomer unit is, for example, 50% by weight or less, preferably 40% by weight or less. In detail, when the content of the styrene monomer unit is 50% by weight or more, the impact strength and elongation of the resin composition are lowered, so that the balance of physical properties such as transparency and impact strength required for the present invention cannot be achieved.

Further, in the styrene-diene block copolymer solution having a concentration of styrene as a solvent of 5% by weight, the solution viscosity of the styrene-diene block copolymer of the present invention is, for example, 5 cps. Up to 20 cps, more preferably 8 cps to 16 cps. In detail, when the solution viscosity of the styrene-diene block copolymer is less than 5 cps, the impact resistance of the resin composition is deteriorated and the elongation is lowered, and when the styrene-diene block copolymerizes When the solution viscosity of the substance is higher than 20 cps, the transparency of the resin composition is deteriorated.

< Styrene resin copolymer continuous phase >

The continuous phase of the styrene resin copolymer may be from 25 parts by weight to 64 parts by weight of the styrene monomer, from 35 parts by weight to 74 parts by weight of the (meth) acrylate monomer, and from 1 part by weight to 20 parts by weight of the propylene. The nitrile monomer is copolymerized, but is not limited thereto. In an embodiment of the present invention, the continuous phase of the styrene resin copolymer may include 27 parts by weight to 50 parts by weight of the styrene monomer unit, and 40 parts by weight to 70 parts by weight of the (meth) acrylate series The bulk unit and 2 parts by weight to 16 parts by weight of the acrylic monomer unit.

Examples of the styrene monomer used in the continuous phase of the styrene resin copolymer of the present invention may be, for example, styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, ortho- Methylstyrene, ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, α-methyl-p-methylstyrene, chloro-styrene or bromine-styrene Wait. The above styrene monomers may be used singly or in combination of several kinds.

Examples of the (meth) acrylate type monomer used in the continuous phase of the styrene resin copolymer of the present invention may include, but are not limited to, methacrylates and acrylates. The methacrylates may, for example, be methyl methacrylate, ethyl methacrylate or butyl methacrylate, cyclohexyl methacrylate, octadecyl methacrylate, phenyl methacrylate, Benzyl methacrylate or 2-ethylhexyl methacrylate, etc., and the acrylates may be, for example, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, acrylic acid. Phenyl ester, benzyl acrylate, 2-ethylpentyl acrylate or octyl acrylate, etc., of which methyl methacrylate and methyl acrylate are preferred.

Examples of the acrylic monomer used in the continuous phase of the styrene resin copolymer of the present invention may include, but are not limited to, acrylonitrile or α-methacrylonitrile. The above acrylonitrile-based monomers may be used singly or in combination.

< Rubber modified styrene resin copolymer >

The rubber-modified styrenic resin copolymer of the present invention may comprise a dispersed phase formed by 1% by weight to 25% by weight of rubber particles and a continuous phase formed by 75% by weight to 99% by weight of a styrene-based resin copolymer.

The method for producing the rubber-modified styrene resin copolymer may include, but is not limited to, the styrene monomer, the (meth) acrylate monomer, and the acrylonitrile monomer in the presence of the rubbery polymer. Batch or continuous block polymerization, solution polymerization or emulsion graft polymerization. Taking the continuous solution polymerization reaction as an example, the method for producing the rubber-modified styrene resin copolymer of the present invention comprises: first, a rubbery polymer and the above in a dissolution tank having a conventional high shear stress and a high stirring speed. Various monomers are added to a suitable solvent for dissolution to form a raw material mixed solution. In detail, in a dissolution tank having a belt-shaped spiral stirring blade, a propeller type stirring blade or other stirring blade which can generate high shear stress, the rubbery polymer can be completely dissolved into rubber in a sufficient time. The state of the solution is carried out in order to facilitate the pumping of it to the reactor.

In an embodiment of the present invention, a solvent type which can be used in the method for producing a rubber-modified styrene-based resin copolymer includes an aromatic hydrocarbon such as toluene, ethylbenzene or xylene; a ketone such as methyl ethyl ketone; Esters such as ethyl acetate. However, the invention is not limited thereto. In other embodiments, an aliphatic hydrocarbon such as n-hexane, cyclohexane or n-heptane may also be used as a part of the solvent.

Next, the raw material mixed solution and, if necessary, the monomer solution are continuously added to the first reactor and/or the second reactor, and/or the subsequent reactor thereof, and the chain transfer agent is required in combination. The graft polymerization is carried out with the addition of the starter to the first and/or second and/or subsequent reactors. The reactor may be one of a continuous stirred reactor (CSTR), a plug flow reactor (PFR) or a static mixing reactor or a combination of different kinds.

In an embodiment of the invention, the first reactor of the method for producing a rubber-modified styrenic resin copolymer preferably employs a continuous stirred reactor, followed by a second and/or subsequent reactor. The subsequent reactor may be a continuous stirred reactor, a plug flow reactor or a static hybrid reactor. In general, the monomer conversion of the first reactor is from about 1% to about 30% by weight, preferably from 2% to 25% by weight, more preferably from 3% to 22% by weight. The monomer conversion rate of the first reactor described above is adjusted depending on the content, type, or viscosity of the rubbery polymer to be used. That is, in the method for producing the rubber-modified styrene-based resin copolymer of the present embodiment, it is sought to prevent the reverse rotation phenomenon of the rubber from being generated in the first reactor, and in the subsequent reactor (such as the second or third The reverse rotation occurs in the reactor) in order to obtain good physical properties. Further, in the method for producing a rubber-modified styrene-based resin copolymer of the present embodiment, the reaction temperature in the reactor is controlled to be between 70 ° C and 230 ° C, and the final monomer conversion rate may be 30% to 95. %, but 50% to 90% is preferred.

Further, the polymerization reaction of the rubber-modified styrene-based resin copolymer can be initiated, for example, by a radical initiator, which is not particularly limited and can be used singly or in combination, and is 100 parts by weight. The initiator may be added in an amount of from 0 part by weight to 2 parts by weight, preferably from 0.001 part by weight to 0.7 part by weight, based on the total of the monomers of the continuous phase of the styrene resin copolymer.

Specific examples of the radical initiator include, but are not limited to: (1) azo compounds: 2,2'-Azobis-(isobutyronitrile, AIBN for short), 2,2'-Azobis(2-methylbutyronitrile) [2,2'-Azobis-(2-methylbutyronitrile), abbreviated as AMBN] or 2,2'-azobis(2,4-dimethyl [2,2'-Azobis-(2,4-dimethylvaleronitrile), abbreviated as ADVN]; (2) diacyl peroxides: dilauroyl peroxide, peroxidation Decanoyl peroxide or dibenzoyl peroxide (BPO); (3) dialkyl peroxides: 2,5-dimethyl-2,5-di (2,5-dimethyl-2,5-di-(t-butylperoxy)hexane, dicumyl peroxide or 1,3-double (three) (1,3-bis-(t-butyl peroxy isopropyl)benzene]; (4) Peroxyesters: tertiary butyl peroxypivalate (t-butyl peroxypivalate) or 2,5-dimethyl-2,5-di(2-ethylhexanol peroxy)hexane [2,5-dimethyl-2,5-di(2-ethy) Lhexanoylperoxy) hexane] et al; (5) peroxycarbonates: 2-ethylhexyl-tert-amylperoxy 2-ethylhexyl carbonate or 2-ethylhexyl-tertiary Tert-butylperoxy 2-ethylhexyl carbonate, etc.; (6) peroxydicarbonates: dimyristyl peroxydicarbonate or di(4-trisyl) Butylcyclohexyl peroxydicarbonate, etc.; (7) Peroxyketal compounds: 1,1-di(tertiary butyl peroxidation) -3,3,5-trimethylcyclohexane [1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane] or 2,2-bis(4,4-di-tert-butyl Oxidation) 2,2-di(4,4-di(tert-butylperoxy) cyclohexylpropane]; (8) Hydroperoxides: tert-butyl hydroperoxide Or isopropylcumyl hydroperoxide, etc.; (9) other compound: 2,3-dimethyl-2,3-diphenylbutane (2,3-dimethyl-2, 3-diphenyl Butane), Potassium persulfate, sodium persulfate or Ammonium persulfate, among which 1,1-di(tri-butyl peroxide)-3,3,5- Trimethylcyclohexane and 2,2-bis(4,4-di-tert-butylperoxy)cyclohexylpropane are preferred.

In the method for producing a rubber-modified styrene resin copolymer of the present invention, the chain transfer agent to be used in combination may be a monofunctional chain transfer agent or a polyfunctional chain transfer agent. Specifically, when a monofunctional chain transfer agent is used, it is added in an amount of from 0 part by weight to 2 parts by weight, preferably 0.01%, based on 100 parts by weight of all monomers of the continuous phase of the styrene resin copolymer. Parts to 0.7 parts by weight. Examples of the monofunctional chain transfer agent include: (a) mercaptans such as methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, n-dodecyl mercaptan , stearyl mercaptan, t-dodecyl mercaptan (TDM), n-propyl mercaptan, n-octyl mercaptan, third-octyl mercaptan Or a third-mercaptothiol or the like; (ii) an alkylamines such as monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, single Butylamine, di-n-butylamine or tri-n-butylamine; (3) Other species, such as pentaphenylethane, α-methylstyrene dimer (α-methyl styrene dimer) ), terpinolene or the like, wherein n-dodecyl mercaptan or t-dodecyl mercaptan in the mercaptan is preferred.

In addition, examples of the polyfunctional chain transfer agent include: pentaerythritol tetrakis (3-mercapto propionate), pentaerythritol tetrakis(2-mercaptoacetate) (pentaerythritol tetrakis (2-mercapto ethanate)), trimethylolpropane tris (2-mercapto ethanate), tris-(3-mercaptopropionic acid) trimethylolpropyl ester (trimethylolpropane tris (3-mercapto propionate), abbreviated as TMPT) or trimethylolpropane tris (6-mercapto hexanate).

Next, after completion of the aforementioned polymerization reaction, the polymer obtained by the polymerization reaction is taken out from the reactor and treated through a devolatilization apparatus to remove low-volatile components such as unreacted monomers and solvents. Thereafter, the rubber-modified styrene-based resin copolymer of the present invention can be obtained by recovering the polymer.

The above devolatilization device may be a uniaxial extruder or a twin-axis extruder with a detachment port. In addition, a devolatizing agent such as water, cyclohexane, carbon dioxide or the like may be added to the extruder as needed, and a kneading zone, a push section, etc. may be provided in the extruder as needed. And the screw speed is from 120 rpm to 350 rpm. Further, the devolatilizer may be a devolatilizer tank with a vacuuming device. The devolatilization tank may be used in one or several series, and the temperature of the devolatilization tank is controlled at 180 ° C to 350 ° C, preferably 200 ° C to 320 ° C, more preferably 220 ° C to 300 ° C. The vacuum degree of the devolatilization tank is controlled to be 300 or less, preferably 200 torr or less, and most preferably 100 torr or less. Further, the above devolatilization apparatus may be, for example, another suitable devolatilizer such as a thin film evaporator.

After the treatment with the devolatilizer, the low-volatile components such as residual monomers, solvents, dimers, and triads in the resin composition can be reduced to 1% by weight or less, preferably 0.8% by weight or less, more preferably Up to 0.5% by weight or less.

Other components, including but not limited to colorants, fillers, flame retardants, flame retardant additives (eg, antimony trioxide, etc.), light, may be added to the range of effects that do not significantly impair the resin composition of the present invention. Additives such as stabilizers, heat stabilizers, plasticizers, tackifiers, charge inhibitors, oxidation inhibitors or conductive agents. Examples of the above additives include: mineral oil; ester-based plasticizers such as butyl stearate; polyester-based plasticizers; organic polyoxyalkylenes such as polydimethylsiloxane; higher fatty acids and metal salts thereof; Amine-resistant antioxidants, glass fibers, and the like, which may be used singly or in combination. The above additives may be added and mixed as needed in the polymerization reaction stage or after completion of the reaction.

The ester-based plasticizer or mineral oil is generally used in an amount of from 0% by weight to 5% by weight, preferably from 0.05% by weight to 2% by weight, based on 100% by weight of the total weight of the rubber-modified styrene-based resin copolymer. The organopolyoxane is generally used in an amount of from 0% by weight to 0.5% by weight, preferably from 0.002% by weight to 0.2% by weight.

Further, in the case where the transparency of the resin composition of the present embodiment is not significantly impaired, other resins may be further formulated, including but not limited to styrene-(meth)acrylate-acrylonitrile-based copolymer. , styrene-based (meth)acrylate copolymer, styrene-based (meth)acrylate-acrylonitrile-maleimide copolymer, styrene-(meth)acrylate A copolymer of a maleic acid-based copolymer, a (meth)acrylate-maleimide copolymer, or a modified (or graft modified) diene rubber.

On the other hand, the use of the rubber-modified styrene-based resin copolymer of the present invention is not particularly limited, and it can be applied to various molded articles for injection molding and compression molding, or can be applied to extrusion molding, blow molding, and thermoforming. The finished products made by vacuum forming or hollow molding, such as: plate, film molded products, etc., can be formulated according to the formula to achieve high fluidity, high heat resistance and the like.

The addition and mixing of the other components or resins may be carried out by mixing and kneading a general mixing and kneading machine such as a Brabender plastometer, a Banbury mixer, a kneading-mixer, a roller press, a single-axis or a double-axis extruder. . Usually, the kneaded product is cooled and granulated by mixing and kneading through the above-mentioned extruder or the like. The above kneading is generally carried out at a temperature of from 160 ° C to 280 ° C, and preferably from 180 ° C to 250 ° C, and the mixing and kneading of the respective components is not particularly limited in order.

<( methyl ) Acrylate - Styrene copolymer >

The (meth) acrylate-styrene copolymer of the present invention comprises 40% by weight to 80% by weight of (meth) acrylate monomer units and 20% by weight to 60% by weight of styrene monomer units . Preferably, the (meth) acrylate-styrene copolymer comprises 40% by weight to 50% by weight of a (meth) acrylate monomer unit and 50% by weight to 60% by weight of a styrene system. Monomer unit. In detail, when the styrene monomer unit is less than 20% by weight, that is, when the (meth) acrylate monomer unit content is more than 80% by weight, the (meth) acrylate system is - the styrene-based copolymer has high hygroscopicity, so that the dimensional stability of the subsequently obtained molded article is poor; when the styrene-based monomer unit exceeds 60% by weight, that is, the (meth) acrylate system When the content of the monomer unit is less than 40% by weight, the weather resistance of the (meth) acrylate-styrene copolymer is poor, so that the molded article obtained later may cause coloring and mechanical property degradation under long-time illumination. problem. However, the present invention is not limited thereto, and more preferably, the (meth) acrylate-styrene copolymer may further include 0% by weight to 40% by weight of a copolymerizable monomer unit.

The styrene monomer used for the polymerization of the (meth) acrylate-styrene copolymer may be the same as the styrene monomer or copolymer used for forming the styrene-diene block copolymer. The styrene-based monomer used in the phase, and the (meth) acrylate-based monomer used for the polymerization of the (meth) acrylate-styrene-based copolymer can be exemplified as used in the continuous phase of the copolymer ( The methyl acrylate monomer is not described here. Other copolymerizable monomer units for polymerizing the (meth) acrylate-styrene copolymer may, but not limited to, (1) an unsaturated carboxylic acid or an anhydride thereof: acrylic acid, methacrylic acid, or horse. Acid or itaconic acid; (2) Maleic imines: N-methyl maleimide, N-phenyl maleimide, N-cyclohexyl mala Imine, etc.; (3) hydroxyl group-containing (meth) acrylate compound: acrylic acid monoglyceride or 2-hydroxyethyl (meth) acrylate, etc.; (4) other Propylene group-containing compound: acrylamide, acrylonitrile, allyl glycidyl ether or glycidyl (meth)acrylate .

The (meth) acrylate-styrene copolymer may have a weight average molecular weight ranging from 80,000 to 200,000, more preferably from 90,000 to 170,000. The melt flow index of the (meth)acrylate-styrene copolymer (Melt Index, MI; also known as Melt Flow Index, MFI; also known as Melt Volume Rate, MVR) has a real value of 1.2 cubic centimeters per minute. (cm ³ /10 min) to 2.9 cubic centimes / 10 minutes (melting coefficient measurement conditions: temperature 200 ° C, load 5 kg), with good processability. The (meth) acrylate-styrene copolymer may have a softening point temperature ranging from 100 ° C to 110 ° C to give good thermal stability.

The (meth) acrylate-styrene copolymer of the present invention can be produced by a solution polymerization method or a bulk polymerization method, but is not limited thereto. It is preferred to carry out the polymerization in the presence of a solvent. The boiling point of the solvent is preferably similar to the boiling point of the main monomer used for the polymerization reaction, for example, a solvent having a boiling point close to that of the (meth) acrylate monomer or the styrene monomer is selected so that the solvent The mixture of the above monomers has a narrower boiling point range, which reduces the chance of the mixture mixing contaminants during recycle, eliminating the need for intermediate fractionation of the mixture. Preferably, the solvent has a boiling point in the range of 40 ° C to 225 ° C, more preferably 60 ° C to 180 ° C. More specifically, the solvent may be, for example, a hydrocarbon solvent or an aromatic hydrocarbon solvent having a boiling point range as described above, and may be used singly or in combination, and specific examples of the solvent include, but are not limited to, hexane, heptane. , octane, benzene, toluene, p-xylene, o-xylene, m-xylene, ethylbenzene, cyclohexane, cyclodecane or isooctane.

Further, the polymerization reaction of the (meth) acrylate-styrene copolymer may be initiated, for example, by a radical initiator, which is not particularly limited and may be, for example, modified with rubber. The radical initiator used in the polymerization reaction of the styrene resin copolymer is the same, but is not limited thereto. The radical initiator may be used in an amount ranging from 0.01 to 1 part by weight, preferably from 0.03 to 0.5 part by weight, more preferably 0.07, based on 100 parts by total of the total of the monomer mixture fed. To 0.1 parts by weight.

The polymerization reaction of the (meth)acrylate-styrene copolymer can be carried out at normal temperature, and the reaction system can be heated to increase the rate of polymerization. The reaction temperature of the polymerization reaction of the (meth) acrylate-styrene copolymer may range from 25 ° C to 200 ° C, preferably from 50 ° C to 180 ° C. The polymerization time of the polymerization reaction of the (meth) acrylate-styrene copolymer may range from 6 hours to 10 hours.

The resin composition of the present invention will be more specifically described below with reference to several experiments. Although the following experiments are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively based on the experiments described below.

Each of the components used in the experimental examples and comparative examples was prepared as follows:

Synthesis example 1

Preparation of rubbery polymer

98% by weight of block copolymer (styrene-diene block copolymer) with increasing composition of styrene-butadiene and 2% by weight of polybutadiene rubber (polydiene rubber) The phases are mixed to obtain a rubbery polymer. In the block copolymer in which the styrene-butadiene composition is gradually increased, the weight ratio of styrene to butadiene is 25/75. Further, in the 5% by weight styrene solution, the block copolymer having an increasing composition of styrene-butadiene has a solution viscosity of 10 cps, a weight average molecular weight of 130,000, and a polystyrene block content of 18% by weight. . Further, the polybutadiene rubber was a low cis polybutadiene rubber, and the solution viscosity of the polybutadiene rubber was 170 cps and the weight average molecular weight was 630,000 in a 5% by weight styrene solution.

Preparation of rubber modified styrene resin copolymer

13.6 parts by weight of the above rubbery polymer and 38 parts by weight of styrene (styrene monomer), 58 parts by weight of methyl methacrylate (meth) acrylate monomer, 4 weight A portion of acrylonitrile (acrylonitrile monomer), 38 parts by weight of ethylbenzene (solvent), 0.15 parts by weight of dibenzoguanidine peroxide, 0.18 parts by weight of n-dodecyl mercaptan (chain transfer agent) a feed solution consisting of 0.111 parts by weight of pentaerythritol tetrastearate (pentaerythritol ester compound) and 0.18 parts by weight of benzoic acid peroxide (starter), continuously pumped at a flow rate of 35 kg/hour The polymerization was carried out in a 40 liter fully mixed liquid-type reactor continuous polymerization apparatus, wherein the temperature of the first reaction tank was set to 98 ° C, the stirring rod rotation speed was 300 rpm, and the temperature of the second reaction tank was set to 104 ° C, the stirring rod rotation speed is 200 rpm; the temperature of the third reaction tank is set to 115 ° C, the stirring rod rotation speed is 150 rpm, the temperature of the fourth reaction tank is set to 127 ° C, the stirring rod rotation speed is 90 rpm, and the fourth reaction tank is The composition conversion rate α at the outlet is 65%, wherein the composition conversion rate α is defined : The binder resin weight / (feed rubbery polymer weight + weight of the total monomer feed) × 100%.

Next, after completion of the polymerization reaction, the obtained resin composition was treated by a devolatilization apparatus, and the degree of vacuum was controlled at 130 torr to separate volatile substances such as unreacted monomers and organic solvents, thereby completing Synthesis Example 1. Rubber modified styrenic resin copolymer.

Synthesis example 2

( methyl ) Acrylate - Preparation of styrene copolymer

49% by weight of styrene, 41% by weight of methyl methacrylate and 10% by weight of ethylbenzene were continuously fed into a fully mixed reactor for continuous solution polymerization, and the reaction temperature was maintained at 100 ° C. The pressure is 600 torr. The mixture was thoroughly stirred in the fully mixed reactor to uniformly mix the components to form a reactant, and after about 3.5 hours of residence, the reactant was continuously fed to the laminar flow reactor. In a laminar flow reactor, the reaction temperature was ramped from 115 ° C to 160 ° C and a polymer solution was formed after about 5 hours of residence. Then, the polymer solution is sent to a devolatilizer, the polymer solution is heated to 235 ° C, and the polymer solution is subjected to a devolatilization step under a reduced pressure environment to obtain Synthesis Example 2 (A Acrylate-styrene copolymer. The (meth) acrylate-styrene copolymer contains 56% by weight of a methyl methacrylate monomer unit, 44% by weight of a styrene monomer unit, a weight average molecular weight of 90,000, and a melt flow rate (MVR (200°). C × 5kg)) = 1.4.

Hereinafter, a plurality of examples and comparative examples are enumerated to verify the efficacy of the present invention.

Example 1~3 And comparative examples 1~8

The components of Table 1 were mixed according to the amounts shown in Table 2 to prepare the resin compositions of Examples 1 to 3 and Comparative Examples 1 to 8.

The melt flow index, softening point temperature, impact strength, tensile strength, elongation, printability, warpage degree and odor test of each of the resin compositions obtained in the above experiment were measured by the following measurement methods. The results are shown in Table 3.

(1) Melt Flow Index (MVR): According to ISO 1133, the test is carried out at a load of 10 kg at a temperature of 220 ° C or a load of 5 kg at a temperature of 200 ° C (unit: cm ³ /10 min).

(2) Vicat softening temperature (SP): According to ISO 306, the resin compositions of Experimental Examples 1 to 3 and Comparative Examples 1 to 7 were subjected to a load of 10 Newtons (N) at a heating rate of The softening point temperature was measured under an hour at 50 ° C in units of ° C.

(3) Impact resistance test (Charpy): measured at ISO 23, using a 80 mm × 10 mm × 4 mm test piece with a notch (Notched, opening depth of 2 mm) at 23 ° C (unit, kJ / m ² ).

(4) Tensile strength (Tsy): Tested in accordance with ISO 527 (unit: MPa).

(5) Elongation (EL): Tested in accordance with ISO 527 (unit: %).

(6) Printability: A strip having a diameter of 0.4 mm formed of the resin compositions of Experimental Examples 1 to 3 and Comparative Examples 1 to 7 was used, and a 3D printing machine (model: MakerBot Replicator 2X) was used. A printing test was carried out at 230 ° C, and a 10 cm × 10 cm × 10 cm three-dimensional "concave" structure having a wall thickness of 1 cm (9 cm × 9 cm × 9 cm hollow) was printed. The printability was evaluated according to the following criteria: ○: The extrusion head was printed smoothly. △: The extrusion head is still printable (it can be broken after 2 hours of continuous production). ╳: The extrusion head often breaks when printing the glue (the wire breaks within 30 minutes).

(7) Degree of warpage: On a flat horizontal surface, the central portion of the bottom surface (the notch facing upward) of the aforementioned three-dimensional concave structure is in contact with the horizontal plane, and the difference in height between the central portion and the maximum warpage is measured (unit: mm ).

(8) Odor test: Evaluation was carried out by using an olfactory measurement method, and the tester used a rubber strip having a diameter of 0.4 mm formed of the resin compositions of Experimental Examples 1 to 3 and Comparative Examples 1 to 7, respectively, and was subjected to column at 230 ° C. The odor was evaluated while the printing was carried out, and the odor of Comparative Example 3 was used as a control. When the odor was worse than Comparative Example 3 or the two were equivalent, it was evaluated as ╳, and when the odor was better than Comparative Example 3 (smell) When it is less, it is rated as ○.

Table 1         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Ingredients</td><td> Source</td><td> Description of Content < /td></tr><tr><td> Rubber modified styrene resin copolymer</td><td> Synthesis Example 1 </td><td> (Meth)acrylate-Acrylonitrile-butyl Diene-styrene copolymer</td></tr><tr><td> (meth)acrylate-styrene copolymer</td><td> Synthesis Example 2 </td><td > (Meth)acrylate-styrene copolymer</td></tr><tr><td> Acrylonitrile-butadiene-styrene copolymer</td><td> Chi Mei PA-747 </ Td><td> emulsified polymerized acrylonitrile-butadiene-styrene copolymer</td></tr><tr><td> Chimei PA-705N </td><td> bulk polymerized acrylonitrile- Butadiene-styrene copolymer</td></tr><tr><td> styrene-acrylonitrile copolymer</td><td> Chi Mei PN-117-L100 </td><td> benzene Ethylene-acrylonitrile copolymer</td></tr><tr><td> poly(methyl) acrylate</td><td> Chi Mei CM-207 </td><td> poly(methyl Methyl acrylate</td></tr></TBODY></TABLE>

Table 2         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> ingredient source</td><td> unit</td><td> Example 1 < /td><td> Example 2 </td><td> Example 3 </td><td> Comparative Example 1 </td><td> Comparative Example 2 </td><td> Comparative Example 3 < /td></tr><tr><td> Synthesis Example 1 </td><td> Weight % </td><td> 95 </td><td> 90 </td><td> 80 < /td><td> 100 </td><td> 70 </td><td> - </td></tr><tr><td> Synthesis Example 2 </td><td> Weight % < /td><td> 5 </td><td> 10 </td><td> 20 </td><td> - </td><td> 30 </td><td> - </td ></tr><tr><td> PA-747 </td><td> % by weight </td><td> - </td><td> - </td><td> - </td ><td> - </td><td> - </td><td> 100 </td></tr><tr><td> PA-705N </td><td> % by weight </td ><td> - </td><td> - </td><td> - </td><td> - </td><td> - </td><td> - </td>< /tr><tr><td> PN-117-L100 </td><td> Weight % </td><td> - </td><td> - </td><td> - </td ><td> - </td><td> - </td><td> - </td></tr><tr><td> CM-207 </td><td> % by weight </td ><td> - </td><td> - </td><td> - </td><td> - </td><td> - </td><td> - </td>< /tr></TBODY></TABLE>

Table 2 (continued)         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> ingredient source</td><td> unit</td><td> comparison example 4 < /td><td> Comparative Example 5 </td><td> Comparative Example 6 </td><td> Comparative Example 7 </td><td> Comparative Example 8 </td></tr><tr> <td> Synthesis Example 1 </td><td> Weight % </td><td> - </td><td> - </td><td> - </td><td> - </td ><td> - </td></tr><tr><td> Synthesis Example 2 </td><td> Weight % </td><td> - </td><td> - </td ><td> - </td><td> - </td><td> - </td></tr><tr><td> PA-747 </td><td> % by weight </td ><td> - </td><td> - </td><td> - </td><td> - </td><td> - </td></tr><tr><td > PA-705N </td><td> wt% </td><td> 100 </td><td> 90 </td><td> 90 </td><td> 70 </td>< Td> 70 </td></tr><tr><td> PN-117-L100 </td><td> wt% </td><td> - </td><td> 10 </td ><td> - </td><td> 30 </td><td> - </td><td> </td></tr><tr><td> CM-207 </td>< Td> wt% </td><td> - </td><td> - </td><td> 10 </td><td> - </td><td> 30 </td><td > </td></tr><tr height="0"><td></td><td></td><td></td><td></td><td></ Td><td></td><td></td><td></td><td></td><td></td><td></td></tr> </TBODY></TABLE>

table 3         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td></td><td> Units</td><td> Example 1 </td ><td> Example 2 </td><td> Example 3 </td><td> Comparative Example 1 </td><td> Comparative Example 2 </td><td> Comparative Example 3 </td ></tr><tr><td> Total Rubber Content (RC%) </td><td> Weight % </td><td> 17.1 </td><td> 16.2 </td><td> 14.4 </td><td> 18 </td><td> 12.6 </td><td> 21 </td></tr><tr><td> MVR-200°C *5KG </td> <td> cm³/10min </td><td> 2.75 </td><td> 2.7 </td><td> 2.43 </td><td> 2.81 </td> <td> 2.4 </td><td> - </td></tr><tr><td> MVR-220°C *10KG </td><td> cm³/ 10min </td><td> - </td><td> - </td><td> - </td><td> - </td><td> - </td><td> 12.26 < /td></tr><tr><td> SP_50°C10N </td><td> °C </td><td> 103 </td><td> 102.9 </td><td> 104 < /td><td> 103.3 </td><td> 104.6 </td><td> 104.5 </td></tr><tr><td> Charpy (Notched) </td><td> kJ/ m²</td><td> 12.6 </td><td> 12 </td><td> 9 </td><td> 13.3 </td><td> 8.6 < /td><td> 34.5 </td></tr><tr><td> Tsy </td><td> MPa </td><td> 42.3 </td><td> 43.9 < /td><td> 46.7 </td><td> 41.7 </td><td> 48 </td><td> 38.2 </td></tr><tr><td> EL </td> <td> % </td><td> 38 </td><td> 37 </td><td> 37.5 </td><td> 38 </td><td> 34 </td><td > 40 </td></tr><tr><td> Printability (Φ=0.4mm) (Processing temperature: 230°C) </td><td> ○ </td><td> ○ < /td><td> ○ </td><td> △ </td><td> ╳ </td><td> △ </td></tr><tr><td> degree of warpage (mm ) </td><td> 0 </td><td> 0 </td><td> 0 </td><td> 7 </td><td> 1.5 </td><td> 7 < /td></tr><tr><td> Odour Test</td><td> ○ </td><td> ○ </td><td> ○ </td><td> ○ </td ><td> ○ </td><td> ╳ </td></tr></TBODY></TABLE>

Table 3 (continued)         <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td></td><td> Units</td><td> Comparative Example 4 </td ><td> Comparative Example 5 </td><td> Comparative Example 6 </td><td> Comparative Example 7 </td><td> Comparative Example 8 </td></tr><tr><td > Total rubber content (RC%) </td><td> Weight % </td><td> 15 </td><td> 13.5 </td><td> 13.5 </td><td> 10.5 < /td><td> 10.5 </td></tr><tr><td> MVR-200°C *5KG </td><td> cm³/10min </td> <td> - </td><td> - </td><td> - </td><td> - </td><td> - </td></tr><tr><td> MVR-220°C *10KG </td><td> cm³/10min </td><td> 31.08 </td><td> 30.99 </td><td> 28.77 < /td><td> 30.47 </td><td> 24.32 </td></tr><tr><td> SP_50°C10N </td><td> °C </td><td> 105.4 < /td><td> 105 </td><td> 106.4 </td><td> 107 </td><td> 106.9 </td></tr><tr><td> Charpy (Notched) < /td><td> kJ/m²</td><td> 13.3 </td><td> 9.1 </td><td> 11.9 </td><td> 4.6 < /td><td> 5.8 </td></tr><tr><td> Tsy </td><td> MPa </td><td> 48.1 </td><td> 50.2 </td> <td> 51.1 </td><td> 54.9 </td><td> 56.2 </td></tr><tr><td> EL </td><td> % </td> <td> 18 </td><td> 16 </td><td> 19 </td><td> 18 </td><td> 26 </td></tr><tr><td> Printability (Φ=0.4mm) (machining temperature: 230°C) </td><td> △ </td><td> △ </td><td> △ </td><td> △ < /td><td> △ </td></tr><tr><td> Warpage degree (mm) </td><td> 2 </td><td> 4 </td><td> 4 </td><td> 5 </td><td> 5 </td></tr><tr><td> odor test</td><td> ○ </td><td> ○ < /td><td> ○ </td><td> ○ </td><td> ○ </td></tr></TBODY></TABLE>

In the evaluation results of Table 3, Experimental Examples 1 to 3 according to the present invention have good printability and hardly warp. In contrast, in Comparative Example 1, Comparative Example 3 to Comparative Example 8, only the partial components of the present invention were contained, and the obtained resin composition was inferior to the experimental examples 1 to 3, and the warpage was as high as 7 mm. In practical applications, it is easy to cause printing to fail.

In summary, the resin composition for three-dimensional printing of the present invention hardly causes warpage during processing, so that the three-dimensional printing has good processability, and does not cause puncturing or obvious odor during processing, and conforms to the indoor space. The need for operation.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

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Claims (10)

A resin composition for three-dimensional printing comprising: more than 70% by weight to 95% by weight of a rubber-modified styrene-based resin copolymer; and 5% by weight to less than 30% by weight of (meth) acrylate-styrene a copolymer, wherein the rubber-modified styrenic resin copolymer comprises: 1% by weight to 25% by weight of a dispersed phase formed of rubber particles, the rubber particles being formed of a rubbery polymer; and 75% by weight to 99% by weight a continuous phase formed of a styrene-based resin copolymer comprising a first styrene-based monomer unit and a first (meth) acrylate-based monomer unit, wherein the styrene-based monomer The content of the first styrene monomer unit ranges from 25 parts by weight to 65 parts by weight and the content of the first (meth) acrylate monomer unit ranges from 35 parts by weight based on 100 parts by weight of the resin copolymer. To 75 parts by weight, wherein the (meth) acrylate-styrene copolymer comprises: 40% by weight to 80% by weight of the second (meth) acrylate monomer unit; and 20% by weight to 60% % by weight of the second styrenic monomer unit. The resin composition for three-dimensional printing according to the first aspect of the invention, wherein the styrene resin copolymer further comprises an acrylonitrile monomer unit, and the styrene resin copolymer content is 100 parts by weight. The content of the first styrene monomer unit ranges from 25 parts by weight to 64 parts by weight, and the content of the first (meth) acrylate monomer unit ranges from 35 parts by weight to 74 parts by weight, and the propylene The content of the nitrile monomer unit ranges from 1 part by weight to 20 parts by weight. The resin composition for three-dimensional printing according to the first aspect of the invention, wherein the styrene resin copolymer further comprises an acrylonitrile monomer unit, and the styrene resin copolymer content is 100 parts by weight. The content of the first styrene monomer unit ranges from 27 parts by weight to 50 parts by weight, and the content of the first (meth) acrylate monomer unit ranges from 40 parts by weight to 70 parts by weight, and the propylene The content of the nitrile monomer unit ranges from 2 parts by weight to 16 parts by weight. The three-dimensional printing resin composition according to claim 1, wherein the rubbery polymer comprises a polydiene rubber. The resin composition for three-dimensional printing according to claim 4, wherein the polydiene rubber is selected from the group consisting of butadiene rubber, isoprene rubber, chloroprene rubber, and styrene-two. A group consisting of olefinic rubber and acrylonitrile rubber. The three-dimensional printing resin composition according to claim 1, wherein the rubbery polymer comprises 92% by weight to 99% by weight of the styrene-diene block copolymer and 1% by weight to 8 % by weight of polydiene rubber. The three-dimensional printing resin composition according to claim 1, wherein the rubbery polymer comprises 94% by weight to 99% by weight of the styrene-diene block copolymer and 1% by weight to 6 % by weight of polydiene rubber. The resin composition for three-dimensional printing according to the first aspect of the invention, wherein the (meth)acrylate-styrene copolymer further comprises 40% by weight or less of a copolymerizable monomer unit. The three-dimensional printing resin composition according to claim 1, wherein the (meth) acrylate-styrene copolymer has a softening point temperature of from 100 ° C to 110 ° C. A three-dimensionally-printed molded article is formed from the resin composition for three-dimensional printing according to any one of claims 1 to 9.