JP6246406B2 - Thermomelt lamination method thermoplastic resin composition for three-dimensional modeling and molded article - Google Patents

Description

The present invention relates to a thermoplastic resin composition for three-dimensional modeling of a hot melt lamination method in which adhesion strength between laminations of a modeled object is improved, and a modeled object.

  Based on a computer-aided design (CAD) model, 3D printing technology is known in which modeling materials are arranged in three dimensions to form a model. 3D printing technology has made it possible to create shapes and sizes that were difficult in the past, and it has become widespread in a wide range of fields because it can produce parts, jigs, and products without using molds. ing. One method of 3D printing technology is a method (FDM method) in which a filament-shaped thermoplastic resin is melt-extruded and laminated.

As a thermoplastic resin used in the FDM method, for example, a modified acrylonitrile-butadylene-styrene (ABS) resin (Patent Document 1) is disclosed. Also,
A composition comprising a copolymer obtained by graft copolymerizing an aromatic vinyl compound in the presence of a specific rubbery polymer, and a polymer obtained by polymerizing the aromatic vinyl compound (Patent Document 2) Is disclosed.

  However, since the filament-shaped thermoplastic resin is melt-extruded and laminated in the FDM method, it is necessary to have sufficient adhesive strength between the laminates in order to obtain a strong molded article, but it is still not satisfactory. .

Special table 2010-521339

JP 2007-51237 A

An object of the present invention is to provide a thermoplastic resin composition for three-dimensional modeling of a hot melt lamination method and a modeled object in which the adhesion strength between the layers of the modeled object is improved.

  As a result of intensive studies, the present inventors have found that a conjugated diene polymer, a graft copolymer obtained by graft polymerization of a monomer containing an aromatic vinyl monomer, and a monomer containing an aromatic vinyl monomer. The inventors have found that the above problems can be solved by defining the fluidity of a rubber-reinforced styrene resin composed of a copolymer obtained by polymerizing a monomer within a specific range, and have completed the present invention.

That is, melt volume rate (220 ° C., 10 kgf) is contained rubber-reinforced styrene resin is 20 ^(cm 3/10 min) or more, the rubber-reinforced styrene resin, a conjugated diene polymer, an aromatic vinyl A graft copolymer (A) obtained by graft polymerization of a monomer containing a monomer and a copolymer (B) obtained by polymerizing a monomer containing an aromatic vinyl monomer. Provided is a thermoplastic resin composition for hot melt lamination type three-dimensional modeling.

It is preferable that the thermoplastic resin composition for three-dimensional modeling of the hot melt lamination method does not substantially contain a resin other than the rubber-reinforced styrene resin.

  Furthermore, the modeling thing which consists of a thermoplastic resin composition for hot melt lamination system three-dimensional modeling is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition for hot melt lamination system three-dimensional shaping | molding and the molded article in which the adhesive strength between lamination | stacking of a molded article was improved can be provided.

Hereinafter, the present invention will be described in detail.

Hot melt lamination method 3D molded thermoplastic resin composition of the present invention has a melt volume rate (220 ° C., 10 kgf) is contained rubber-reinforced styrene resin is 20 (cm ^3/10 min) or more, the rubber Reinforced styrene resin is a conjugated diene polymer, a graft copolymer (A) obtained by graft polymerization of a monomer containing an aromatic vinyl monomer, and a single amount containing an aromatic vinyl monomer It consists of the copolymer (B) formed by polymerizing the body.

  Examples of the conjugated diene polymer constituting the graft copolymer (A) include polybutadiene rubber, styrene-butadiene rubber (SBR), and acrylonitrile-butadiene rubber (NBR).

  There is no restriction | limiting in particular about the polymerization method of a conjugated diene type polymer, It can manufacture by emulsion polymerization, suspension polymerization, block polymerization, solution polymerization, or these combination.

  Although there is no restriction | limiting in particular in the weight average particle diameter of a conjugated diene type polymer, 0.01-2.0 micrometers is preferable from a physical property balance, such as impact resistance, fluidity | liquidity, and coloring property, 0.1-1.0 micrometer is preferable. More preferred. Moreover, it can also adjust by agglomerating and enlarging the rubber-like polymer whose weight average particle diameter is 0.05-0.3 micrometer.

  The graft copolymer (A) of the present invention is obtained by graft polymerization of the conjugated diene polymer described above and a monomer containing an aromatic vinyl monomer.

  Examples of the aromatic vinyl monomer constituting the graft copolymer (A) include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and one or more of them can be used. In particular, styrene and α-methylstyrene are preferable.

  As the graft copolymer (A), other monomers copolymerizable with an aromatic vinyl monomer can be used. Other monomers that can be copolymerized include vinyl cyanide monomers, (meth) acrylate monomers, maleimide monomers, amide monomers, unsaturated carboxylic acid monomers Body etc. are mentioned and it can use 1 type (s) or 2 or more types. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and examples of (meth) acrylic acid ester monomers include methyl (meth) acrylate and (meth) acrylic acid. Ethyl, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, phenyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, (di) bromo (meth) acrylate Examples thereof include phenyl and chlorophenyl (meth) acrylate. Examples of maleimide monomers include N-phenylmaleimide and N-cyclohexylmaleimide. Examples of amide monomers include acrylamide and methacrylamide. Unsaturated carboxylic acid monomers include acrylic acid and methacrylate. Acid, maleic acid, fumaric acid, and itaconic acid can be exemplified.

  The content of the conjugated diene polymer in the graft copolymer (A) is preferably 20 to 80% by weight, and preferably 40 to 70% by weight from the viewpoint of balance of physical properties such as impact resistance, fluidity and color developability. More preferred.

  There is no particular limitation on the composition ratio of the above monomer graft-polymerized to the conjugated diene polymer, but the aromatic vinyl monomer is 50 to 90% by weight, the vinyl cyanide monomer is 10 to 50% by weight. And other copolymerizable monomers at 0 to 40% by weight, aromatic vinyl monomer at 30 to 80% by weight, (meth) acrylic acid ester monomer at 20 to 70% by weight and copolymerization Possible composition ratio of 0 to 50% by weight of other vinyl monomers, 20 to 70% by weight of aromatic vinyl monomers, 20 to 70% by weight of (meth) acrylate monomers, vinyl cyanide The composition ratio is preferably 10 to 60% by weight of the monomer and 0 to 50% by weight of another copolymerizable monomer (the total amount of monomers graft-polymerized to the conjugated diene polymer is 100 %).

  The graft ratio of the graft copolymer (A) and the reduced viscosity of the acetone-soluble component are not particularly limited, but the graft ratio is preferably 10 to 150%, more preferably 20 to 100%. The reduced viscosity of the acetone-soluble component is preferably 0.1 to 0.8 dl / g, and more preferably 0.2 to 0.7 dl / g. By adjusting so that it may become the said range, the balance of fluidity | liquidity, impact resistance, and coloring property can be improved.

  The graft ratio and the reduced viscosity of the acetone-soluble component can be determined as follows.

<Graft ratio>
About 2 g of the corresponding graft copolymer (A) powder is immersed in 60 mL of acetone for 24 hours, and then separated into an acetone insoluble part and an acetone soluble part by a glass filter. The separated acetone insoluble part was vacuum-dried for 24 hours, and then its weight was measured.
Graft rate (%) = (XY) / Y × 100
X: Acetone insoluble part after vacuum drying (g)
Y: amount of rubbery polymer in the graft copolymer (g)

<Reduced viscosity of acetone-soluble matter (dl / g)>
The acetone-soluble component is dried, dissolved in N, N-dimethylformamide to give a solution having a concentration of 0.4 g / 100 ml, and the reduced viscosity is determined from the flow-down time measured at 30 ° C. using a Cannon Fenceke type viscosity tube. Ask.

  The graft copolymer (A) obtained as described above usually mainly contains a grafted polymer obtained by grafting a monomer containing an aromatic vinyl monomer to a conjugated diene polymer, A copolymer obtained by copolymerizing a monomer containing an aromatic vinyl monomer not grafted to the conjugated diene polymer is included. In the present invention, a copolymer not grafted to the conjugated diene polymer is also included in the copolymer (B).

  The copolymer (B) is obtained by polymerizing a monomer containing an aromatic vinyl monomer.

  Examples of the aromatic vinyl monomer constituting the copolymer (B) include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and one or more of them can be used. In particular, styrene and α-methylstyrene are preferable.

  As the copolymer (B), other monomers copolymerizable with the aromatic vinyl monomer can be used. Other monomers that can be copolymerized include vinyl cyanide monomers, (meth) acrylate monomers, maleimide monomers, amide monomers, unsaturated carboxylic acid monomers Body etc. are mentioned and it can use 1 type (s) or 2 or more types. Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile, and examples of (meth) acrylic acid ester monomers include methyl (meth) acrylate and (meth) acrylic acid. Ethyl, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, phenyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, (di) bromo (meth) acrylate Examples thereof include phenyl and chlorophenyl (meth) acrylate. Examples of maleimide monomers include N-phenylmaleimide and N-cyclohexylmaleimide. Examples of amide monomers include acrylamide and methacrylamide. Unsaturated carboxylic acid monomers include acrylic acid and methacrylate. Acid, maleic acid, fumaric acid, and itaconic acid can be exemplified.

  Although there is no restriction | limiting in particular in the composition ratio of the monomer which comprises a copolymer (B), Aromatic vinyl-type monomer 50 to 90 weight%, vinyl cyanide-type monomer 10 to 50 weight%, and copolymerization Other possible monomer composition ratio of 0 to 40% by weight, aromatic vinyl monomer 30 to 80% by weight, (meth) acrylic acid ester monomer 20 to 70% by weight and other copolymerizable monomers Composition ratio of 0-50% by weight of vinyl monomer, 20-70% by weight of aromatic vinyl monomer, 20-70% by weight of (meth) acrylic acid ester monomer, vinyl cyanide monomer The composition ratio is preferably 10 to 60% by weight of the body and 0 to 50% by weight of the other copolymerizable monomer.

  Although there is no restriction | limiting in particular in the reduced viscosity of the acetone soluble part of a copolymer (B), 0.1-0.8 dl / g is preferable and 0.2-0.7 dl / g is more preferable. By adjusting so that it may become the said range, the balance of fluidity | liquidity and impact resistance can be improved.

  The said reduced viscosity can be calculated | required by a following formula.

  The copolymer (B) is dissolved in N, N-dimethylformamide to obtain a solution having a concentration of 0.4 g / 100 ml, and the reduced viscosity is determined from the flow-down time measured at 30 ° C. using a Cannon-Fenske type viscosity tube. Ask.

  The polymerization method of the graft copolymer (A) and the copolymer (B) is not particularly limited, and for example, produced by an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or a combination of these methods. can do.

  The thermoplastic resin composition for three-dimensional modeling of the hot melt lamination system of the present invention contains a rubber-reinforced styrene resin composed of a graft copolymer (A) and a copolymer (B), and is a thermoplastic resin composition. The content of the conjugated diene polymer in the product is preferably 5 to 30% by weight, more preferably 10 to 20% by weight, and most preferably 13 to 19% by weight. By adjusting so that it may become the said range, the balance of fluidity | liquidity and impact resistance can be improved.

In The fluidity of the rubber-reinforced styrene resin constituting the hot-melt lamination method 3D molded thermoplastic resin composition of the present invention, melt volume rate (220 ° C., 10 kgf) is 20 (cm ^3/10 min) or higher There must be. By adjusting to be in the above range, when used for a filament of a hot melt lamination type 3D printer, the bond strength of the melt extruded strand is increased, and a solid shaped article is obtained by eliminating gaps between the laminations. be able to. Furthermore, the lamination speed is increased and the modeling time can be shortened. Preferably at 50 ^(cm 3/10 min) or more, more preferably 60 ^(cm 3/10 min) or more. Further, the upper limit of fluidity, it is preferable that the balance between the impact resistance is 150 ^(cm 3/10 min) or less, more preferably at most 120 ^(cm 3/10 min), 100 (cm and most preferably ^3/10 min) or less.

  Resins other than rubber-reinforced styrene resins can be mixed in the thermoplastic resin composition for three-dimensional modeling of the hot melt lamination system of the present invention. As such other resins, for example, acrylic resins such as polymethyl methacrylate, polycarbonate resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polyamide resins, polylactic acid resins and the like can be used. In addition, it is preferable that resin other than rubber-reinforced styrene resin is substantially not included from the viewpoint of improving the balance of fluidity, impact resistance and color developability. “Substantially free” means that the resin content other than the rubber-reinforced styrene-based resin is less than 5% by weight with respect to the entire thermoplastic resin composition.

  Furthermore, the thermoplastic resin composition for three-dimensional modeling of the hot melt lamination system of the present invention includes a hindered amine light stabilizer, a hindered phenol-based, a sulfur-containing organic compound-based, a phosphorus-containing organic compound-based antioxidant, Phenol-based, acrylate-based heat stabilizers, benzoate-based, benzotriazole-based, benzophenone-based, salicylate-based UV absorbers, organonickel-based, higher fatty acid amides and other lubricants, phosphate esters and other plasticizers, poly Bromophenyl ether, tetrabromobisphenol-A, brominated epoxy oligomers, halogenated compounds such as brominated compounds, phosphorus compounds, flame retardants and flame retardants such as antimony trioxide, odor masking agents, carbon black, titanium oxide It is also possible to add pigments, dyes and the like. Furthermore, reinforcing agents and fillers such as talc, calcium carbonate, aluminum hydroxide, glass fibers, glass flakes, glass beads, glass wool, carbon fibers, and metal fibers can be added. In addition, when used for the filament of the hot melt lamination type 3D printer, from the viewpoint of further improving the adhesive strength of the melt-extruded strand, a higher fatty acid amide lubricant is added to the thermoplastic resin composition in an amount of 0. It is preferable to contain 5-5 weight part, and it is more preferable to contain 0.7-3 weight part. Examples of lubricants of higher fatty acid amides include ethylene / bisstearic acid amide.

  The thermoplastic resin composition for three-dimensional modeling of the hot melt lamination system of the present invention can be obtained by kneading each component using a commonly used roll, Banbury mixer, extruder, kneader or the like.

  When the thermoplastic resin composition for three-dimensional modeling of the hot melt lamination method of the present invention is used in the FDM method, it is filamentized. Filamentization can be obtained by known extrusion molding.

  The thermoplastic resin composition for three-dimensional modeling of the hot melt lamination method of the present invention can obtain a molded article by a hot melt lamination method 3D printer.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by these. In the examples, parts and% are based on weight.

Production of Graft Copolymer (A) A glass reactor was charged with 50 parts by weight of agglomerated and enlarged styrene-butadiene rubber latex (weight average particle size 0.25 μm) in terms of solid content, and nitrogen substitution was performed. After nitrogen substitution, when the temperature inside the tank reached 65 ° C., 0.2 parts by weight of lactose, 0.1 parts by weight of anhydrous sodium pyrophosphate and 0.005 parts by weight of ferrous sulfate were added to 10 parts by weight of deionized water. After the aqueous solution dissolved in the solution was added, the temperature was raised to 70 ° C. Thereafter, 15 parts by weight of acrylonitrile, 35 parts by weight of styrene, 0.05 part by weight of tertiary decyl mercaptan, 0.3 part by weight of cumene hydroperoxide and 1.0 part by weight of potassium oleate were added to 20 parts by weight of deionized water. The dissolved aqueous emulsifier solution was continuously added dropwise over 4 hours. After dripping, it was kept for 3 hours to obtain a graft copolymer latex. Thereafter, salting out, dehydration and drying were performed to obtain a powder of the graft copolymer (A). When the graft ratio and the reduced viscosity of the acetone soluble part were measured by the method described above, the graft ratio was 37.0% and the reduced viscosity of the acetone soluble part was 0.39 dl / g.

After adding 120 parts of ion-exchanged water to the production reactor for copolymer (B-1) , nitrogen substitution was performed. Thereafter, the temperature of the reactor was raised to 60 ° C., and a 3% aqueous solution in which 0.3 part by weight of potassium persulfate was dissolved was added as a polymerization initiator. Then, a 5% aqueous solution in which 75 parts by weight of styrene, 25 parts by weight of acrylonitrile, 25 parts by weight of tert-lead decyl mercaptan and 1.5 parts by weight of potassium oleate were dissolved was heated at 65 ° C. for 4 hours. It was dripped continuously. Then, it hold | maintained at 65 degreeC for 3 hours, and superposition | polymerization was complete | finished. The obtained copolymer latex was salted out, dehydrated and dried to obtain copolymer (B-1) powder. The reduced viscosity measured by the method described above was 0.60 dl / g.

Production of copolymer (B-2) Except for changing to 0.48 parts by weight of tararyid decyl mercaptan, polymerization was performed in the same manner as copolymer (B-1), and the reduced viscosity measured by the method described above was It was 0.42 dl / g.

Lubricant (C)
Ethylene bisstearic acid amide: Kao Wax EB-FF manufactured by Kao Corporation

Examples 1-2 and Comparative Example 1
After mixing the graft copolymer (A), the copolymer (B) and the lubricant (C) at the blending ratio shown in Table 1, the main screw speed was 300 rpm in a φ35 mm twin screw extruder set at a cylinder temperature of 250 ° C. The mixture was melt-kneaded and pelletized at a discharge rate of 15 kg / hr. The following evaluation was performed using the obtained pellet.

<Evaluation of fluidity>
In accordance with ISO 1133, the melt volume rate (220 ° C., 10 kgf) was measured and evaluated.
Unit: ^cm 3/10 minutes

<Evaluation of impact resistance>
A test piece was molded in accordance with ISO 294.
Based on ISO179, the Charpy impact value with a notch was measured at 4 mm thickness. Unit: kJ / m ²

<Evaluation of peelability of shaped objects>
The obtained pellet was formed into a filament having a diameter of 1.8 mm, and a hollow rectangular solid product having a size of 40 mm × 40 mm × 70 mm (length × width × height) was obtained using a 3D printer of FDM method. . The obtained shaped object was visually observed to confirm whether there was a gap between the layers.
○: No gap ×: There is a gap

<Evaluation of adhesive strength>
A test piece (I) obtained in conformity with ISO 294 and a test piece (P) obtained using a 3D printer of the FDM method with the same shape as this, in conformity with ISO 179, 4 mm thick, notched Charpy The impact value was measured. And the Charpy impact value of the test piece (P) with respect to the Charpy impact value of the test piece (I) obtained by the following formula (1) was defined as the impact retention ratio (%). The higher the impact retention rate, the closer the impact value is to that of an injection-molded product, and the higher the bond strength of the strand melt-extruded from the 3D printer of the FDM method, the stronger the molded product is obtained. It shows that.

Impact retention ratio (%) = Charpy impact value of test piece (P) / Charpy impact value of test piece (I) × 100 (1)

  These evaluation results are shown in Table 1.

As is clear from Table 1, Examples 1 and 2 using the thermoplastic resin composition of the present invention were all excellent in the balance of fluidity, impact resistance and adhesion strength of the molded article. And since it was excellent in peelability (there is no space | gap) and was excellent also in the impact retention, the solid molded article was obtained.
In Comparative Example 1, the fluidity was lower than that of the present invention, the peelability (having voids) was inferior, and the impact retention was also inferior, so that a strong molded article could not be obtained.

As described above, the thermoplastic resin composition for three-dimensional modeling of the hot melt lamination method of the present invention is excellently used as a filament for a 3D printer because of its excellent balance of fluidity, impact resistance, and bonding strength of a modeled object. can do.

Claims (2)

A rubber-reinforced styrene resin having a melt volume rate (220 ° C., 10 kgf) of 50 (cm 3/10 min) or more is contained, and the rubber-reinforced styrene resin is a conjugated diene polymer (however, a hydrogenated conjugate). A diene polymer) , a graft copolymer (A) obtained by graft polymerization of a monomer containing an aromatic vinyl monomer, and a monomer containing an aromatic vinyl monomer. comprising Te copolymer (B) Tona is, hot melt lamination method 3D molded thermoplastic resin composition characterized by containing no resin other than rubber-reinforced styrene resin substantially. A molded article comprising the thermoplastic resin composition for three-dimensional modeling of the hot melt lamination method according to claim 1 .