JP2020116788A - Composition for hot melt laminating type three-dimensional printer - Google Patents

Abstract

To provide a composition for a hot melt laminating type three-dimensional printer capable of forming a three-dimensional object excellent in flexibility, transparency, adhesiveness and mechanical strength, and a filament or pellet containing the composition.SOLUTION: A composition for a hot melt laminating type three-dimensional printer includes a styrenic thermoplastic elastomer (A) and a softening agent (B). The styrenic thermoplastic elastomer (A) contains, at least, styrene-ethylene-butylene-styrene block copolymer (a1), amine-modified styrene-ethylene-butylene-styrene block copolymer (a2) and styrene-ethylene-ethylene-propylene-styrene block copolymer (a3). A weight average molecular weights Mw of the block copolymers a1 to a3 are 50,000 to 200,000, respectively. A styrene content of the styrene-ethylene-butylene-styrene block copolymer (a1) or the amine-modified styrene-ethylene-butylene-styrene block copolymer (a2) is 20 to 55 wt.%. A blending ratio of the block copolymers a1 to a3 is a2/(a1+a2+a3)=0.08 to 0.8 and a3/a1=0.35 to 3.5 in weight ratio. A blending ratio of the styrene thermoplastic elastomer (A) and the softening agent (B) is B/(A+B)=0.5 to 0.7 in weight ratio.SELECTED DRAWING: None

Description

The present invention relates to a resin composition used when molding with a three-dimensional printer, and more specifically, to a resin composition for molding with a hot melt laminated three-dimensional printer.

In recent years, a three-dimensional modeling device called a 3D (three-dimensional) printer has been applied in various fields. In particular, the heat-dissolving laminated type (FDM type) 3D printer is relatively inexpensive as compared with other type 3D printers, and is therefore becoming popular not only for industrial use but also for home use. The hot melt laminating method is a method in which pellets or filaments made of a thermoplastic resin are ejected in a molten state from a nozzle and laminated in the height direction while drawing a pattern on a plane to form a three-dimensional object. In the FDM type 3D printer, various molding materials such as pellets and filaments are put on the market in order to obtain a molded article having desired physical properties such as color, hardness and strength. As the thermoplastic resin constituting the molding material such as pellets and filaments, relatively hard resins such as polycarbonate resin, polyphenylsulfone resin, polycarbonate/acrylonitrile-butadiene-styrene resin, and ABS resin are mainly used. However, in recent years, along with the increase in demand for flexible shaped objects, there has been a demand for a soft resin material that can be used as a material for forming an FDM 3D printer.

Therefore, various resin materials have been developed and proposed to meet this need. For example, Patent Document 1 describes a resin material having a specific filament shape of a flexible polypropylene resin containing a soft component such as olefin rubber, and Patent Document 2 discloses a resin material containing a polyamide polymer as a main component. Is proposed. Further, Patent Document 3 proposes a filament containing a polylactic acid-based resin and a core-shell type rubber composed of a thermoplastic elastomer, and Patent Document 4 discloses a biodegradable thermoplastic resin and an acrylic block polymer. A filament containing is proposed. Further, in Patent Document 5, a block copolymer containing a polymer block derived from a vinyl aromatic compound and at least one of a polymer block derived from a conjugated diene and isobutylene, and hydrogenated block copolymers thereof. Filaments made of at least one block copolymer from the group of block copolymers and having specific dynamic viscoelastic properties have been proposed.

On the other hand, a modeled object of an FDM type 3D printer has been generally opaque, and it has been difficult to confirm the internal structure of the modeled object from the outside. Further, recently, a transparent shaped article is often demanded from the viewpoint of designability. Therefore, in addition to the above-mentioned need for a resin material capable of forming a flexible shaped object, a new need arises for a resin material capable of forming a molded object having transparency. With respect to the need to obtain a shaped article having both flexibility and transparency, the resin materials such as filaments disclosed in Patent Documents 1 to 5 have room for improvement in transparency. Therefore, in Patent Document 6, a flexural elastic modulus measured according to ISO178 is 1200 to 1600 MPa, which includes a styrene-based copolymer composed of a styrene-based hydrocarbon block and a conjugated diene-based hydrocarbon block. A filament having an MFR value of 0.8 to 2.4 g/10 minutes and a haze value of 15% or less, which is measured according to the conditions of 230° C./1.2 kg, is proposed.

JP, 2008-035461, A JP, 2018-043525, A JP, 2016-169456, A JP, 2017-160349, A JP, 2016-203633, A JP, 2016-141094, A

However, although the molded article formed by using the filament disclosed in Patent Document 6 has excellent transparency, there is still room for improvement in flexibility, and a resin material that achieves both improved flexibility and transparency. Was desired.

In addition, it is also performed to form each component of an assembly with a 3D printer and to bond the obtained components to each other to produce an assembly, which also has adhesiveness (peeling adhesion strength) of the molded article. It was also desired.

The present invention has been devised in view of the above-mentioned points, and an object thereof is a heat-melting laminated type three-dimensional printer capable of forming a three-dimensional object excellent in flexibility, transparency, adhesiveness and mechanical strength. The present invention provides a composition for use and a filament or pellet containing the same.

In order to solve the above problems, as a result of intensive research conducted by the present inventors, empirical findings that the transparency decreases due to the state of the lamination interface during melt lamination even when a transparent resin material is used. Based on the above, in a resin material having transparency, flexibility, adhesiveness, and mechanical strength, it is possible to improve the interlayer fusion property (also referred to as “interlayer adhesion property”) at the lamination interface with the heat-melting lamination type three-dimensional printer. It was found that it is important for improving the transparency of the obtained shaped product. The present invention has been completed based on these findings.

That is, the composition for hot melt laminated three-dimensional printer of the present invention is a composition containing a styrene-based thermoplastic elastomer (A) and a softening agent (B), wherein the styrene-based thermoplastic elastomer (A) is At least a styrene-ethylene-butylene-styrene block copolymer (a1), an amine-modified styrene-ethylene-butylene-styrene block copolymer (a2) and a styrene-ethylene-ethylene-propylene-styrene-block copolymer (a3). And a weight average molecular weight Mw of the block copolymers a1 to a3 is 50,000 to 200,000, respectively, and styrene-ethylene-butylene-styrene block copolymer (a1) or amine-modified styrene-ethylene-butylene. -The styrene content of the styrene block copolymer (a2) is 20 to 55% by weight, and the mixing ratio of the block copolymers of a1 to a3 is a2/(a1+a2+a3)=0.08 to 0.8 and a3/a1=0.35-3.5, and the mixing ratio of the styrene-based thermoplastic elastomer (A) and the softening agent (B) is B/(A+B)=0. It is 5 to 0.7.

By setting the weight average molecular weight Mw of each block copolymer (a1 to a3) of the styrene-based thermoplastic elastomer (A) to be 50,000 to 200,000, the dischargeability at the time of melt lamination and the interlayer fusion property at the time of hot melt lamination can be achieved. A composition capable of being improved to form a shaped article having excellent transparency, flexibility and mechanical strength is obtained. Further, by including the amine-modified styrene-ethylene-butylene-styrene block copolymer (a2), the adhesiveness with other materials on the surface of the modeled product is improved. Further, when the styrene content of the styrene-ethylene-butylene-styrene block copolymer (a1) or the amine-modified styrene-ethylene-butylene-styrene block copolymer (a2) is 20 to 55% by weight, tearing occurs. It is possible to obtain a composition capable of forming a molded article which is excellent in mechanical strength such as strength and is excellent in transparency of appearance. Further, the mixing ratio of the block copolymers (a1 to a3) of the styrene-based thermoplastic elastomer (A) is a2/(a1+a2+a3)=0.08 to 0.8 and a3/a1=0. By setting it to 35 to 3.5, a composition capable of forming a shaped article having excellent adhesiveness, heat resistance and mechanical strength can be obtained. Then, by setting the blending ratio of the styrene-based thermoplastic elastomer (A) and the softening agent (B) to B/(A+B)=0.5 to 0.7, the ejection property and the interlaminar fusion property at the time of melt lamination are obtained. Therefore, it is possible to obtain a composition capable of producing a shaped article having excellent flexibility and transparency and also having adhesiveness, mechanical strength, and heat resistance. The mechanical strength of the molded article as used herein means the total strength of the mechanical strength of the molded article (resin material) of the composition itself and the peel strength between the layers due to the interlayer adhesion formed by hot melt lamination.

Further, in the composition for a heat-melting laminated type three-dimensional printer of the present invention, it is also preferable that the softening agent (B) is a paraffinic oil having a molecular weight of 400 to 1200. As a result, in addition to flexibility and transparency, suitable structural components capable of improving mechanical strength, adhesiveness on the surface of the molded article (peeling adhesive strength), dischargeability at the time of melt lamination and interlayer fusion property are provided. Selected.

Further, the composition for hot melt laminated three-dimensional printer of the present invention has a melt mass flow rate (according to JIS K7210-1B method) measured at a temperature of 150 to 200° C. and a load of 2.16 kg of 15 to 3000 g/10 min. It is also preferable to have. As a result, stable ejection properties and fusion properties at the laminated interface when melt-laminated are ensured. Therefore, modeling with excellent shape accuracy is possible, light scattering at the lamination interface is reduced, the transparency of the molded article is maintained, and the adhesion at the lamination interface is increased, so that the molded article of the composition ( In combination with the mechanical strength of the resin material itself, it is possible to obtain a composition capable of forming a molded article having flexibility and excellent overall mechanical strength.

Further, the resin material for a heat-melting laminated type three-dimensional printer of the present invention contains the above-mentioned composition for a heat-melting laminated type three-dimensional printer as a main component, and has a haze value (JIS K7136:2000 compliant) of 15%. It is below, and it is also preferable that the hardness is Asker C50 or less (SRIS 0101 standard). This makes it possible to obtain a resin material capable of forming a molded article having excellent flexibility and transparency. In addition, the resin material for a heat-melting laminated type three-dimensional printer in the present specification refers to a wide range of resin materials formed from the above-mentioned composition and used for manufacturing a modeled object in the heat-melting laminated type three-dimensional printer. Shall be pointed out.

Further, the filament for a heat-melting laminated type three-dimensional printer or the pellet for a heat-melting laminated type three-dimensional printer of the present invention contains the above-mentioned composition for a heat-melting laminated type three-dimensional printer as a main component. By supplying the filaments or pellets containing the above composition for a heat-melting laminated type three-dimensional printer as a main component to a heat-melting laminated type three-dimensional printer for molding, excellent transparency, flexibility, mechanical strength and other members are obtained. It is possible to obtain a shaped article having excellent adhesiveness with.

INDUSTRIAL APPLICABILITY The composition for a heat-melting laminated type three-dimensional printer of the present invention is excellent in ejection property and interlayer adhesion at the time of heat-melting laminated layer when it is supplied to a heat-melting laminated type three-dimensional printer for molding, and has a transparent design. It is possible to form a three-dimensional modeled article having excellent mechanical strength, adhesiveness, and heat resistance as well as excellent properties, soft touch and cushioning properties.

The constitution of the test piece prepared for the peeling adhesion strength test of the molded product made of the composition for the heat-melting laminated type three-dimensional printer and the modeled by the heat-melting laminated type three-dimensional printer in the examples and the comparative examples is shown. It is the schematic (A) top view and (B) front view. It is a figure explaining the method of the peeling adhesive strength test performed using the test piece of FIG. It is a figure explaining the method of the heat resistance test of the molded object which consists of a composition for hot melt lamination type three-dimensional printers in an Example and a comparative example.

First, the styrene-based thermoplastic elastomer (A) that constitutes the composition for a hot-melt laminated type three-dimensional printer of the present invention will be described. The styrene-based thermoplastic elastomer (A) includes styrene-ethylene-butylene-styrene block copolymer (a1), amine-modified styrene-ethylene-butylene-styrene block copolymer (a2) and styrene-ethylene-ethylene-propylene-. It contains three types of block copolymers of styrene block copolymer (a3). Among these, the styrene-ethylene-butylene-styrene block copolymer (a1), that is, SEBS, also includes a hydrogenated block copolymer obtained by hydrogenating a styrene-butadiene-styrene block copolymer. The amine-modified styrene-ethylene-butylene-styrene block copolymer (a2), that is, the amine-modified SEBS also includes a hydrogenated product of the amine-modified styrene-butadiene-styrene block copolymer. The styrene-ethylene-ethylene-propylene-styrene block copolymer (a3), that is, SEEPS, also includes a hydrogenated product of a styrene-ethylene-isoprene-styrene block copolymer. The weight average molecular weight Mw of each of the block copolymers a1 to a3 is preferably 50,000 or more from the viewpoint of mechanical strength, and from the viewpoint of adhesiveness, fluidity during discharge and interlayer adhesion during hot melt lamination. It is preferably less than 200,000, that is, 50,000 to 200,000. By setting the weight average molecular weight Mw of the block copolymers of a1 to a3 to be within this range, a molded article having excellent dischargeability during melt lamination and interlayer fusion property, and also having transparency, flexibility, and mechanical strength can be obtained. can get. In addition, the molecular weight in this invention is a weight average molecular weight Mw and means the value measured by the gel permeation chromatography (GPC) method. Further, from the viewpoint of transparency of the composition and the obtained molded article, the dispersion range (difference between the maximum value and the minimum value) of each refractive index of the block copolymers of the components a1 to a3 is within 0.1. preferable.

The blending ratio of the styrene-based thermoplastic elastomer (A) that constitutes the composition for a heat-melting laminated type three-dimensional printer of the present invention is such that the block copolymers (a1 to a3) are included in terms of adhesiveness, heat resistance and mechanical strength. In terms of weight ratio, it is preferable that a2/(a1+a2+a3)=0.08 to 0.8 and a3/a1=0.35 to 3.5, and a2/(a1+a2+a3)=0.1. ˜0.7 and a3/a1=0.45 to 2.5 are more preferable. The compounding ratio a2/(a1+a2+a3) is the compounding ratio of the amine-modified SEBS(a2) in the styrene-based thermoplastic elastomer (A), but if it is less than 0.08, the adhesiveness is poor and exceeds 0.8. The mechanical strength and adhesiveness tend to decrease, and the heat resistance tends to decrease. Further, the blending ratio a3/a1 is the blending ratio of SEEPS(a3) to SEBS(a1), but if it is less than 0.35, the adhesiveness tends to be poor and the heat resistance tends to be low. If it exceeds the limit, the physical properties become unstable, such as deterioration in mechanical strength and adhesiveness. Therefore, by setting the blending ratio of each block copolymer within the above range, it is possible to obtain a composition capable of forming a shaped article having excellent adhesiveness, mechanical strength and heat resistance.

Further, the styrene content of the block copolymers a1 to a3 is the SEBS block copolymer having a styrene content of SEBS of a1 or amine-modified SEBS of a2, which is a SEBS block copolymer, from the viewpoint of improving transparency and mechanical strength. It is preferably from 20 to 55% by weight, more preferably from 25 to 45% by weight. When the styrene content is less than 20% by weight, the mechanical strength is insufficient, and when it exceeds 55% by weight, the transparency of the appearance is deteriorated. Therefore, by setting the styrene content within this range, a composition having excellent mechanical strength and excellent appearance transparency can be obtained. The styrene content of SEEPS of a3 is not particularly limited, but as an example, 25 to 35 wt% is preferable.

Next, the softening agent (B) that constitutes the composition for a heat-melting laminated type three-dimensional printer of the present invention will be described. The softening agent is added mainly for the purpose of imparting flexibility to the composition and improving interlayer fusion during melt lamination. Regarding the blending ratio of the softening agent (B), the blending ratio of the softening agent (B) to the sum of the styrene-based thermoplastic elastomer (A) and the softening agent (B) is 0.5 to 0.7 by weight ratio. It is preferably, and more preferably 0.55 to 0.65. When the value of B/(A+B) is less than 0.5, sufficient flexibility cannot be obtained, and when it exceeds 0.7, heat resistance and mechanical strength are deteriorated and adhesiveness due to bleeding of softening agent (bleeding). Occurs. Therefore, by setting the blending ratio of the softening agent within the above range, the flexibility can be adjusted without deteriorating other physical properties.

In the present embodiment, as the softener, for example, paraffin oil, process oil such as naphthenic oil or aromatic oil, synthetic resin softener such as liquid polybutene or low molecular weight polybutadiene, rosin, etc. are used, Those having a specific heat larger than that of the styrene-based thermoplastic elastomer (A) are preferable from the viewpoint of the interlayer fusion property during hot melt lamination. Of these, paraffinic oils are preferably used among process oils from the viewpoint of transparency of appearance, and paraffinic oils having a weight average molecular weight of 400 to 1200 are particularly preferably used. From the viewpoint of peel adhesion strength and mechanical strength, the weight average molecular weight is preferably 400 or more, and from the viewpoint of fluidity during molding, the weight average molecular weight is preferably 1200 or less. Therefore, by using a paraffinic oil having a weight average molecular weight of 400 to 1200, excellent dischargeability (fluidity) and interlayer fusion during hot melt lamination, and flexibility and adhesiveness (while maintaining transparency) are obtained. It is possible to obtain a composition capable of forming a molded article having better peel adhesion strength and mechanical strength.

The melt viscosity of the composition for a heat-melting laminated type three-dimensional printer of the present invention has a melt mass flow rate (MFR) according to JIS K7210-1B method of 15 to 3000 g at a temperature of 150 to 200° C. and a load of 2.16 kg. /10 min is preferable, 15 to 2000 g/10 min is more preferable, 15 to 1000 g/10 min is further preferable, and 15 to 300 g/10 min is particularly preferable. If the MFR is less than 15 g/10 min, the ejected material is less likely to spread when it is laminated on the previously formed layer, and the interlayer adhesion area is reduced, resulting in a decrease in adhesion between layers and light scattering between layers. It may become large and the transparency and mechanical strength of the molded article may decrease. Further, when the MFR exceeds 3000 g/10 min, it may be difficult to maintain the shape when ejected materials are stacked. Therefore, by setting the MFR to the above range, excellent shape accuracy, mechanical strength and transparency are obtained. Stable modeling can be performed.

Further, the haze value (according to JIS K7136:2000) of the resin material comprising the composition for a hot melt laminated three-dimensional printer of the present invention is 15% or less, and the hardness is 50 or less asker C (SRIS 0101 standard). It is preferable to show. Therefore, the resin material composition of the present invention is useful as a resin material for molding a molded article having a high appearance transparency and flexibility in modeling with a hot melt laminated three-dimensional printer. Further, since the interlayer fusion property at the time of hot melt lamination is excellent, it is possible to obtain a molded article having excellent mechanical strength in combination with the mechanical strength of the molded article (resin material) of the composition itself.

Further, the composition for a heat-melting laminated type three-dimensional printer of the present invention may contain other additives as long as the effects of the present invention are not impaired. Examples of the additive include a pigment, a colorant, a lubricant, a release agent, an antioxidant, an antibacterial agent, an ultraviolet absorber, a light stabilizer or a heat-resistant agent. These may be used alone or in combination of two or more.

The composition for hot melt laminated three-dimensional printer of the present invention is manufactured by a known method for manufacturing a resin composition. Specifically, as an example, using a melt kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer or a heating roll, the blending components such as the component A and the component B are added at a predetermined ratio. It is obtained by heating the blended components and uniformly kneading the components in a molten state. The specific manufacturing process is not particularly limited, but a weighing process of weighing each constituent component to a predetermined mixing ratio and a softening agent (B) for at least a part of the components constituting the styrene-based thermoplastic elastomer (A) It is preferable to have a pre-dispersion step of absorbing the above and a kneading step of mixing the components constituting the styrene-based thermoplastic elastomer (A) in which the softening agent (B) has been absorbed and kneading with heating. As a result, a composition in which the constituent components are more uniformly dispersed during kneading can be obtained. Further, in this preliminary dispersion step, the unit weight of each of the block copolymer constituting the styrene-based thermoplastic elastomer (A), that is, the a1 component, the a2 component, and the a3 component, in the order of higher melt viscosity at the same temperature, It is preferable to increase the distribution ratio of the softening agent (B) per hit. As a result, the melt viscosities of the components a1 to a3 that have absorbed the softening agent (B) are close to each other, and a composition in which the constituent components are more uniformly dispersed during kneading can be obtained. Furthermore, in the above-mentioned preliminary dispersion step, the softening agent (B) is dispersed in each of the block copolymer constituting the styrene-based thermoplastic elastomer (A), that is, the a1 component, the a2 component, and the a3 component. Regarding the melt mass flow rate (MFR: JIS K7210-1B method 190° C.) of each component in the state of absorbing B), the difference in MFR value between the component having the highest MFR and the component having the lowest MFR is 108 (g/10 min). It is particularly preferable that the distribution amount of the softening agent (B) is adjusted so as to be as follows. As a result, the uniform dispersibility of each component in the kneading process is further improved, the characteristics such as transparency, mechanical strength, and hardness are excellent, and the variations in these characteristics are reduced. The fusion property is also improved.

The resin composition for a heat-melting laminated type three-dimensional printer can be obtained from the composition for a heat-melting laminated type three-dimensional printer of the present invention by a known method such as extrusion molding. Specifically, a filament for a heat-melting laminated type three-dimensional printer can be processed into a filament shape, and a pellet for a heat-melting laminated type three-dimensional printer can be obtained by processing it into a pellet shape. The cross-sectional shape in the radial direction of the filament for a heat-melting laminated type three-dimensional printer depends on the design specifications of the heat-melting laminating method and the system structure and ability to be used for molding, etc., but normally a circular shape is preferable, and its diameter is 1. The range of 0 to 4.0 mm is preferable. Further, the pellet form is not particularly limited as long as it has a shape and a size that can be supplied to the hot melt stacking type three-dimensional printer.

Hereinafter, the present invention will be described in detail with reference to examples. The evaluation methods of the composition for a heat-melting laminated type three-dimensional printer and the resin material (molded product) comprising the same in the following Examples and Comparative Examples are as follows.

(1) Haze value (transparency)
Based on JIS K7136:2000, haze measurement of each test piece was performed using the haze meter (Haze meter by Suga Test Instruments Co., Ltd., HZ-1). As the test piece, the one prepared by molding each of the compositions for hot melt laminated type three-dimensional printer in Examples and Comparative Examples into a length of 50 mm×width of 50 mm×thickness of 3 mm was used. When the haze value was 15% or less, it was judged as excellent (◯), and when it exceeded 15%, it was judged as unacceptable (x).

(2) Hardness The hardness of each test piece was measured using an Asker C durometer (SRIS 0101 standard) according to JIS K6253. As the test piece, the one prepared by molding each of the compositions for heat-melting laminated type three-dimensional printer in Examples and Comparative Examples into a length of 60 mm×a width of 60 mm×a thickness of 12 mm was used. Asker C of 50 or less was judged to be good “◯”, and when it exceeded 50, it was judged to be unsuitable “x”.

(3) Tear strength (strength)
In accordance with JIS K6252-1 B method, the tensile tester (for 5 test pieces in which the composition for each of the heat-melting laminate type three-dimensional printers in Examples and Comparative Examples was formed into a non-cut angle shape (dumbbell B type) Shimadzu Corporation Autograph (registered trademark), AT-100N) was used to measure the maximum load value F[N] until breakage at a pulling speed of 500 mm/min and divided by the thickness t[m] of the test piece. And the tear strength was calculated. The tear strength (kN/m) was defined as the average value of the two values sandwiching the median tear strength of the five test pieces. A tear strength value of 6 kN/m or more was judged as excellent “◯”, and a tear strength value of less than 6 kN/m was judged as unacceptable “x”.

(4) Peel adhesion strength (in Tables 2 to 6, described as "bond strength")
The peel adhesion strength of each test piece was measured according to JIS K6854-3. A method for testing the peel adhesion strength will be specifically described with reference to FIGS. 1 and 2. FIG. 2 schematically shows the structure of the sample piece 50, and FIG. 2 illustrates a peeling adhesive strength test method for the sample piece. The sample piece 50 shown in FIG. 2 was manufactured as follows. Each of the heat-meltable laminated type three-dimensional printer compositions in Examples and Comparative Examples was molded into a strip shape (width 20 mm x length 60 mm x thickness 3 mm), and the strip surface was treated with a urethane coating agent to give a test piece. It was set to 51. The test piece 51 was bonded to a urethane piece 52 (Kuraray Co., Ltd., Kuramil U2195, width 20 mm×length 60 mm×thickness 3 mm), which was also produced in a strip shape, with an adhesive 53 to obtain a sample piece 50. More specifically, the surfaces of the test piece 51 and the urethane piece 52 were wiped with Kimwipe (registered trademark) dipped in methyl ethyl ketone (MEK), and then dried at 60° C. for 3 minutes. A primer (G-6626 manufactured by No-Tape Industrial Co., Ltd.) was applied to the surface of the test piece 51 treated with the urethane coating agent and one surface of the urethane piece 52, and dried at 60° C. for 5 minutes. An adhesive (No. 4950, manufactured by No-Tape Kogyo Co., Ltd.) was applied thereon, and after drying at 60° C. for 5 minutes, the test piece 51 and the urethane piece 52 were quickly attached. The sample piece 50 was obtained by placing the test piece 51 side up and pressing it with a hand roller to apply a force of ^{2 to 3} kgf/cm ² . After curing the sample piece 50 for 12 hours, as shown in FIGS. 2(A) and 2(B), the sample piece 50 was subjected to a tensile tester (Autograph (registered trademark) AT-100N manufactured by Shimadzu Corporation). The test piece 51 and the urethane piece 52 were peeled off and the peeling adhesive strength was measured. In FIG. 3, 54 is a fixed-side pulling jig, and 55 is a movable-side pulling jig. The load cell was 1 kN (100 kgf), the test speed was 50 mm/min, and the initial gap between the fixed side pulling jig 54 and the movable side pulling jig 55 was 20 mm.

(5) Adhesion state Regarding the peeling state of each sample piece after the peeling adhesive strength test, the adhesion state of each test piece was evaluated by visual observation or microscope observation. The case where material destruction (destruction of adherend) has occurred is designated as “AF”, and the case where interfacial peeling occurs at the interface between the molded body of the composition for melt-laminating three-dimensional printer and the protective layer formed by the urethane coating agent. "IP1" was set, and "IP2" was set when interfacial peeling occurred at the interface between the urethane coating 52 and the urethane piece 52 (adhesion material).

As the evaluation of the adhesiveness, the peeling adhesive strength of 4 kgf/20 mm or more and the material fractured test piece is evaluated as excellent adhesiveness "○", and the peeling adhesive strength of less than 4 kgf/20 mm or the interface peeled test piece The adhesiveness was evaluated as "poor".

(6) Heat resistance A heat resistance test method will be described with reference to FIG. The composition for each of the heat-melting laminated type three-dimensional printers in Examples and Comparative Examples was molded into a strip of 35 mm×10 mm×thickness of 3 mm to obtain a test piece for a heat resistance test. As shown in FIG. 3(A), the test piece 60 was tilted at 30° from the vertical direction, and was attached to the test piece gripper 61 in the shape of a single beam with the one end 30 mm portion of the test piece 60 exposed. In this state, the test piece was placed in an oven (DKN602 manufactured by Yamato Scientific Co., Ltd.) together with a jig and heated at a temperature of 85° C. for 10 minutes. After heating, the test piece 60 together with the jig was taken out of the oven and cooled to room temperature. After cooling, as shown in FIG. 3(B), with respect to the ridge line on the front surface side of the test piece 60 in a side view, a line obtained by extending the linear ridge line of the portion P fixed to the test piece gripper 61, and the test The crossing angle θt ₁ with the tangent line of the outer free end Q, which was obtained by thermal deformation of the piece 60 and was curved, was measured using a measuring microscope (MM-800/LFA manufactured by Nikon Corporation). Similarly, regarding the ridge line on the other surface (back surface) side of the test piece 60 in side view, the line extending from the linear ridge line of the portion P fixed to the test piece gripper 61 and the test piece 60 are heated. The intersection angle θt ₂ with the tangent line of the deformed and curved inner free end Q was measured. Of the measured crossing angles θt, the one with the larger measured value was defined as the thermal deformation angle θt. When the thermal deformation angle θt was 90° or less, it was judged as excellent “◯”, when it was over 90° to 125°, it was judged as good “Δ”, and when it exceeded 125°, it was judged as unsuitable “x”.

(7) Melt mass flow rate (MFR)
According to JIS K7210-1B method, the melt mass flow rate at a temperature of 150° C., 170° C. and 190° C. was measured with a load of 2.16 kg. As the measuring device, a melt indexer MP600 manufactured by Tinius Olsen was used.

Further, in the following Examples and Comparative Examples, the evaluation methods of the molded products obtained by molding the composition for a heat-melting laminated type three-dimensional printer with a heat-melting laminated type three-dimensional printer are as follows.

(1) Haze value (transparency)
Based on JIS K7136:2000, haze measurement of each test piece was performed using the haze meter (Haze meter by Suga Test Instruments Co., Ltd., HZ-1). As the test piece, the composition for each of the heat-melting laminated type three-dimensional printers in Examples and Comparative Examples was prepared by using the heat-melting laminated type three-dimensional printer (in-house prototype device, nozzle diameter 0). .8 m), each of which was shaped. Specifically, the discharge temperature of the printer nozzle is 190° C., the drawing speed (head moving speed) is 10 mm/sec, the discharge speed is 5 mg/sec, the drawing width (the pitch at which the head shifts when moving to adjacent line drawing) is 1.2 mm. Further, a drawing layer was formed so that a square of 50 mm in length×50 mm in width was filled by repeating straight line folding in one direction under the condition of a gap (stacking pitch) of 0.5 mm between the nozzle and the surface to be drawn. After that, the head is raised by the stacking pitch under the same conditions, the direction is changed by 90 degrees, and linear folding back is repeated in the direction orthogonal to the drawing direction of the previous drawing layer, so that a square with a length of 50 mm and a width of 50 mm is filled. The process of forming and stacking different drawing layers was repeated. In this way, the drawing layers were laminated so that the drawing directions of the adjacent layers were orthogonal to each other, and modeling was performed until the thickness became 3 mm to obtain a test piece. The case where the haze value of the test piece was 60% or less was judged as excellent (◯), and the case where it exceeded 60% was judged as unacceptable (x).

(2) Hardness The hardness of each test piece was measured using an Asker C durometer (SRIS 0101 standard) according to JIS K6253. As a test piece, the composition for each of the heat-melting laminated type three-dimensional printers in Examples and Comparative Examples had a length of 60 mm×width of 60 mm×thickness of 12 mm. 0.8 mm) was used, and each modeled was used. Specifically, the discharge temperature of the printer nozzle is 190° C., the drawing speed (head moving speed) is 10 mm/sec, the discharge speed is 5 mg/sec, the drawing width (the pitch at which the head shifts when moving to adjacent line drawing) is 1.2 mm. Further, a drawing layer was formed so as to fill a square of 60 mm in length×60 mm in width by repeating straight line folding in one direction under the condition of a gap (stacking pitch) of 0.5 mm between the nozzle and the surface to be drawn. After that, the head is raised by the stacking pitch under the same conditions, the direction is changed by 90 degrees, and linear folding back is repeated in a direction orthogonal to the drawing direction of the previous drawing layer, so that a square of 60 mm in length × 60 mm in width is newly filled. The process of forming and stacking different drawing layers was repeated. In this way, the drawing layers were laminated so that the drawing directions of the adjacent layers were orthogonal to each other, and modeling was performed until the thickness became 12 mm, and a test piece was obtained. When the hardness of the test piece of the test piece was Asker C50 or less, it was judged as “good”, and when it exceeded 50, it was judged as unsuitable as “x”.

(3) Adhesion between layers The test piece used in the hardness test (2) above was clamped at both ends in the longitudinal or transverse directions with a tensile test jig, and the tensile speed was reduced to 150% of the original dimension at 500 mm/min. Check the condition of the layers when they are tensile deformed until it is visible or under a microscope.No peeling between the layers or a material breakdown between the layers is good.○, no peeling between the layers is possible. It was judged as "x".

Table 1 shows the specifications of the respective constituents used in the following Examples and Comparative Examples. Here, the molecular weight Mw in Table 1 is a weight average molecular weight measured by a gel permeation chromatography (GPC) method. Specifically, the molecular weight Mw is measured by SHODEX (registered trademark) GPC-104 (a product of Showa Denko KK) [separation column LF-404 (three connected), guard column LF-G, RI detector RI-. 74S (both manufactured by Showa Denko KK)] was used as the eluent, and the measurement was performed under the conditions of a sample concentration of 10 mg/4 ml, an eluent flow rate of 0.3 ml/min, and a column temperature of 40°C.

[Example 1]
The composition for a hot melt laminated three-dimensional printer of this example was manufactured by the following procedure, and its effect was evaluated. Among the styrene-based thermoplastic elastomers (component A) shown in Table 1, as SEBS (a1), 615 g (20.5% by weight) of SEBS (A104) having a styrene content of 42% and a weight average molecular weight of 150,000, amine-modified SEBS 210 g (7% by weight) of amine-modified SEBS (A201) having a styrene content of 30% and a weight average molecular weight of 67,000 is used as (a2), and SEEPS (A301) having a styrene content of 30% and a weight average molecular weight of 85,000 is used as SEEPS (a3). 330 g (11% by weight) was weighed individually. Next, of the softening agent (B component) shown in Table 1, 1845 g (61.5% by weight) of paraffin oil (B103) having a weight average molecular weight of 1200 was weighed. Of this paraffin oil, 1020 g (34% by weight) was added to the a1 component, 210 g (7% by weight) to the a2 component, and 615 g (20.5% by weight) to the a3 component. After each block copolymer and paraffin oil were mixed at room temperature, the mixture was heated at 100° C. for 12 hours to disperse the paraffin oil in each of the components a1 to a3 (preliminary dispersion step). After dry blending the block copolymers of a1 to a3 in which paraffin oil has been absorbed by hand stirring, a batch type twin-screw kneader (TD3-10MDX type manufactured by Toshin Co., Ltd.) at 160 to 180° C. and a rotation speed of 40 rpm are used. The mixture was kneaded for 15 minutes (kneading step) to obtain 3 kg of a composition for a hot melt laminated three-dimensional printer. This composition was injection-molded under the condition of 150 to 170° C. into a predetermined test piece shape used in each evaluation method of the composition for a heat-melting laminated type three-dimensional printer described above, and the obtained test piece was used for physical properties and the like. Was evaluated.

On the other hand, granular pellets were prepared as a resin material for a three-dimensional printer from the composition for a heat-melting laminated type three-dimensional printer obtained in Example 1. Using these pellets, a thermal melting laminated type three-dimensional printer (in-house prototype device, nozzle diameter 0.8 m), discharge temperature 190° C., drawing speed (head moving speed) 10 mm/sec, discharge speed 5 mg/sec, drawing Modeling by the above-mentioned heat-melting stacking type three-dimensional printer under the conditions of width (pitch at which the head shifts when moving to adjacent line drawing) 1.2 mm and gap between nozzle and drawing surface (stacking pitch) 0.5 mm. Predetermined test pieces used in each evaluation method of the product were obtained as a three-dimensional printer molded product. The test pieces were used to evaluate physical properties and the like.

[Examples 2 to 8]
Except that the styrene-based thermoplastic elastomer (component A), the softening agent (component B), and the compounding ratios thereof, which are the constituent components of the composition for a heat-melting laminated type three-dimensional printer, are changed as shown in Table 2 below. In the same manner as in Example 1, the hot-melt laminated type three-dimensional printer composition of each Example was obtained. In the same manner as in Example 1, a test piece for physical property evaluation was molded using the obtained composition for hot melt laminated three-dimensional printer, and physical properties and the like were evaluated. Further, in the same manner as in Example 1, pellets were prepared using the composition for a heat-melting laminated type three-dimensional printer of each Example, and a predetermined test piece was three-dimensionally formed by using the pellets in a heat-melting laminated type three-dimensional printer. It was manufactured as a printer model and evaluated for physical properties and the like.

The results of Examples 1 to 8 are shown in Table 2. Here, the “MFR difference after pre-dispersion” in Table 3 means the component having the highest melt viscosity with respect to the melt viscosity (MFR: melt mass flow rate) of the components a1 to a3 in the state in which the softening agent (B) is dispersed. And the difference in melt viscosity of the lowest component. Specifically, for the a1 to a3 components after the preliminary dispersion treatment, the melt mass flow rate at 190° C. was measured in accordance with JIS K7210-1B method, and the melt viscosity of the component having the highest value and the component having the lowest value were measured. It is a value obtained by calculating the difference in melt viscosity (the same applies to Tables 3 to 6 below).

[Examples 9 to 16]
Except that the styrene-based thermoplastic elastomer (component A), the softening agent (component B), and the compounding ratios thereof, which are the constituent components of the composition for a heat-melting laminated type three-dimensional printer, are changed as shown in Table 3 below. In the same manner as in Example 1, the hot-melt laminated type three-dimensional printer composition of each Example was obtained. In the same manner as in Example 1, a test piece for physical property evaluation was molded using the obtained composition for hot melt laminated three-dimensional printer, and physical properties and the like were evaluated. Further, in the same manner as in Example 1, pellets were prepared using the composition for a heat-melting laminated type three-dimensional printer of each Example, and a predetermined test piece was three-dimensionally formed by using the pellets in a heat-melting laminated type three-dimensional printer. It was manufactured as a printer model and evaluated for physical properties and the like. The results of Examples 9 to 16 are shown in Table 3.

[Examples 17 to 24]
Except that the styrene-based thermoplastic elastomer (component A) and the softening agent (component B), which are the constituent components of the composition for a heat-melting laminated type three-dimensional printer, and their compounding ratios were changed as shown in Table 4 below. In the same manner as in Example 1, the hot-melt laminated type three-dimensional printer composition of each Example was obtained. In the same manner as in Example 1, a test piece for physical property evaluation was molded using the obtained composition for hot melt laminated three-dimensional printer, and physical properties and the like were evaluated. Further, in the same manner as in Example 1, pellets were prepared using the composition for a heat-melting laminated type three-dimensional printer of each Example, and a predetermined test piece was three-dimensionally formed by using the pellets in a heat-melting laminated type three-dimensional printer. It was manufactured as a printer model and evaluated for physical properties and the like. The results of Examples 17 to 24 are shown in Table 4.

[Comparative Examples 1 to 4]
A composition of each comparative example was obtained in the same manner as in Example 1 except that the styrene-based thermoplastic elastomer (component A), the softening agent (component B), and their compounding ratios were changed as shown in Table 5 below. It was In the same manner as in Example 1, a test piece for physical property evaluation was molded using the obtained composition and physical properties and the like were evaluated. Further, in the same manner as in Example 1, pellets were prepared from the composition obtained in each comparative example, and a predetermined test piece was prepared as a three-dimensional printer molded article by a hot-melt layered three-dimensional printer using the pellets. The physical properties were evaluated. The results of Comparative Examples 1 to 4 are shown in Table 5.

[Comparative Examples 5 to 10]
A composition of each comparative example was obtained in the same manner as in Example 1 except that the styrene-based thermoplastic elastomer (component A), the softening agent (component B) and their compounding ratios were changed as shown in Table 6 below. It was In the same manner as in Example 1, pellets were prepared from the composition obtained in each comparative example, and a predetermined test piece was prepared as a three-dimensional printer model by a hot-melt laminating three-dimensional printer using the pellets, and physical properties and the like were obtained. Was evaluated. The results of Comparative Examples 5-10 are shown in Table 6.

From the results of Examples 1 to 24 shown in Tables 2 to 4, a molded article (resin material) excellent in transparency, flexibility, mechanical strength and heat resistance was obtained by using the composition of the present invention. It was found that a hot melt laminated type three-dimensional printer composition which forms Further, it was found that the three-dimensional printer model formed by using the composition for hot melt laminated three-dimensional printer has excellent adhesiveness to other members.

Comparing the results of Examples 4 to 5 and Comparative Examples 1 to 2, if the molecular weight range of the components a1 to a3 constituting the styrene-based thermoplastic elastomer (A) deviates from the range of 50,000 to 200,000, it is compared with other members. It was found that the transparency (haze property) and the interlayer adhesion of the shaped article were poor because the adhesiveness of No. 1 decreased and the fusion adhesion at the time of hot melt lamination decreased. Further, when the results of Examples 7 to 8 and Comparative Examples 3 to 4 are compared, when the styrene content of the block copolymers a1 and a2 falls outside the range of 20 to 55%, the tear strength decreases. It was found that when the styrene content is out of the range of 20 to 55% and becomes high, the transparency decreases. Further, from the comparison between Examples 9 to 16 shown in Table 4 and Comparative Examples 5 to 8 shown in Table 7, the mixing ratio of the block copolymers a1 to a3 is a weight ratio, a2/(a1+a2+a3)=0. If it is out of the range of 08 to 0.8 or a3/a1=0.35 to 3.5, the adhesiveness of the composition for the heat-melting laminated type three-dimensional printer to other members of the molded article is deteriorated. If the value of a2/(a1+a2+a3) exceeds 0.8 (Comparative Example 6) or the value of a3/a1 exceeds 3.5 (Comparative Example 8), the tear strength also decreases, and a2/(a1+a2+a3) When the value of) is more than 0.8 (Comparative Example 6) or when the value of a3/a1 is less than 0.35 (Comparative Example 7), the blending amount of the component a3 is small, so that the heat-melting laminated type is used. It was found that the heat resistance of the molded body of the composition for three-dimensional printer was inferior. Further, from the comparison between Examples 17 to 22 in Table 4 and Comparative Examples 9 to 10 in Table 6, the mixing ratio of the styrene-based thermoplastic elastomer (A) and the softening agent (B) was B/(A+B). If the value of) is less than 0.5, the hardness becomes high and the flexibility is poor, and if it exceeds 0.7, the softening agent (B) is excessively added, and therefore, the adhesion of the molded product of the composition for a heat-melting laminated type three-dimensional printer. It was found that the range of B/(A+B)=0.5 to 0.7 is effective because the heat resistance and the heat resistance also decrease. From the results of Example 1 in Table 1 and Examples 23 and 24 in Table 5, when paraffin oil was applied as the softening agent (B), the present invention was used when the molecular weight of paraffin oil was at least 400 to 1200. It was confirmed to have the effect of.

The present invention is not limited to the above-described embodiments or examples, and various modifications of the design are also included in the technical scope within the scope not departing from the gist of the invention described in the claims. It is a thing.

50 sample pieces 51 test pieces (molded articles of the compositions of Examples or Comparative Examples)
52 Urethane piece 53 Adhesive 54 Fixed-side tension jig 55 Movable-side tension jig 60 Test piece (for heat resistance test)
61 Test piece gripping tool 62 Jig (support arm)
θt Crossing angle (thermal deformation angle)
P Part of the test piece 60 fixed to the test piece gripper 61 Q Free end part of the heat deformed test piece 60

Claims (6)

A composition containing a styrene thermoplastic elastomer (A) and a softening agent (B), comprising:
The styrene-based thermoplastic elastomer (A) is at least styrene-ethylene-butylene-styrene block copolymer (a1), amine-modified styrene-ethylene-butylene-styrene block copolymer (a2) and styrene-ethylene-ethylene. -Propylene-styrene block copolymer (a3) is contained,
The weight average molecular weights Mw of the block copolymers a1 to a3 are respectively 50,000 to 200,000,
The styrene-ethylene-butylene-styrene block copolymer (a1) or the amine-modified styrene-ethylene-butylene-styrene block copolymer (a2) has a styrene content of 20 to 55% by weight,
The blending ratio of the block copolymers of a1 to a3 is a2/(a1+a2+a3)=0.08 to 0.8 and a3/a1=0.35 to 3.5 by weight.
The blending ratio of the styrene-based thermoplastic elastomer (A) and the softening agent (B) is B/(A+B)=0.5 to 0.7 in weight ratio. Composition for printer. The composition for a hot melt laminated three-dimensional printer according to claim 1, wherein the softening agent (B) is a paraffinic oil having a molecular weight of 400 to 1200. The melt mass flow rate (according to JIS K7210-1B method) measured in a temperature range of 150 to 200° C. and a load of 2.16 kg is 15 to 3000 g/10 min, and the hot melt laminating method according to claim 1 or 2. Composition for mold three-dimensional printer. The composition for hot-melt laminated type three-dimensional printer according to any one of claims 1 to 3 is a main component, haze value (JIS K7136:2000 compliant) is 15% or less, and hardness is Asker C50 or less ( SRIS 0101 standard), which is a resin material for a heat-melting laminated type three-dimensional printer. A filament for a heat-melting laminated type three-dimensional printer, which comprises the composition for a heat-melting laminated type three-dimensional printer according to any one of claims 1 to 3 as a main component. A pellet for a heat-melting laminated type three-dimensional printer, which comprises the composition for a heat-melting laminated type three-dimensional printer according to any one of claims 1 to 3 as a main component.

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