JP3117359B2 - Thermoplastic material for molding - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material for medical use, art, play equipment, construction, civil engineering and the like.

[0002]

2. Description of the Related Art Conventionally, molding materials have (1) low viscosity as much as possible at the time of molding and good shape followability to a prototype, and (2) use after solidification (generally at room temperature). A material that was sufficiently reinforced was an essential condition. Materials that meet these requirements generally include silicone rubber,
Materials such as urethane are used.

On the other hand, recently, from the viewpoint of environmental destruction, the recyclability of such industrial waste has been regarded as an important issue. However, among these materials, silicone rubber and urethane were hardly recyclable because they were reactive thermoplastic materials.

[0004] Commercially available thermoplastic materials are also conceivable, but these materials have recyclability, but have a considerably high melting temperature and an extremely high viscosity even in a molten state, so that they have poor shape following ability. However, because of the high raw material cost, it is generally unsuitable as a molding material.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a molding material having recyclability in addition to conventional characteristics.

[0006]

According to the present invention, there is provided a thermoplastic material for molding, which is a thermoplastic material for copying a solid surface having irregularities or patterns, wherein the material is composed of a high molecular organic material and a low molecular material. A mixture of which the main component is a mixture in which the content of the high-molecular-weight organic material is lower than the content of the low-molecular-weight material.
A polymeric blend material obtained by high shear mixing forces, it becomes configured using a polymer blend material that led to the polymeric organic material by the high shear forces mixed has a network skeleton structure of a three-dimensional continuous It is characterized by the following.

Further, the molding material of the present invention is characterized in that the polymer blend material is composed mainly of a polymer material having a number average molecular weight of 20,000 or more and a low molecular material having a number average molecular weight of 20,000 or less, and And the low molecular material has a solubility parameter of 3.0 or less.

[0008]

At present, the molding material is required to have good shape followability, a sufficiently reinforced material, recyclability, and the like. However, in the conventional silicone rubber and urethane, etc., these materials are reactive thermoplastic materials, so that recyclability could hardly be expected. However, according to the thermoplastic material for molding of the present invention, (1) comparatively, (2) It is a low-temperature (up to 100 ° C.) low-viscosity melt and is a thermoplastic material that is in a solid state at room temperature, so that it can be easily poured into a mold and has good shape following properties to a prototype. 50 ~
Because it softens at 70 ° C, the shape of the prototype can be accurately reproduced by pressing and cooling to the prototype in a temperature range above this temperature. (3) Since the high-molecular organic material has a three-dimensional continuous network skeleton structure, The liquid has good releasability inside it,
(4) Since it is a thermoplastic material, it can be used repeatedly (recycled).

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, the high molecular weight organic material has a number average molecular weight of 2
0,000 or more, especially 30,000 or more, especially 4
Preferred is a thermoplastic high molecular weight organic material of at least 000,
For example, styrene-based (butadiene-styrene-based, isoprene-styrene-based, etc.), ester-based, amide-based, urethane-based and other thermoplastic elastomers, and hydrogenated and modified products thereof, styrene-based, ABS-based, and olefin-based (Ethylene type, propylene type, ethylene propylene type, ethylene styrene type, propylene styrene type, etc.), vinyl chloride type, acrylate type (methyl acrylate type, etc.), methacrylate type (methyl methacrylate type, etc.) carbonate System, acetal system, nylon system, halogenated polyether system (chlorinated polyether system, etc.), halogenated olefin system (ethylene tetrafluoride system, fluorinated ethylene chloride system, fluoroethylene propylene system, etc.), cellulose system ( Acetyl cellulose, ethyl cellulose Scan system, etc.), vinylidene, vinyl butyral thermoplastic resins, such as alkylene oxide-based (propylene oxide-based, etc.), and rubber-modified products of these resins.

As a specific thermoplastic polymer material, it is particularly preferable to use a thermoplastic polymer material having both a portion which easily forms a hard block such as a crystal structure and an aggregated structure and a soft block such as an amorphous structure. Specific examples include the following.

A block copolymer of polyethylene and an ethylene / butylene-styrene random copolymer obtained by hydrogenating a block copolymer of polybutadiene and a butadiene-styrene random copolymer. A block copolymer of polybutadiene and polystyrene, or a block copolymer of polyethylene / butylene and polystyrene obtained by hydrogenating a block copolymer of polybutadiene or a random copolymer of ethylene-butadiene and polystyrene. Ethylene-propylene rubber. Of these, a block copolymer of polyethylene and an ethylene-styrene random copolymer is particularly preferred.

[0012] These various thermoplastic high molecular organic materials are mainly used alone, but two or more kinds may be blended and used.

On the other hand, the low molecular weight material has a viscosity at 100 ° C. of 5 × 10 ⁵ centipoise or less, especially 1 × 1 centipoise.
0 ⁵ centipoise or less, and from the viewpoint of molecular weight, the number average molecular weight of the low molecular weight material is 20,
000 or less, especially 10,000 or less, especially 5,000
It is preferably 0 or less. Usually, a liquid or liquid material at room temperature is suitably used as such a low molecular material. Further, both hydrophilic and hydrophobic low molecular materials can be used. Although the low molecular material is not particularly limited, the following are suitable.

Softeners: Softeners for various rubbers or resins, such as mineral oils, vegetable oils, and synthetic oils. Examples of the mineral oils include aromatic, naphthenic, and paraffinic process oils. Vegetable oils include castor oil, cottonseed oil, sweet oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, wood wax, pine oil, olive oil, and the like.

Plasticizers: Various ester plasticizers such as phthalic acid ester, phthalic acid mixed ester, aliphatic dibasic acid ester, glycol ester, fatty acid ester, phosphoric acid ester, stearic acid ester, epoxy plasticizer, etc. Plasticizers for plastics or phthalates, adipates, sebacates, phosphates,
NBR plasticizers such as polyethers and polyesters.

Tackifiers: Various tackifiers (tackifiers) such as coumarone resins, coumarone-indene resins, phenol terpene resins, petroleum hydrocarbons, and rosin derivatives.

Oligomer: crown ether, fluorine-containing oligomer, polyisobutylene, xylene resin, chlorinated rubber, polyethylene wax, petroleum resin, rosin ester rubber, polyalkylene glycol diacrylate,
Various oligomers such as liquid rubbers (polybutadiene, styrene-butadiene rubber, butadiene-acrylonitrile rubber, polychloroporene, etc.), silicone oligomers, and poly-α-olefins.

Lubricants: hydrocarbon lubricants such as paraffin and wax; fatty acid lubricants such as higher fatty acids and oxy fatty acids; fatty acid amide lubricants such as fatty acid amides and alkylene bis fatty acid amides; fatty acid lower alcohol esters; fatty acid polyhydric alcohol esters , Ester lubricants such as fatty acid polyglycol esters, fatty alcohols,
Various lubricants such as alcoholic lubricants such as polyhydric alcohol, polyglycol and polyglycerol, metal soaps, and mixed lubricants.

In addition, latex, emulsion, liquid crystal, bituminous composition, clay, natural starch, sugar, inorganic silicon oil, phosphazene, etc. are also suitable as low molecular weight materials. In addition, beef oil, pork oil, animal oil such as horse oil,
Bird oil or fish oil: honey, fruit juice or dairy products such as chocolate, yogurt, hydrocarbons, halogenated hydrocarbons, alcohols, phenols, ethers, acetals, ketones, fatty acids, esters,
Organic solvents such as nitrogen compounds and sulfur compounds: or various medicinal ingredients, soil modifiers, fertilizers, petroleum,
Water, an aqueous solution and the like are also used.

These low molecular weight materials may be used alone or as a mixture of two or more.

In the present invention, in order to obtain a polymer blend material containing a large amount of a low molecular weight material by a large amount of a low molecular weight material and a high molecular weight organic material, each solubility parameter of the low molecular weight material and the high molecular weight organic material is used. Value δ = (ΔE /
V) ^1/2 (ΔE = molar evaporation energy, V = molar volume)
So that the difference is 3.0 or less, preferably 2.5 or less.
It is preferred to select both materials. If this difference exceeds 3.0, it is difficult to maintain a large amount of low molecular weight material due to the compatibility of the two materials, which hinders the lowering of the elasticity of the obtained polymer blend material. It is not preferable because it easily occurs.

The polymer blend material according to the present invention may further contain the following fillers, if necessary. That is, clay, diatomaceous earth, carbon black, silica, talc, barium sulfate, calcium carbonate,
Scale-like inorganic fillers such as magnesium carbonate, metal oxides, mica, graphite, and aluminum hydroxide; various metal powders, wood chips, glass powders, ceramic powders, and granular or powdery solid fillers such as granular or powdery polymers, etc. And various natural or artificial short fibers and long fibers (for example, straw, hair, glass fiber, metal fiber, and other various polymer fibers).

The weight can be reduced by blending a hollow filler, for example, an inorganic hollow filler such as a glass balloon or a silica balloon, or an organic hollow filler made of polyvinylidene fluoride or a polyvinylidene fluoride copolymer. Furthermore, it is also possible to mix various foaming agents to improve various physical properties such as weight reduction.
It is also possible to mechanically mix the gas such as during mixing.

In order to provide such characteristics, the three-dimensional continuous network skeleton structure formed of the high molecular weight organic material constituting the high molecular weight blend material has an average diameter of the skeleton of 50 μm.
m, preferably 30 μm or less, the average diameter of the cells (mesh) is 500 μm or less, preferably 300 μm or less, and the volume fraction of the high molecular organic material is [volume of high molecular organic material / (high molecular organic material) Volume + volume of low molecular material)]
When defined as × 100 (%), it is desirable that the volume fraction of the high molecular weight organic material is 30% or less, particularly 25% or less.

The polymer blend material used in the present invention comprises a predetermined amount of a high-molecular organic material and a low-molecular material, and if necessary, other compounding agents. The high-molecular organic material forms a three-dimensional continuous network skeleton structure. It can be obtained by mixing under possible mixing conditions, in this case, while having a uniform three-dimensional continuous network skeleton structure of a high molecular organic material,
In order to obtain a high molecular weight blended material which satisfies the above-mentioned characteristics with less bleeding of the low molecular weight material, it is preferable to use a high shear type mixer as the mixer, and in particular, between the fixed wall and the rotating rotor. Can provide high shearing force and high shearing speed with fixed wall and rotating part (rotor)
The distance (clearance) to the rotor is t (m), the rotational peripheral speed of the rotor is v (m / sec), and the shearing speed V of the rotor is
Is defined as V = v / t (sec ⁻¹ ), V ≧ 5.0 × 10 ² (sec ⁻¹ ), preferably V ≧ 1.0 × 10 ³ (sec ⁻¹ ), more preferably V ≧ 2 the .5 × 10 ³ (sec ^-1) and most preferably it is advantageous to use a high shear special mixer satisfying ^{V ≧ 5.0 × 10 3 (sec} -1).

The polymer blend material according to the present invention is in a normal bulk state. Although not particularly limited, such as a gel and a foam, those in a gel state, particularly those in a gel state having a three-dimensional continuous uniform network skeleton structure made of a thermoplastic polymer material, are particularly effective for the present invention.

The mold-forming thermoplastic material of the present invention is not particularly limited. For example, the thermoplastic material used as a mold (FIG. 1)
(A)-(b)) and those used as solid supports (see FIGS. 2 (a)-(c)).

Further, when the molded thermoplastic material of the present invention is used as a mold, it is used for medical purposes (prostheses, artificial hands, dentures, etc.), works of art (sculptures, paintings, foreheads, etc.), games, etc. It can be used as a mold for toys (general toys, natural objects, etc.). On the other hand, when used as a solid support, it can be used as a mold for architectural purposes (decorative panels for interior and exterior of buildings, floors, etc.) and for civil engineering (road pavement, decorative panels for wall surfaces, etc.).

Further, when the molded thermoplastic material of the present invention is used as a solid support and an injecting material, various pigments are added to the molded thermoplastic material for coloring,
Alternatively, harmony with the structure can be achieved by inserting a different material such as stone, cloth, plastic, or the like.

The following is a specific description of an example of the use of the molded thermoplastic material of the present invention. (1) One Example of Use as a Mold Mold FIG. 1 is a schematic diagram showing an example in which the molded thermoplastic material of the present invention is used as a rubber mold. In the process (a), the molded thermoplastic material of the present invention is closely adhered, and the molded thermoplastic material of the present invention is melted and poured at about 100 ° C. or softened at a temperature of 50 ° C. or more. Crim the mold and cool to room temperature. Thereafter, the desired mold is obtained by removing the prototype. Next, in the process (b), a new injection material (for example, an organic material such as plastic or rubber, or an inorganic material such as cement or gypsum, etc.) is injected into the obtained mold and solidified. By removing, a desired pattern can be obtained.

(2) One example of use as a solid support FIG. 2 is a schematic diagram showing an example of using the molded thermoplastic material of the present invention as a solid support. In the process (a), a solid (for example, an organic material such as plastic or rubber, or an inorganic material such as cement or gypsum or the like) to be fixed to the molded thermoplastic material of the present invention in a molten state or a softened state is injected. Cooling. Next, in the process (b), an injection material (for example, a material such as plastic or rubber (for example, an organic material such as plastic or rubber, or a cement or gypsum material) is provided on the side opposite to the molding thermoplastic material of the present invention. Finally, in the process (c), a decorative panel having an uneven surface can be obtained by removing the molded thermoplastic material of the present invention.

Hereinafter, the present invention will be described more specifically with reference to an embodiment of the molded thermoplastic material of the present invention. (1) Method for producing a molded thermoplastic material A block composed of polystyrene and an ethylene-butylene random copolymer obtained by hydrogenating a block copolymer composed of polystyrene and polybutadiene, which are high-molecular organic materials, as raw materials. Copolymer (number average molecular weight 1
A high-shear special mixer (T.K., 50,000, δ = 8.5) obtained by adding 85 vol% of polyisobutylene (molecular weight: 500, δ = 7.4), which is a low-molecular material, to 15 vol%. Auto homoxer "manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation speed of 3000 rpm and a shearing speed of 1.0 × 10 ⁴ sec.
The mixture was mixed under the mixing conditions of c ^-1 , a mixing temperature of 140 ° C., and a mixing time of 40 minutes to obtain a polymer blend material having a uniform appearance. Further, a section of this polymer blend material was cut out and confirmed with an optical microscope. As a result, a three-dimensional continuous network skeleton structure (average skeleton diameter of 15 μm,
It was confirmed that an average cell diameter of 25 μm was formed.

[0033]

As described above, the molding material of the present invention is (1) a thermoplastic material which is a melt having a low viscosity at a relatively low temperature (up to 100 ° C.) and which is in a solid state at room temperature. Therefore, it is easy to pour into a mold and has good shape followability to the prototype. (2) Since it softens at 50 to 70 ° C., it is pressed against the prototype in a temperature range not lower than this temperature and cooled to produce the prototype. (3) Since the high molecular organic material has a three-dimensional continuous network skeleton structure, the liquid has good releasability inside it, and (4) it is a thermoplastic material. It has excellent effects that can be used.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example in which a molded thermoplastic material of the present invention is used as a rubber mold.

FIG. 2 is a schematic view showing an example in which the molded thermoplastic material of the present invention is used as a solid support.

[Explanation of symbols] 1: Polymer blend material 2: Prototype 3: Frame 4: Injection material 5: Material to be fixed

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-118117 (JP, A) JP-A-2-18453 (JP, A) JP-A-64-49564 (JP, A) JP-A-62-1984 263256 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 B29C 33/38-33/40

Claims (2)

(57) [Claims] 1. A mold-forming thermoplastic material for copying a solid surface having irregularities or patterns, wherein the material is a thermoplastic material.
Elastomers and their modified products or thermoplastics
Fats and rubber modified products of these resins, having a crystal structure,
A part such as a cohesive structure that is easy to form a hard block
With soft blocks such as morphus structure
Selected from the group consisting of thermoplastic polymer materials,
High molecular weight organic materials having a number average molecular weight of 20,000 or more and rubbers selected from mineral oils, vegetable oils, and synthetic oils.
Or a softening material for resin having a number average molecular weight of 5,000
A high molecular weight blended material obtained by mixing a mixture having a low molecular weight material as a main component and a mixture of a high molecular weight organic material having a content lower than that of the low molecular weight material at a high shear force, A thermoplastic material for molding, characterized in that a high molecular weight organic material is formed by using a high molecular weight blend material having a three-dimensional continuous network skeleton structure by high shear mixing. 2. The polymer blend material according to claim 1, wherein the polymer material has a number average molecular weight of 20,000 or more and a number average molecular weight of 50,000 or more.
2. The heat for molding according to claim 1, wherein a difference in solubility parameter between the high molecular material and the low molecular material is 3.0 or less. Plastic material.