WO2012046858A1 - 高分子ナノ配向結晶体材料の二次成型方法 - Google Patents
高分子ナノ配向結晶体材料の二次成型方法 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/52—Heating or cooling
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/222—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length characterised by the shape of the surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/24—Calendering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/44—Compression means for making articles of indefinite length
- B29C43/46—Rollers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
Definitions
- the present invention relates to a secondary molding method (molding, fusion, bonding, etc.) of a polymer nano-oriented crystal material.
- PE polyethylene
- PP polypropylene
- PS polystyrene
- PVC polyvinyl chloride
- the general-purpose plastic has drawbacks such as insufficient mechanical strength and low heat resistance. Therefore, the above-mentioned general-purpose plastic does not have sufficient characteristics required for materials used in machine products such as automobiles and various industrial products such as electrical, electronic, and information products, and its application range is The current situation is that it is restricted.
- the softening temperature is usually about 90 ° C.
- PP has insufficient transparency compared to polycarbonate (hereinafter referred to as “PC”), polyethylene terephthalate (hereinafter referred to as “PET”), PS, and the like, and therefore cannot be used as an optical material, a bottle, or a transparent container.
- PC polycarbonate
- PET polyethylene terephthalate
- PS polystyrene
- engineering plastics such as PET, PC, fluororesin (Teflon (registered trademark)), nylon, polymethylpentene, polyoxymethylene, acrylic resin, etc. are excellent in mechanical strength, heat resistance, transparency, etc. Usually, it does not soften at 150 ° C. Therefore, engineering plastics are used as materials for various industrial products and optical materials that require high performance such as automobiles, mechanical products, and electrical products. However, engineering plastics have serious drawbacks such as being expensive and having a very high environmental impact because monomer recycling is difficult or impossible.
- the general-purpose plastics can be used as an alternative to engineering plastics, or as an alternative to metal materials, It is possible to greatly reduce the costs of various industrial products and daily products made of molecules and metals, and to save energy and improve operability by reducing the weight.
- PET is currently used as a bottle for beverages including soft drinks, but if such PET can be replaced with PP, the cost of the bottle can be greatly reduced.
- PET can be monomer-recycled, but it is not easy, after used PET bottles are cut and then reused once or twice for low-quality uses such as clothing fibers and films. It has been discarded.
- PP can be easily recycled, complete recycling can be realized, and there is an advantage that consumption of fossil fuels such as petroleum and generation of carbon dioxide (CO 2 ) can be suppressed.
- CO 2 carbon dioxide
- PP and PE crystals It is required to produce a crystal body consisting only of crystals that substantially increase the degree of conversion), and more preferably contains almost no PP or PE amorphous material.
- PP has the advantage of higher mechanical strength and higher heat resistance than PE, so it is highly expected and is an important polymer that maintains a high annual output rate of several percent. It is.
- a method of adding a nucleating agent to the polymer melt is known.
- the nucleating agent is an impurity, so it is inevitable to mix impurities, (b) the crystallinity is not increased sufficiently, and (c) the nucleating agent is significantly more expensive than the resin. Therefore, there are drawbacks such as increased costs. Therefore, a method for dramatically improving the crystallinity in a polymer such as a general-purpose plastic and a method for producing a polymer crystal have not been completed at present.
- a polymer melt (referred to as an “isotropic melt”) in which molecular chains in the melt exist in a disordered form (for example, a string shape (random coil))
- a disordered form for example, a string shape (random coil)
- the characteristic crystalline form of thin fibers with a diameter of a few ⁇ m oriented along the flow, and 10 nm thick lamellar crystals and amorphous It has been clarified that the form (kebab) laminated in a sandwich shape is sparsely formed in the melt (see Non-Patent Document 1).
- the above state is called “shish-kebab” (meaning yakitori “skewer” and “meat”).
- shish is generated sparsely at the beginning of shish-kebab generation.
- the structure of shish is “extended chain crystal (ECC)” in which the molecular chain is extended and crystallized (see Non-Patent Document 5), and the structure of the crystal part of kebab is that the molecular chain is a thin plate crystal. It is considered to be a “Folded chain crystal (FCC)” that is folded on the surface of the film.
- FCC folded chain crystal
- the molecular mechanism of shish-kebab was not clear because there were no examples based on kinetic studies. Folded chain crystals are thin plate crystals (referred to as lamellar crystals) that are most commonly found in polymer crystals.
- a thin crystalline film with a thickness of several hundreds of micrometers called “skin” on the surface, and a “laminated structure (laminated lamellar structure) of folded chain crystals called amorphous and amorphous inside. It is well known that an aggregate of “)” is formed (see Non-Patent Document 6).
- the skin is thought to be made of shish-kebab, but it has been confirmed that shish exists only sparsely.
- the generation mechanism of the skin structure has not been elucidated because there are no examples based on kinetic studies.
- the present inventors have studied the kinetics of the shish formation mechanism for the first time, and some molecular chains in the melt are stretched at the foreign substance interface due to “topological interaction” with the interface. Clarified the mechanism that shish is formed in a part of the melt in order to become a liquid crystal-oriented melt (called “oriented melt” or “Oriented ⁇ ⁇ ⁇ melt”) (for example, non-patent literature) 2 and 3).
- oriented melt or “Oriented ⁇ ⁇ ⁇ melt” (for example, non-patent literature) 2 and 3).
- the “topological interaction” means an effect of “stretching each other because the string-like polymer chains are entangled”, and is known as an interaction inherent to the polymer.
- the present inventors have proposed the theory of topological crystallization mechanism of polymers for the first time, and have elucidated the origin of extended chain crystals and folded chain crystals. This theory is called “slip diffusion theory” and is recognized worldwide (see Non-Patent Document 7).
- critical elongation strain rate a large elongation strain rate exceeding the “critical” elongation strain rate (referred to as critical elongation strain rate) in the polymer melt to make the entire polymer melt into an oriented melt. It was considered that the crystallization of the polymer is likely to occur and the crystallinity can be increased. If the entire polymer melt can be crystallized in the state of the oriented melt, it has been considered that a crystal having a structure in which most of the molecular chains of the polymer are oriented can be produced.
- nucleation is further accelerated, and innumerable nucleation occurs between molecular chains without adding a nucleating agent, so that contamination of impurities can be avoided and the crystal size can be reduced to the nanometer order. It was possible to obtain a polymer crystal body having high transparency and dramatically increased mechanical strength and heat resistance.
- polymer melt a polymer melt
- elongation strain rate equal to or higher than the critical elongation strain rate
- the NOC material is referred to as “polymer oriented crystal” or “polymer crystal”.
- the NOC material is a material that is extremely excellent in properties such as mechanical strength, heat resistance, and transparency, and is expected as a new material that can replace conventional industrial materials.
- Patent Documents 1 and 2 uniquely found by the present inventors, a polymer alignment melt is formed into a film, and crystallization is performed while maintaining the alignment state.
- a film-like NOC material), or a molded product containing NOC that is, a molded product made of NOC material that crystallizes while maintaining the orientation state by placing a polymer oriented melt in a predetermined mold. It became possible to do.
- the invention described in Patent Documents 1 and 2 made it possible to produce a primary molded product made of NOC material.
- the NOC material can be processed by press molding or the like into a molded product having a different shape, or the NOC materials can be fused together. Techniques for joining, so-called secondary molding techniques are required. If a pellet-like or powder-like NOC material can be fused, another molded product can be produced using the pellet-like or powder-like NOC material as a raw material. Further, if the NOC material fragments can be fused, a product (NOC product) made of used NOC material can be cut and reused for manufacturing another NOC product.
- the NOC material has a higher heat resistance temperature than non-NOC materials (materials containing non-NOC polymer crystals or polymer amorphous materials), and mechanical strength is dramatically increased. Therefore, it is difficult to perform secondary molding as compared with non-NOC materials.
- the NOC material is melted at a high temperature, it will no longer be a polymer oriented melt. Therefore, when trying to obtain a secondary molded product of the NOC material, the polymer melt obtained by melting the NOC material is critically stretched. It was thought that a polymer oriented melt was prepared by stretching again at an elongation strain rate equal to or higher than the strain rate, and crystallization was performed while maintaining the orientation melt state. Therefore, there has been a problem that the secondary molding of the NOC material takes time and cost.
- an object of the present invention is to provide a secondary molding technique for NOC materials in order to further improve the convenience of NOC materials as industrial materials.
- the NOC contained in the NOC material is in an order phase (“highly ordered”). also referred to as degree phase “. particularly NOC cases referred to as” alpha 2 phase “.) mobile phase from the PP (also referred to as” high-temperature crystal phase “. particularly when the NOC of PP as” alpha 2 'phase “.) to the phase transition
- the molecular chain of the polymer eventually becomes isotropic (also called “Equilibrium melt”, hereinafter referred to as “thermal equilibrium melt”). ) was found to transfer to.
- the crystal part (NOC) in the entangled network structure is melted, but the entangled network structure is maintained. It has been newly discovered that it goes through a state of “Dense Entanglement Network-melt”: DEN melt.
- DEN melt a state of “Dense Entanglement Network-melt”
- the present inventors have found that the NOC material in the mobile phase or DEN melt has plasticity and can be subjected to secondary molding such as press molding. Surprisingly, it was found that the mobile phase or the DEN melt returned to the order phase NOC material by cooling to about room temperature (however, in the case of the DEN melt, the melt was changed so that there was no volume change).
- the secondary molding method of the NOC material according to the present invention is a heating step in which the NOC material is heated to form a mobile phase or DEN melt; A molding step of molding the NOC material that has become a mobile phase or DEN melt by the heating step; and A cooling step of cooling the NOC material after the molding step until the phase transitions to the order phase.
- the present invention also includes a secondary molded product of NOC material obtained by the secondary molding method of NOC material according to the present invention, wherein a plurality of NOC materials are fused together.
- NOC materials are excellent in mechanical strength (breaking strength, rigidity, toughness, etc.), heat resistance, transparency and other properties, and in particular have mechanical strength equivalent to that of metals, so they can be used not only as a substitute for polymer materials. Use as a substitute for metal is greatly expected. If NOC material can be used as a substitute for metal, it is possible to reduce the weight of any product without reducing the mechanical strength. For example, if used as an interior or exterior material for vehicles, the weight of the vehicle can be reduced by a fraction of the weight and fuel consumption can be greatly improved, which can contribute to significant energy savings.
- the NOC material can be reused, oil resources can be saved and the burden on the environment can be reduced.
- (B) shows the result of X-ray exposure from a direction (edge) parallel to TD
- (c) shows the result of X-ray exposure from a direction (end) parallel to MD.
- Scattering vector (q) -small angle X-ray scattering created based on a two-dimensional scattering pattern obtained by exposing X-rays from the direction perpendicular to MD and TD for the NOC material used in the examples. It is an intensity
- (B) shows the result of X-ray exposure from a direction (edge) parallel to TD
- (c) shows the result of X-ray exposure from a direction (end) parallel to MD
- 2A shows a two-dimensional scattering pattern by WAXS method of a sample that has been operated at room temperature ⁇ 135 ° C. ⁇ room temperature, (a) is a sample before heating, (b) is a sample after heating, and (c) is a restraint condition. The results of the samples allowed to cool in are shown.
- ⁇ room temperature is shown, (a) is a sample before heating, (b) is a sample after heating, and (c) is a constraint condition.
- the two-dimensional scattering pattern by the WAXS method of a sample that has been operated at room temperature ⁇ 165 ° C. ⁇ room temperature is shown, (a) shows the result of the sample before heating, and (c) shows the result of the sample allowed to cool under restraint conditions, respectively Show.
- 2D shows a two-dimensional scattering pattern according to the SAXS method of a sample (one example) subjected to an operation of room temperature ⁇ 165 ° C. ⁇ room temperature, (a) is a sample before heating, (b) is a sample after heating, and (c) Indicates the results of the samples allowed to cool under restraint conditions. It is a photograph of the secondary molded product obtained by performing secondary molding after heating a sample to 165 degreeC. The result of measuring the tensile strength of the sample before heating and the sample after heating to 165 ° C. and then allowing to cool under restraint conditions is shown, (a) is the sample before heating, and (b) is after cooling. Sample results are shown for each.
- 2A shows a two-dimensional scattering pattern by WAXS method of a sample that has been operated at room temperature ⁇ 175 ° C. ⁇ room temperature, (a) is a sample before heating, (b) is a sample after heating, and (c) is a restraint condition. The results of the samples allowed to cool in are shown.
- 2D shows a two-dimensional scattering pattern by SAXS method of a sample that has been operated at room temperature ⁇ 175 ° C. ⁇ room temperature, (a) is a sample before heating, (b) is a sample after heating, and (c) is a constraint condition. The results of the samples left to cool are shown below.
- FIG. 3 is a chart showing enthalpy change ( ⁇ H) when stretched at an elongation strain rate of 419 (sec ⁇ 1 ) and then cooled at a cooling rate of 10 K / min.
- the solid line shows the result when the NOC material is heated to 188 ° C.
- the broken line shows the result when the NOC material is heated to 230 ° C.
- T c when recrystallization temperature of the molded samples at various elongation strain rate and (T c) of the static yard and (? T c), showing the relationship between the elongation strain rate.
- the diamond symbol indicates the result when the NOC material is heated to 180 to 190 ° C.
- the square symbol indicates the result when the NOC material is heated to 190 to 200 ° C.
- the secondary molding method of the NOC material according to the present invention includes (1) a heating step of heating the NOC material into a mobile phase or DEN melt; (2) a molding step of molding the NOC material that has become a mobile phase or DEN melt by the heating step; and (3) including a cooling step of cooling the NOC material after the molding step until the phase transition to the order phase.
- “secondary molding of NOC material” means that molding such as press molding is performed on the NOC molded product that has once become the NOC material.
- Secondary molding means molding processing performed after primary molding for producing the NOC material.
- “molding” is used as a Chinese character notation for primary molding, and “molding” is used for secondary molding.
- processes that can be performed in the technical field related to the molding of polymer materials for example, processes such as press molding, stretch molding, rolling molding, drawing molding, pressure molding, fusion molding, vacuum molding, etc. It may be included in the next molding method.
- the heating step in the secondary molding method of the present invention is a step of heating the polymer nano-oriented crystal material (NOC material) to form a mobile phase or DEN melt.
- NOC material means a material containing NOC (polymer nano-oriented crystal) as a main component.
- the above “including as a main component” means that NOC is contained by 70% or more, preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.
- NOC means a polymer crystal constituting the NOC material, and is distinguished from “NOC material”.
- NOC material examples include polymer crystals described in Patent Documents 1 and 2.
- the NOC material is produced by stretching a polymer melt at an elongation strain rate equal to or higher than the critical elongation strain rate to obtain a polymer orientation melt and crystallizing the polymer melt in the state of the polymer orientation melt.
- NOC materials are attracting attention as various industrial materials because they have excellent properties such as mechanical strength, heat resistance, and transparency. In particular, it is expected to be used as an alternative to metal materials.
- the polymer constituting the NOC material is not particularly limited, and even a so-called general-purpose plastic such as polyethylene (PE), polypropylene (hereinafter referred to as “PP”), polystyrene (PS), polyethylene terephthalate (PET), What is called engineering plastics, such as fluororesins, such as nylon and Teflon (trademark), may be sufficient. If it can be used as an alternative to engineering plastics by improving the mechanical properties, heat resistance, transparency, etc. of inexpensive general-purpose plastics, the cost of resin-made industrial parts will be greatly reduced. Therefore, it can be said that it is useful to use a general-purpose plastic as the NOC material. Among general-purpose plastics, PP is particularly preferable.
- PP has preferable characteristics such as relatively high heat resistance and high mechanical strength as compared with other general-purpose plastics.
- isotactic polypropylene hereinafter referred to as “iPP” where appropriate
- iPP isotactic polypropylene
- isotactic polypropylene has a structure in which methyl groups are arranged in the same direction, so that it has good crystallinity and a NOC material can be obtained more easily.
- the NOC crystal size of the obtained NOC material is likely to be finer than that of normal PP, and a highly transparent NOC material can be produced.
- NOC and NOC materials are not produced only from PP or iPP because of the principle of NOC generation.
- the molecular chains in all polymer melts are usually present in a string shape.
- the molecular chain of the polymer is stretched to obtain an oriented melt.
- the molecular chains of the polymer are likely to associate with each other, and uniform nucleation tends to occur.
- NOC is generated. From this it can be said that NOC and NOC materials can be made from any polymer.
- the NOC material may be composed of a single polymer or a mixture of a plurality of types of polymers.
- PP, PE, polybutene 1 and the like can be appropriately combined.
- other polymers can compensate for the physical properties of one type of polymer. What is necessary is just to set the mixing ratio of a polymer
- the NOC material has a crystallinity of 70% or more, preferably 80% or more, more preferably 90% or more, and most preferably 95% or more.
- “NOC material crystallinity” means the proportion of crystals contained in the NOC material.
- the crystallinity of the NOC material can be measured by a known method. For example, the crystallinity can be determined by a density method using mass M and volume V (LE Alexander, “X-ray diffraction of polymer (top)”, Kagaku Dojin, 1973, p.171. See The crystallinity ⁇ c of the NOC material is obtained by the following equation.
- ⁇ the density of the sample
- ⁇ a the amorphous density
- ⁇ c the crystal density.
- literature values are available for ⁇ a and ⁇ c (see Qirk RP and Alsamarriaie MAA, Awiley-interscience publication, New York, Polymer Handbook, 1989).
- M the mass (g) of the sample
- V the volume (cm 3 ).
- the size d of the crystal contained in the NOC material is 300 nm or less, preferably 100 nm or less, more preferably 50 nm or less, further preferably 30 nm or less, and further preferably 20 nm or less.
- the size d of the crystal can be measured by, for example, a known small angle X-ray scattering method (SAXS method) or a wide angle X-ray scattering method (WAXS method).
- the X-ray scattering method can be performed by, for example, a small-angle X-ray scattering method (SAXS method) or a wide-angle X-ray scattering method (WAXS method).
- SAXS method small-angle X-ray scattering method
- WAXS method wide-angle X-ray scattering method
- Experimental facilities that can perform X-ray scattering are, for example, High Brightness Optical Science Research Center (JASRI) SPring-8, Beamline BL40B2, High Energy Accelerator Research Organization (KEK) Photon Factory (PF), Beamline BL10C etc. are mentioned.
- a detector an imaging plate (Imaging Plate) or a position sensitive detector (PSPC) can be used.
- the primary peak of the scattering vector (q) -small angle X-ray scattering intensity (I x ) curve is the closest distance between the microcrystals when the microcrystals of the average size d are randomly packed together.
- orientation function f c indicating the degree of orientation of crystals in the polymer chains comprised in the NOC material 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more.
- Orientation function f c of the structure can be determined by, for example, known wide-angle X-ray scattering method (WAXS method). Measurement of orientation function f c by WAXS method, for example, when using an imaging plate (Imaging Plate) as a detector, X-rays scattering intensity analysis software (manufactured by Rigaku Corporation, R-axis display) may be measured by using a .
- a method for calculating the orientation function f c the description of embodiments to be described below is referenced. In the case of crystalline polymers, the mechanical strength in the MD direction as orientation function f c is large increases, orientation function is important in obtaining a high performance material.
- the NOC material includes a rod-like higher order structure in which bead-like bodies formed by connecting NOC particles (nano-oriented crystal particles) in a bead-like shape are bundled.
- a schematic diagram of the rod-like higher-order structure is shown in FIG.
- FIG. 1A shows an example of a NOC material in which rod-like higher order structures having a diameter of about 70 nm are arranged.
- the broken line in Fig.1 (a) shows a cut end.
- the bar-like higher order structure is uneven in height.
- NOC particles are arranged like irregular beads, and a series of about a dozen beads are bundled.
- FIG. 1B is an enlarged view of the inside of the bar-like higher order structure. According to FIG. 1B, it can be seen that the NOC particles and the polymer chains are oriented in the extension direction. One polymer chain reciprocates and penetrates between a plurality of NOC particles.
- the diameter ⁇ of the rod-like higher order structure contained in the NOC material is 300 nm or less, preferably 200 nm or less, more preferably 100 nm or less.
- the diameter ⁇ of the rod-like higher order structure can be measured by, for example, a known small angle X-ray scattering method (SAXS method).
- SAXS method the scattering vector (q 2 ) -small-angle X-ray diffuse scattering intensity (I x ) curve gives the shape factor due to its own scattering in each rod-like higher order structure (reference: A.
- the NOC material made of iPP has a tensile fracture strength of 100 MPa or more, preferably 0.21 GPa or more, and a tensile modulus of 3 GPa or more, preferably 4 GPa or more, as measured by a method based on the tensile test method of JIS K7127. It is.
- the tensile testing machine used for the measurement is a precision universal testing machine (Autograph AG-1kNIS) manufactured by Shimadzu, the distance between marked lines is 7 to 10 mm, the width of narrow parallel part is 1.5 to 3.0 mm, and the thickness is 0.2. Use specimens with a size of ⁇ 0.4 mm. For details of the tensile test, refer to the description of Examples described later.
- the tensile modulus (Young's modulus, longitudinal elastic modulus) is a constant that determines the value of strain with respect to stress in the elastic range.
- [Strain ⁇ ] [stress ⁇ ] / [tensile modulus E] (Hooke's law)
- a tensile elasticity modulus is calculated
- the tensile fracture strength and tensile modulus were measured at room temperature of 25 ° C.
- the NOC material made of iPP has a haze value (thickness of 0.3 mm) of a test piece having a thickness of 0.3 mm measured by the haze measurement method devised by the inventors of the present invention, which is 10% or less (preferably 5% or less, More preferably, it is 1% or less.
- the “haze value (thickness 0.3 mm)” is an “optical density-haze calibration curve” shown below by measuring an optical density using a test piece having a thickness of 0.3 mm. "Converted haze”. The haze measurement method is performed by measuring the amount of transmitted light that has passed through the test piece.
- haze measurement method for example, an optical microscope (BX51N-33P-OC manufactured by Olympus Corporation) using a halogen lamp as a white light source, a CCD camera (cooled digital camera QICAM manufactured by QImaging), and an image that can quantify the optical density.
- An apparatus equipped with analysis software Media Cybernetics, Image-Pro PLUS
- the white light which is measurement light should just make it enter into a test piece with a circle of 1 mm in diameter.
- the optical density can be converted to haze by using an “optical density-haze calibration curve”.
- the “optical density-haze calibration curve” is a plot of haze against optical density using the haze of 20 polypropylene sheets measured according to JIS K7105 and the optical density of the polypropylene sheet measured by the haze measurement method. Can be created.
- the NOC material made of iPP has a heat resistant temperature measured by a test piece size direct reading method using an optical microscope of 160 ° C. or higher, preferably 170 ° C. or higher, more preferably 175 ° C. or higher.
- the test piece size direct reading method is a method originally devised by the present inventors, and the heat-resistant temperature can be measured according to the method described below.
- the equipment used for the measurement was an optical microscope with a CCD camera (BX51N-33P-OC, manufactured by Olympus Corporation), a hot stage (Linkam, L-600A), and image analysis software (Media Cybernetics, Inc.) that can quantify the size on the screen.
- the test piece had a size of 0.7 mm, a width of 0.7 mm, and a thickness of 0.2 to 0.4 mm.
- the test piece was heated at a heating rate of 1 K / min. At that time, the temperature at which the test piece started to contract or expand 3% or more in the vertical direction (MD) or the transverse direction (TD) was defined as the heat resistant temperature.
- FIG. 2 schematically shows changes in the phase and state of the NOC material.
- NOC room temperature (T R) from the order phase - has a in the temperature range below the mobile phase transition temperature (T om), (in the case of PP of alpha 2 phase) order phase.
- the ordered phase ( ⁇ 2 phase) is a highly ordered phase, and the ⁇ 2 phase has a structure that is superior to the ⁇ 1 phase in properties such as mechanical strength and heat resistance.
- the ⁇ 1 phase is a low-order phase having a disordered structure (see M. Hikosaka, Polymer Journal 1973 5 111-127).
- the order phase ( ⁇ 2 phase) NOC has a structure in which NOC particles oriented in the extension direction (MD direction) are tightly entangled with each other by a polymer molecular chain (high density entangled network structure). ; Dense Entanglement Network Structure: DEN structure).
- the phase transition from the order phase ( ⁇ 2 phase) to the mobile phase ( ⁇ 2 ′ phase) occurs at the order phase-mobile phase transition temperature (T om ).
- T om order phase-mobile phase transition temperature
- the mobile phase ( ⁇ 2 ′ phase) is a crystalline phase that is stable at high temperature, and has a form that is almost the same as that of the aforementioned NOC material.
- the mobile phase ( ⁇ 2 ′ phase) has plasticity unlike the order phase ( ⁇ 2 phase), and secondary molding such as press molding becomes possible.
- the melting point (T m ) changes from the mobile phase ( ⁇ 2 ′ phase) to the DEN melt.
- T m the melting point
- an iPP NOC material changes to a DEN melt at about 170 ° C.
- the state of the DEN melt is an oriented melt.
- it since it can be said that it is a form like a liquid crystal, it can also be said to be a nano oriented liquid crystal (NOLC). Since the DEN melt is in an oriented melt state, it naturally has plasticity, and secondary molding such as press molding becomes possible. The existence of such a DEN melt state is a new finding that has been revealed for the first time by the inventors.
- this DEN melt When this DEN melt is heated, it changes from a DEN melt to a thermal equilibrium melt at the isotropic melt transition temperature (T iso ). For example, in the case of an iPP NOC material, it changes to a thermal equilibrium melt (isotropic melt) at about 215 ° C. In this state, the DEN structure is completely broken, and the molecular chain of the polymer is a non-oriented melt.
- T iso isotropic melt transition temperature
- each temperature (T om , T m , T iso ) can be determined by performing a WAXS method or a SAXS method on a sample heated to raise the temperature and confirming the phase and state of the sample.
- Each temperature is determined according to the type of polymer constituting the NOC material, the molecular weight, the crystallization rate, the degree of orientation, and the like, and thus can be determined for each NOC material.
- T om is about 157 ° C.
- T m is about 170 ° C.
- T iso is about 215 ° C.
- the NOC material is heated and changed into the mobile phase ( ⁇ 2 ′ phase) or the DEN melt, and then subjected to secondary molding such as press molding, and then cooled. It has been found that returning to a temperature below T om returns to NOC or NC material again.
- the NOC material is heated to a temperature range equal to or higher than T om and lower than T iso , a sample within the temperature range is secondarily molded, and then returned to a temperature lower than T om , the order phase ( ⁇ 2 It can be said that a secondary molded product of the phase (NOC material) or NC material is obtained.
- NC material containing a polymer nanocrystal (NC) in which the molecular chain orientation is relaxed.
- NC materials are materials that are extremely excellent in properties such as mechanical strength, heat resistance, and transparency as compared with ordinary folded chain crystals (FCC), and can be used in the same manner as NOC. .
- the DEN melt is in a melt state, it is easier to perform secondary molding. Therefore, from the viewpoint of ease of secondary molding, it can be said that it is more preferable to perform secondary molding in the state of DEN melt than the mobile phase.
- it is more preferable to perform fusing after the NOC material is made into a DEN melt because the fusing can be performed more firmly.
- secondary molding is performed in a state where the temperature is less than Tom , that is, secondary molding is performed in order to perform the secondary molding on the NOC material in the order phase because it does not have plasticity. I can't. If secondary molding is performed with an excessive force, physical destruction of the structure of the NOC material occurs.
- the NOC material is in a desired temperature range ( Tom or more and less than Tiso , more preferably Tm or more and less than Tiso ).
- the heating means is not particularly limited as long as it can be heated, and known heating means can be appropriately employed depending on the shape and size of the NOC material, the method of secondary molding, and the like.
- the NOC material may be placed in a heating furnace (electric furnace, gas furnace, etc.) and heated to a desired temperature, or heated to a desired temperature on a plate heater.
- the NOC material is placed on a conveying means such as a belt conveyor and is conveyed into the heating furnace by the belt conveyor, and the NOC material is conveyed through the heating furnace as desired. It may be a mode in which it is heated to a temperature of.
- the molding step is a step of molding the NOC material that has become the mobile phase ( ⁇ 2 ′ phase) or the DEN melt by the heating step.
- the molding method in the molding process is not particularly limited, but for example, press molding, stretch molding, rolling molding, drawing molding, pressure molding, fusion molding, vacuum molding, etc., and molding into an arbitrary shape Can be mentioned. More specifically, if a sheet-like NOC material in the mobile phase ( ⁇ 2 ′ phase) or DEN melt is pressed with a mold having an appropriate shape, the NOC material (or NC material) having a desired shape is obtained.
- a secondary molded product consisting of The secondary molded product finally obtained by secondary molding of the NOC material obtained by the secondary molding method of the present invention is referred to as “NOC secondary molded product”.
- a plurality of NOC materials may be laminated, fused, and joined. More specifically, if a sheet-like or film-like NOC material is laminated and fusion-bonded, a thick NOC secondary molded product that could not be produced conventionally can be finally produced.
- the sheet-like or film-like NOC material to be laminated here may be the same NOC material or different types of NOC materials (for example, a combination of PP NOC and PE NOC). Further, a combination of a NOC material and a non-NOC material may be used. Combining different types of NOC materials, or combining NOC materials and non-NOC materials, finally produce a new sheet-like NOC secondary molded product that combines the specific properties of each NOC material. be able to.
- the present invention also includes an NOC secondary molded product obtained by fusing a plurality of NOC materials obtained by the secondary molding method of the present invention.
- the NOC secondary molded product exhibits characteristics such as mechanical strength, heat resistance, and transparency equivalent to the primary molded product because a plurality of NOC materials are fused together.
- a raw material obtained by fusing a powdered or particulate NOC material may be cast in a mold, or extrusion molding may be performed.
- Powdered and particulate NOC materials can be packed in packing materials such as bags at a high density and have the advantage of being easily distributed as industrial raw materials.
- a high-performance NOC secondary molded product can be manufactured using this NOC material as a raw material.
- judged the product which consists of used NOC material can be utilized as said powdery or particulate NOC material.
- the NOC material can be reused, and valuable resources (such as petroleum resources) can be saved.
- the molding in the main molding step is not limited to one molding, and the same type of molding may be performed a plurality of times, or different types of molding methods may be appropriately combined. Thereby, it becomes possible to produce a NOC secondary molded product having a more complicated shape.
- the present molding process may include a mode in which the NOC material once turned into the mobile phase ( ⁇ 2 ′ phase) or the DEN melt is simply left without being molded.
- Cooling step is a step of cooling to a phase transition of the NOC material after the molding step in order phase (alpha 2 phase). In other words, it is a step of bringing the NOC material after the molding step to a temperature lower than Tom .
- the cooling method is not particularly limited, and the temperature may be forcibly set to less than Tom using a conventionally known cooling means, or the NOC material after the molding step is allowed to stand at room temperature or the like to be less than Tom . You may let it cool until it becomes. That is, in this cooling process, the cooling rate is not particularly limited. Note that the cooling step may be performed in the gas phase or in the liquid phase.
- the mobile phase ( ⁇ 2 ′ phase) that has undergone the molding process or the NOC material that has become the DEN melt is again transformed into the order phase ( ⁇ 2 phase), and a NOC secondary molded product is obtained.
- ⁇ 2 ′ phase the mobile phase that has undergone the molding process or the NOC material that has become the DEN melt
- ⁇ 2 phase the order phase
- NOC secondary molded product is obtained.
- Whether or not the NOC material returns to the ⁇ 2 phase again to become a NOC secondary molded product can be confirmed by the WAXS method and the SAXS method described above. For details, refer to the embodiments described later.
- the secondary molding method of the present invention may be carried out batchwise, but industrially is preferably carried out continuously.
- the following aspects are exemplified.
- (2) The NOC material is conveyed by a belt conveyor to a heating furnace capable of performing a heating process. At this time, the belt conveyor is designed to pass through the heating furnace.
- the NOC material on the belt conveyor reaches a temperature range of a predetermined temperature ( Tom or more and less than Tiso , more preferably Tm or more and less than Tiso ) while moving in the heating furnace. ⁇ 2 ′ phase) or DEN melt.
- the molding means (press molding machine, etc.) installed in the heating furnace, or installed immediately downstream of the heating furnace
- Secondary molding is performed by the formed molding means (press molding or the like). While the secondary molding (molding process) is performed, the belt conveyor may be operating or may be temporarily stopped.
- the NOC material that has undergone the secondary molding (molding process) is transported outside the heating furnace by the belt conveyor (if secondary molding is performed outside the heating furnace, it is transported as it is). During the conveyance, the NOC material on the belt conveyor is cooled as it is or by an appropriate cooling means, and becomes less than Tom (cooling step).
- the NOC material of the mobile phase ( ⁇ 2 ′ phase) or DEN melt again undergoes phase transition to the order phase ( ⁇ 2 phase), and becomes a NOC secondary molded product.
- the NOC secondary molded product that has undergone the cooling process is conveyed as it is on the belt conveyor and is collected by the collecting means.
- the secondary molding method of the present invention can be used in the following fields, for example.
- the NOC secondary molded product of PP can be used as the majority of automobile interior materials (90% or more).
- PP NOC secondary molded products make use of high strength and high toughness to replace metals, such as automobiles, aircraft, rockets, trains, ships, motorcycles, bicycles, and other structural members, interior / exterior materials, and various machines. It can be used as an instrument part or a structural member.
- the PP NOC secondary molded product can be used as a diaphragm for a speaker or a microphone by utilizing its high rigidity and light weight.
- the PP NOC secondary molded product can be used as a CD or DVD as an alternative to a PC by taking advantage of high transparency.
- the PP NOC secondary molded product can be used as a mask for liquid crystal or plasma display by making use of high transparency.
- PP NOC secondary molded products can be used as materials for medical supplies such as disposable syringes, infusion devices, and chemical containers by making use of high transparency.
- PP's NOC secondary molded product can be used as a large water tank for business use from various bottles, glasses and small water tanks for household use as an alternative to glass, taking advantage of high transparency.
- the PP NOC secondary molded product can be used as a material for contact lenses, glasses lenses, and various optical lenses by making use of high transparency.
- PP NOC secondary molded products can be used as glass for buildings and houses by utilizing high transparency.
- PP's NOC secondary molded products can be used as materials for a wide range of sports equipment such as ski shoes, skis, boards, rackets, various nets, tents, rucksacks, etc. by utilizing their high rigidity, high toughness and light weight. is there.
- the PP NOC secondary molded product can be used as a material for handicrafts and decorations such as needles, scissors, sewing machines, etc. by utilizing high rigidity, high toughness and light weight.
- PP NOC secondary molded products can be used as materials for commercial products such as show windows and display parts.
- the PP NOC secondary molded product can be used as a material for parks, amusement parks, theme park equipment or facilities such as swings, seesaws, and roller coasters.
- PP's NOC secondary molded products include structural materials and box materials for parts of precision equipment such as electrical, electronic, information equipment, and watches; stationery such as files, folders, pencil cases, writing utensils, scissors; kitchen knives, balls, Cooking materials such as food, confectionery, tobacco packaging materials; food containers, tableware, disposable chopsticks, toothpicks; furniture such as household furniture and office furniture; building materials and interior materials and exterior materials for buildings and houses; roads Or materials for bridges; materials for toys; super-strength fibers and threads; fishing gear, fishing nets, fishing gear; agricultural tools, agricultural supplies; plastic bags, garbage bags; various pipes; garden supplies; , Box; etc.
- the PE PP NOC secondary molded product can be used as a super strong fiber.
- fluorinated NOC secondary molded products such as polyvinylidene fluoride can be used as materials for high-accuracy ultrasonic elements, high-speed switching elements, high-efficiency speakers, or high-sensitivity microphones by taking advantage of high ferroelectric and piezoelectric properties. It is. Further, the NOC secondary molded product of PET can be used as an industrial material requiring high heat resistance of about 200 ° C.
- the secondary molding method of the NOC material according to the present invention is a heating step in which the NOC material is heated to a mobile phase or a DEN melt; A molding step of molding the NOC material that has become a mobile phase or DEN melt by the heating step; and A cooling step of cooling the NOC material after the molding step until the phase transitions to the order phase.
- the NOC material the crystal size d is at 300nm or less
- the orientation function f c indicating the degree of orientation of crystals in the polymer chain is at least 0.7 NOC
- the thing which consists of may be sufficient.
- the NOC material includes a rod-like higher-order structure
- the rod-like higher-order structure is a bundle of bead-like bodies formed by connecting NOC particles in a bead-like shape. Structure.
- the high NOC material may be made of polyolefin.
- the NOC material may be made of polypropylene.
- the molding step may be a step of fusing a plurality of NOC materials.
- the molding step may be a step of laminating and fusing a plurality of sheet-like NOC materials.
- the molding step is any one of press molding, stretch molding, rolling molding, drawing molding, pressure molding, fusion molding, and vacuum molding of the NOC material. Also good.
- the present invention also includes a secondary molded product of NOC material obtained by the secondary molding method of NOC material according to the present invention, wherein a plurality of NOC materials are fused together.
- the secondary molded product may be a laminate formed by laminating a plurality of sheet-like NOC materials.
- the iPP melt melted at 200 ° C. was made into a supercooled melt at 120 to 150 ° C. and discharged from the slit die of the supercooled melt feeder 2 into a sheet form.
- the critical elongation strain rate ⁇ * is a value determined by the inventors' previous studies.
- the NOC material produced above was appropriately cut out and measured for physical properties and structure. Although a plurality of NOC materials were produced, only one example will be shown below.
- NOC material thickness 0.25 mm was observed with a microscope. From a direction perpendicular to both the MD and TD directions (Through), observation was made directly with a polarization microscope system, and changes in morphology and orientation of polymer chains were recorded and measured.
- Olympus BX51N-33P-OC was used for the polarizing microscope
- QImaging a cooled digital camera
- QICAM was used for the CCD camera
- a personal computer was used for recording.
- a sensitive color plate was inserted between the polarizer and the analyzer (polarizing plate) of the polarizing microscope (Reference: Introduction to Polarizing Microscope of Polymer Materials, Hiroshi Ashiya, Agne Technical Center, 2001, p.75-103). Observation with a polarizing microscope was performed at room temperature of 25 ° C.
- FIG. 4 A polarizing microscope photograph is shown in FIG. In FIG. 4, granular spherulites were not seen, and an extremely fine streak shape oriented in the MD direction was seen. In addition, by rotating the sample with the sensitive color test plate inserted, the color in the MD direction (ie, retardation) changed from blue ⁇ magenta ⁇ yellow ⁇ magenta and showed a clear extinction angle (red purple). . Therefore, it was found from this change in retardation that the polymer chains were remarkably oriented in the MD direction.
- retardation changed from blue ⁇ magenta ⁇ yellow ⁇ magenta and showed a clear extinction angle (red purple).
- the crystallinity ⁇ c of the sample of NOC material was measured by the density method. More specifically, the crystallinity of the sample was determined by a density method using mass (M) and volume (V). The measurement was performed at room temperature of 25 ° C. The size of the cut sample was measured using a micrometer and an optical stereomicroscope (Olympus Co., Ltd., SZX10-3141). Moreover, the mass of the sample cut out was measured using the digital electronic balance (The Sartorius company make, ME253S). The measurement was performed at room temperature of 25 ° C.
- Heat resistance test of NOC material The heat resistant temperature of the NOC material was measured by a test piece size direct reading method using an optical microscope. A test piece (length 0.7 mm, width 0.7 mm, thickness 0.25 mm) was placed on a hot stage (Linkam, L-600A), and the temperature inside the hot stage was increased at a temperature increase rate of 1 K / min. . At this time, observation and recording were performed with an optical microscope with a CCD camera (BX51N-33P-OC manufactured by Olympus Corporation).
- SAXS method Small angle X-ray scattering method
- the SAXS method conforms to the description of “Polymer X-ray diffraction Masao Kadodo, Masami Kasai, Maruzen Co., Ltd., 1968” and “Polymer X-ray diffraction version 3.3 Toru Masuko, Yamagata University Cooperative, 1995” was done.
- the camera length is 1654 mm
- the detector is an imaging plate (Imaging Plate).
- Imaging Plate Three directions were observed: a direction perpendicular to MD and TD (through), a direction parallel to TD (edge), and a direction parallel to MD (end).
- the MD direction was set in the Z-axis direction
- the TD direction was set in the Z-axis direction
- the X-ray exposure time was 180 seconds.
- the imaging plate was read with a reader manufactured by Rigaku Corporation and reading software (Rigaku Corporation, raxwish, control) to obtain a two-dimensional image.
- Fig. 5 shows a two-dimensional image.
- (A) through and (b) edge showed a two-point image in the MD direction, indicating that the nano-oriented crystals were very strongly oriented in the MD direction.
- (a) through indicates a streak extending from the center in the equator direction, and
- (c) end indicates non-oriented diffuse scattering extending isotropically from the center. From this fact, it was concluded that the NOC material produced above has a rod-like higher order structure (reference: “Theory and practice of X-ray crystallography” by A. Guinier, Rigaku Electric Co., Ltd.) ), P513, 1967).
- the diameter ⁇ of the rod-like higher-order structure was analyzed using analysis software (Rigaku Corporation, R-axis, display) for the two-dimensional image of end in FIG.
- the square (q 2 ) -small angle X-ray diffuse scattering intensity (I x ) curve of the scattering vector shown in FIG. 6 is integrated for all declinations of the two-dimensional image except for total reflection from the sample surface. It is the result obtained by correcting.
- the NOC material produced above was observed from the three directions of through, edge, and end using a wide angle X-ray scattering method (WAXS method).
- the detection was performed at room temperature of 25 ° C. using an imaging plate (Imaging Plate).
- Imaging Plate Imaging Plate
- the MD direction was set in the Z-axis direction
- the TD direction was set in the Z-axis direction
- the X-ray exposure time 60 seconds.
- the imaging plate was read with a reader manufactured by Rigaku Corporation and reading software (Rigaku Corporation, raxwish, control) to obtain a two-dimensional image. Further, the two-dimensional image was analyzed using analysis software (Rigaku Corporation, R-axis, display), and the volume fraction f ( ⁇ 2 ) of ⁇ 2 phase was measured. More specifically, (formula)
- FIG. 7 shows the result of the two-dimensional image.
- the tensile elastic modulus was determined in accordance with the method described in JIS K7161. The measurement was performed at room temperature of 25 ° C.
- haze haze value: thickness 0.3 mm
- the haze measurement method was carried out by measuring the amount of transmitted light that passed through the test piece.
- the haze measurement method includes an optical microscope (BX51N-33P-OC manufactured by Olympus Corporation), a CCD camera (QImaging cooled digital camera QICAM) that can quantify the amount of light, and image analysis software (Media Cybernetics, Image-Pro). PLUS) was used.
- the size of incident light using a halogen lamp used as measurement light as a white light source was a circle having a diameter of 1 mm.
- the haze (haze value, thickness 0.3 mm) of the NOC material was 0.9%.
- Regeneration test to NOC material and secondary molding test Room temperature (25 ° C.) NOC material was heated to 135 ° C., 165 ° C., 180 ° C., 210 ° C. or 225 ° C., respectively.
- T om the NOC material in the present embodiment is about 157 ° C.
- T m about 170 ° C.
- T iso was about 215 ° C.. Therefore, at 135 ° C, the NOC material remains in the order phase ( ⁇ 2 phase), at 165 ° C. it has changed to the mobile phase ( ⁇ 2 ′ phase), and at 175 ° C. and 210 ° C. it is a DEN melt. At 225 ° C., it is a thermal equilibrium melt.
- Each sample heated to a predetermined temperature was allowed to cool to room temperature.
- the sample before heating, the sample after heating, and the sample after cooling were analyzed by the WAXS method and the SAXS method.
- Specific implementation methods of the WAXS method and the SAXS method are as described above.
- 8 and 9 show the two-dimensional scattering pattern by the WAXS method and the two-dimensional scattering pattern by the SAXS method, respectively, of the sample that has been operated at room temperature ⁇ 135 ° C. ⁇ room temperature. 8 and 9, (a) shows the results of the sample before heating, (b) shows the sample after heating, and (c) shows the results of the sample after cooling the sample after heating at 60 MPa. MD in FIGS. 8 and 9 indicates the tensile direction (hereinafter the same in the same figure). In FIG. 8, the scattering indicated by the arrow is from Kapton.
- the two-point image (see the arrow in FIG. 9) in the SAXS image of FIG. 9 is a typical pattern indicating that it is a NOC material. Since the sample remained in the order phase when heated at 135 ° C., a WAXS pattern and a SAXS pattern indicating that it was a NOC material were shown in all the samples at room temperature ⁇ 135 ° C. ⁇ room temperature.
- the sample after heating to 135 ° C. did not have enough plasticity to perform secondary molding.
- FIGS. 11 and 12 show the two-dimensional scattering pattern by the WAXS method and the two-dimensional scattering pattern by the SAXS method, respectively, of the sample that has been operated at room temperature ⁇ 165 ° C. ⁇ room temperature.
- FIG. 11 shows the result of the sample before heating
- (c) shows the result of the sample that was allowed to cool while pulling the sample after heating at 50 MPa.
- FIG. 12 shows the results of the sample before heating, (b) shows the sample after heating, and (c) shows the result of the sample that was allowed to cool while being pulled at 50 MPa.
- FIGS. 11 and 12 a pattern indicating that each sample is a NOC material was observed (in particular, see a two-point image indicated by an arrow in FIG. 12).
- FIG. 12 (b) the density fluctuation was reduced due to the influence of thermal expansion and the scattering intensity was reduced, but a two-point image indicating that it was a NOC material was observed.
- FIG. 12 (b) it was confirmed that the sample had a phase transition to the mobile phase ( ⁇ 2 ′ phase).
- FIG.11 (b) is blank, this is what abbreviate
- the sample after heating to 165 ° C. had such a degree of plasticity that secondary molding was possible (see FIG. 10).
- a pressure of 50 MPa to the sample heated to 165 ° C. and attempting to deform it, a molded body (NOC secondary molded product) having a crank shape shown in FIG. 13 was obtained.
- FIG. 14 shows the measurement results of the tensile strength of the sample before heating and the sample after heating-tensile cooling.
- the results of the sample before heating are shown in FIG. 14 (a), and the results of the sample after heating-tensile cooling are shown in FIG. 14 (b).
- FIG. 14 there is no change in the tensile strength between the sample before heating and the sample after heating-tension cooling, and the decrease in tensile strength of the NOC secondary molded product obtained by the secondary molding method of the present invention. Etc. were not seen.
- FIGS. 15 and 16 show the two-dimensional scattering pattern by the WAXS method and the two-dimensional scattering pattern by the SAXS method, respectively, of the sample that has been operated at room temperature ⁇ 180 ° C. ⁇ room temperature. 15 and 16, (a) shows the result of the sample before heating, (b) shows the sample after heating, and (c) shows the result of the sample that was allowed to cool while pulling the sample after heating at 10 MPa, respectively.
- the scattering indicated by the arrows is from Kapton.
- FIG. 17 the result of having measured the dynamic elastic modulus at the time of heating NOC material is shown.
- T m 175 ° C.
- Section As a result of conducting a tensile test on the sample (180 ° C.) in this temperature range, it was shown that the sample had sufficient elasticity (see FIG. 18).
- a sample that is in a thermal equilibrium state (referred to as “thermal equilibrium melt”) above the melting point is a liquid and therefore does not have elasticity and cannot be subjected to a tensile test in the first place.
- the sample heated to 175 to 215 ° C. exhibited a sufficient elasticity as shown in FIG. From the results shown in FIG. 16, FIG. 17, and FIG. 18, the present inventors entangled the crystal part (NOC) in the entangled network structure existing in the order phase and the mobile phase when it is transferred to the thermal equilibrium melt.
- the crystal part (NOC) in the network structure is melted, but the entangled network structure is maintained, the state of "Dense Entanglement Network-melt: DEN melt” Newly found that it exists. This is a new finding found by the present inventors. Incidentally, when it exceeds the 215 ° C. (as T iso), changes into thermal equilibrium melt (isotropic melt (Isotropic melt)). In a thermal equilibrium melt, the high-density entangled network structure is completely broken, and the molecular chains of the polymer become a non-oriented melt.
- FIG. 19 shows a polarizing microscope photograph of the fused NOC material, a SAXS image of the fused portion, and a WAXS image.
- FIG. 19A is a polarization micrograph of the fused NOC materials (A piece and B piece), and shows that the two sheet-like NOC materials are completely fused microscopically.
- the dotted line part of Fig.19 (a) is a melt
- SAXS and WAXS analyzes were performed by irradiating the round part of FIG. 19A with X-rays.
- the SAXS image is shown in FIG.
- FIGS. 19 (b) and 19 (c) showed a typical pattern indicating the presence of NOC, indicating that the fused sample was a NOC material. That is, it was confirmed that after the NOC material was heated to a DEN melt, fusion (secondary molding) was performed and the sample was allowed to cool, whereby the fusion sample returned to the NOC material.
- FIG. 20 shows a two-dimensional scattering pattern by a SAXS method of a sample (one example) in which an operation of room temperature ⁇ 210 ° C. ⁇ room temperature was performed under free conditions without constraint.
- FIG. 20 shows the result of the sample before heating, (b) shows the result of the sample after heating, and (c) shows the result of the sample after standing to cool.
- the DEN melt When the DEN melt is made into a DEN melt under free conditions that do not constrain the NOC material and allowed to cool to room temperature, a scattering pattern indicating that the nanocrystal (NC) is disordered (non-oriented) is observed. (See the arrow in FIG. 20 (c)).
- the NOC material was made into a mobile phase ( ⁇ 2 ′ phase) under free conditions, and the cooled sample was a NOC material (data is omitted). Therefore, it was shown that when the DEN melt was formed under free conditions where the NOC material was not restrained and allowed to cool to room temperature, it could be an NC material.
- T c (125.1 ° C.) when the sample heated to 188 ° C. is stretched and recrystallized is the same as the T c (116.1 ° C.) when recrystallized without stretching (in the case of standing). It was also expensive.
- T c (116.1 ° C.) when the sample heated to 230 ° C. was stretched and recrystallized was equivalent to T c in the case of a stationary field.
- FIG. 23 shows the relationship between the difference ( ⁇ T c ) between the T c of samples molded at various elongation strain rates and the T c in the case of a stationary field, and the elongation strain rates.
- the diamond symbol indicates the result when the NOC material is heated to 180 to 190 ° C.
- the square symbol indicates the result when the NOC material is heated to 190 to 200 ° C.
- ⁇ T c increases as the elongation strain rate increases. Further, ⁇ T c was larger as the heating temperature was lower. From these results, it became clear that the ratio of the structure having a long enthalpy relaxation time (DEN structure) increases with an increase in the elongation strain rate and a decrease in the sample temperature.
- NOC materials have excellent properties such as mechanical strength, heat resistance, and transparency. Especially, since they have the same mechanical strength as metals, they are expected to be used not only as substitutes for polymer materials but also as substitutes for metals. .
- the present invention can be used not only in various industries that handle polymer parts, but also in all industries that handle metal parts.
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Abstract
Description
前記加熱工程によってモバイル相またはDEN融液になったNOC材料を成型する成型工程;および、
前記成型工程後のNOC材料をオーダー相に相転移するまで冷却する冷却工程;を含むことを特徴としている。
(2)前記加熱工程によってモバイル相またはDEN融液になったNOC材料を成型する成型工程;および、
(3)前記成型工程後のNOC材料をオーダー相に相転移するまで冷却する冷却工程;を含むことを特徴としている。ここで「NOC材料の二次成型」とは、一旦NOC材料となったNOC成形品に対して、プレス成型などの成型が施されることを意味する。二次成型は、NOC材料を作製する一次成形後に行われる成型加工を意味する。なお、当該技術分野において、一次成形の場合は漢字表記として「成形」を用い、二次成型の場合は「成型」を用いる。
本発明の二次成型方法における加熱工程は、高分子ナノ配向結晶体材料(NOC材料)を加熱してモバイル相またはDEN融液にする工程である。
ここで「NOC材料」とはNOC(高分子ナノ配向結晶体)を主成分として含む材料のことを意味する。上記「主成分として含む」とはNOCを70%以上、好ましくは80%以上、さらに好ましくは90%以上、最も好ましくは95%以上含むこと意味する。なお、「NOC」はNOC材料を構成する高分子結晶体を意味し、「NOC材料」とは区別される。
(式) ρ=M÷V(g/cm3)
ここで、Mはサンプルの質量(g)、Vは体積(cm3)である。
Braggの式: d=2π÷q
Hall-Petch’s law (参考文献: ナノマテリアル光学大系,第2巻,ナノ金属, フジ・テクノシステム,2005年,20頁)によれば、結晶の強度は結晶サイズdの平方根の逆数に比例して増大することが知られているため、例えば、結晶サイズdが1μmから10nmになった場合、√100=10倍の強度となる。
ギニエプロットの式: Ix=Aexp(-Rg 2q2/3)、ここで-Rg 2q2/3<1
(式)
[ひずみ ε ]= [応力 σ ] / [引張弾性率 E ] (フックの法則)
引張弾性率はJIS K7161に記載されている方法に準拠して求める。すなわち、一方向の引っ張りまたは圧縮応力の方向に対するひずみ量の関係から求めることができ、縦軸に応力、横軸にひずみをとった応力ひずみ曲線のフックの法則に従った直線部の傾きに相当する。引張弾性率の算出方法の詳細については、後述する実施例の説明が参照される。なお、引張破壊強さ、引張弾性率の測定は室温25℃で測定された。
既述の通り、本発明者らがNOC材料の温度に対する挙動について検討を行った結果、NOC材料を室温から徐々に温度上昇していくとある温度において、NOC材料に含まれる結晶がオーダー相(α2相)からモバイル相(α2’相)へ相転移し、さらに温度を上昇させるとDEN融液へ変化し、さらに温度を上昇させると最終的に高分子鎖が等方的(isotoropic)になった熱平衡融液へと変化することが分かった。
成型工程は、上記加熱工程によってモバイル相(α2’相)またはDEN融液になったNOC材料を成型する工程である。成型工程における成型方法としては特に限定されるものではないが、例えば、プレス成型、延伸成型、圧延成型、絞り加工成型、圧接成型、融着成型、真空成型等を施して任意の形状に成型することが挙げられる。より具体的には、モバイル相(α2’相)またはDEN融液になったシート状のNOC材料を、適当な形状を持った型でプレスすれば所望の形状のNOC材料(またはNC材料)からなる二次成型品が得られる。なお本発明の二次成型方法によって最終的に得られた、NOC材料を二次成型して得られた二次成型品を「NOC二次成型品」という。
冷却工程は、上記成型工程後のNOC材料をオーダー相(α2相)に相転移するまで冷却する工程である。換言すれば、成型工程後のNOC材料をTo-m未満の温度にする工程である。冷却の方法は特に限定されるものではなく、従来公知の冷却手段を用いて強制的に温度をTo-m未満にしてもよいし、成型工程後のNOC材料を室温等に放置しTo-m未満になるまで放冷してもよい。つまり本冷却工程においては、冷却速度は特に限定されないということである。なお、冷却工程は、気相中で実施されても、液相中で実施されてもよい。
本発明の二次成型方法は、バッチ式で行われてもよいが、工業的には連続式で行なわれることが好ましい。本発明の二次成型方法を連続式で実施する場合の一態様としては、以下の態様が挙げられる。
(1)ベルトコンベア上にNOC材料を載置する。
(2)ベルトコンベアによってNOC材料を、加熱工程を実施し得る加熱炉へ搬送する。この時、ベルトコンベアは加熱炉内を通過するように設計されている。ベルトコンベア上のNOC材料は加熱炉内を移動している間に所定の温度(To-m以上Tiso未満、より好ましくはTm以上Tiso未満)の温度範囲に達し、NOC材料がモバイル相(α2’相)またはDEN融液に変化する。
(3)NOC材料のモバイル相(α2’相)またはDEN融液の状態を維持しつつ、加熱炉内に設置された成型手段(プレス成型機等)、または加熱炉外のすぐ下流に設置された成型手段(プレス成成型等)によって、二次成型(成型工程)が実施される。二次成型(成型工程)を実施される間、ベルトコンベアは動作していてもよいし、一旦停止してもよい。
(4)二次成型(成型工程)を経たNOC材料はベルトコンベアによって、加熱炉外へ搬送される(二次成型を加熱炉外で行った場合はそのまま搬送される)。搬送中にベルトコンベア上のNOC材料は、そのまま放冷または適当な冷却手段によって冷却され、To-m未満となる(冷却工程)。冷却工程によって、モバイル相(α2’相)またはDEN融液のNOC材料がオーダー相(α2相)へ再び相転移し、NOC二次成型品となる。
(5)冷却工程を経たNOC二次成型品は、そのままベルトコンベアで搬送され、回収手段によって回収される。
上記本発明の二次成型方法は、例えば、以下の分野に利用され得る。PPのNOC二次成型品は、自動車用内装材の大部分(90%以上)として利用が可能である。またPPのNOC二次成型品は、高強度および高靱性を活かして金属の代替として自動車、航空機、ロケット、電車、船舶、バイク、および自転車など乗り物の構造部材、内装・外装材、または各種機械器具の部品や構造部材として利用が可能である。またPPのNOC二次成型品は、高剛性かつ軽量を活かしてスピーカーやマイク用振動板として利用が可能である。またPPのNOC二次成型品は、高透明性を活かしてPCの代替としてCDやDVDとして利用が可能である。またPPのNOC二次成型品は、高透明性を活かして液晶やプラズマディスプレイ用マスクなどとして利用が可能である。またPPのNOC二次成型品は、高透明性を活かしてディスポーザブル注射器、点滴用器具、薬品容器などの医療用品の材料として利用が可能である。またPPのNOC二次成型品は、高透明性を活かしてガラスの代替として各種瓶、グラス、家庭用小型水槽から業務用大型水槽として利用が可能である。またPPのNOC二次成型品は、高透明性を活かしてコンタクトレンズ,めがね用レンズ,各種光学レンズの材料として利用が可能である。またPPのNOC二次成型品は、高透明性を活かしてビル用や住宅用ガラスとして利用が可能である。またPPのNOC二次成型品は、高剛性や高靱性や軽量を活かしてスキー靴、スキー板、ボード、ラケット、各種ネット、テント、リュックサックなどの広範なスポーツ用品の材料として利用が可能である。またPPのNOC二次成型品は、高剛性や高靱性や軽量を活かして、針、はさみ、ミシンなどの手芸用品や装飾用品の材料として利用が可能である。またPPのNOC二次成型品は、ショーウインドウやディスプレイ部品などの商業用品の材料として利用が可能である。またPPのNOC二次成型品は、ブランコ,シーソー,ジェットコースターなどの公園、遊園地、テーマパーク用器具または設備の材料として利用が可能である。その他、PPのNOC二次成型品は、電気・電子・情報機器、または時計等精密機器の部品の構造材や箱材;ファイル、フォルダ、筆箱、筆記用具、はさみなどの文房具;包丁、ボール、などの料理用具;食品、お菓子、タバコなどの包装材;食品容器、食器、割り箸、楊枝;家庭用家具、オフィス家具などの家具;ビルや住宅用の建材、内装材、および外装材;道路または橋梁用の材料;玩具用の材料;超強力繊維や糸;漁業用漁具、漁網、つり用具;農業用具、農業用品;レジ袋,ゴミ袋;各種パイプ;園芸用品;および運輸用コンテナ、パレット、箱;等として利用が可能である。
前記加熱工程によってモバイル相またはDEN融液になったNOC材料を成型する成型工程;および、
前記成型工程後のNOC材料をオーダー相に相転移するまで冷却する冷却工程;を含むことを特徴としている。
〔NOC材料の作製〕
NOC材料は、ライオンデルバセル・インダストリーズ社製iPP Adstif HA1152(Mw=34×104,Mw/Mn=30、平衡融点Tm 0=187℃)またはサンアロマー(株)製iPP サンアロマーPM802A(Mw=23×104,Mw/Mn=7、平衡融点Tm 0=187℃)を用いて作製された。なお「Mw」は重量平均分子量を意味し、「Mn」は数平均分子量を意味する。あるMwにおけるTm 0は「K. Yamada, M. Hikosaka et. al, J.Mac.Sci.Prat B-Physics, B42(3&4), 733 (2003)」で決定したMwのTm 0と同じと仮定した。
切出した後のサンプルのたて、およびよこ方向のサイズについては、対物マイクロメーターで校正したスケールを用い、光学式実体顕微鏡(オリンパス株式会社製、SZX10-3141)で測定された。厚みについてはマイクロメーター、または光学式実体顕微鏡(オリンパス株式会社製、SZX10-3141)を用いて測定した。サイズの測定は、室温25℃で行った。なお、サンプルの厚さは0.2~0.4mmであった。
次にNOC材料のサンプルの結晶化度χcを、密度法により測定した。より具体的には、質量(M)と体積(V)を用いた密度法により、サンプルの結晶化度を決定した。測定は、室温25℃で行った。切出したサンプルのサイズは、マイクロメーターと光学式実体顕微鏡(オリンパス株式会社製、SZX10-3141)を用いて測定した。また、切出したサンプルの質量は、デジタル電子天秤(ザルトリウス社製、ME253S)を用いて測定した。測定は、室温25℃で行った。
NOC材料の耐熱温度を、光学顕微鏡を用いた試験片サイズ直読法により測定した。ホットステージ(Linkam社製,L-600A)上に試験片(たて0.7mm、よこ0.7mm、厚さ0.25mm)を置き、昇温速度1K/分でホットステージ内を昇温した。この時、CCDカメラ付光学顕微鏡(オリンパス(株)製BX51N-33P-OC)で観察と記録を行った。画像解析ソフトウェア(Media Cybernetics社製、Image-Pro PLUS)を用いて、試験片のたて方向(MD)、およびよこ方向(TD)を定量的に計測し、MD方向またはTD方向に3%以上収縮(又は膨張)を開始した時の温度を、耐熱温度Tdとして得た。
NOC材料を、小角X線散乱法(以下、「SAXS法」という)を用いて観察した。SAXS法は、「高分子X線回折 角戸 正夫 笠井 暢民、丸善株式会社、1968年」や「高分子X線回折 第3.3版 増子 徹、山形大学生協、1995年」の記載に準じて行われた。より具体的には、(財)高輝度光科学研究センター(JASRI)SPring-8、ビームライン BL40B2 において、X線の波長λ=0.15nm、カメラ長1654mmで、検出器にイメージングプレート(Imaging Plate)を用いて、室温25℃で行った。MDとTDに垂直な方向(through)とTDに平行な方向(edge)とMDに平行な方向(end)の3方向について観察した。throughとedgeの試料についてはMD方向をZ軸方向にセットし、endについてはTD方向をZ軸方向にセットし、X線の露出時間は180秒で行った。イメージングプレートを株式会社リガク製の読取装置と読込みソフトウェア(株式会社リガク、raxwish,control)とで読取り、2次元イメージを得た。
また図5(a)のthroughの2次元イメージについて、解析ソフトウェア(株式会社リガク、R-axis,display)を用いて解析した。図6に示す散乱ベクトル(q)-小角X線散乱強度(Ix)曲線は、2次元イメージを偏角について全周積分し、バックグラウンド補正をして得た。Ix曲線の1次のピークに相当するq=qd=0.238nm-1であった。よって、NOCのサイズd=2π/qd=26nmを得た。
上記で作製したNOC材料において、throughとedgeとendの3方向から広角X線散乱法(WAXS法)を用いて観察した。WAXS法は、(財)高輝度光科学研究センター(JASRI)SPring-8、ビームライン BL40B2 で、X線の波長(λ)はλ=0.072nm、カメラ長(R)はR=270mmで、検出器にイメージングプレート(Imaging Plate)を用いて、室温25℃で行った。throughとedgeの試料についてはMD方向をZ軸方向にセットし、endについてはTD方向をZ軸方向にセットし、X線の露出時間は60秒で行った。イメージングプレートを株式会社リガク製の読取装置と読込みソフトウェア(株式会社リガク、raxwish,control)とで読取り、2次元イメージを得た。さらに、2次元イメージを解析ソフトウェア(株式会社リガク、R-axis,display)を用いて解析し、α2相の体積分率f(α2)を測定した。より具体的には、
(式)
(参考文献:M.Hikosaka, Polymer Journal 1973 5 p.124を参照のこと)を用いてα2分率を求めた。ここで、|F0|はhkl=-2,3,1と-1,6,1との観測から得た構造因子、|Fα2|はα2相100%の時のhkl=-2,3,1と-1,6,1との構造因子である。|F0|は、バックグラウンドを補正して得た広角X線散乱強度(Ix)と、
(式) Ix=|F0|2
の関係にある。
上記で得たの2次元イメージから、NOC材料の配向関数fcを得た。より具体的には、図7(b)edgeについてイメージングプレート読み取りソフトウェア(株式会社リガク、raxwish,control)で得た2次元イメージを、表計算ソフトウェア(WaveMetrics社製、Igor Pro)で解析を行うことにより配向関数fcを得た。図7(b)に示すhkl=040反射について、偏角(β)-広角X線散乱強度(Ix)曲線は、バックグラウンド補正をして得た。より具体的には、
配向関数の式:fc=<3cos2β―1>÷2
ただし、
(式)
上記で作製したNOC材料について、JIS K7127準拠で引張強度の測定を行った。より具体的には、試験片(標線間距離7mm、狭い平行部の幅1.6mm、厚さ0.25mm)を、精密万能試験機((株)島津製作所製、オートグラフAG-1kNIS)にセットし、引張速度10mm/minで引っ張ることによって引張強度の測定を行った。測定は、室温25℃で行った。
NOC材料において、ヘーズ測定法によりヘーズ(ヘーズ値:厚さ0.3mm)を測定した。ヘーズ測定法は、試験片を透過した透過光の光量を測定することにより実施された。ヘーズ測定法には、光学顕微鏡(オリンパス(株)製BX51N-33P-OC)、光量を定量できるCCDカメラ(QImaging社製 冷却デジタルカメラ QICAM)と、画像解析ソフトウェア(Media Cybernetics社製、Image-Pro PLUS)を備える装置が用いられた。測定光として用いたハロゲンランプを白色光源とした入射光のサイズは、直径1mmの円形であった。
室温(25℃)のNOC材料を、135℃、165℃、180℃、210℃または225℃にそれぞれ加熱した。ちなみに本実施例におけるNOC材料のTo-mは約157℃、Tmは約170℃、Tisoは約215℃であった。よって135℃ではNOC材料はオーダー相(α2相)のままであり、165℃ではモバイル相(α2’相)に相転移しており、175℃および210℃ではDEN融液となっており、225℃では熱平衡融液となっている。
NOC材料を188℃に加熱し、伸長ひずみ速度419(sec-1)で伸長成形した。このNOC材料を10K/分の降温速度で冷却した時の再結晶化温度(Tc)は125.1℃であった(図22中の実線を参照のこと)。一方、NOC材料を230℃に加熱して同様に伸長成形を行った場合の、Tcは116.1℃であった(図22中の破線を参照のこと)。
1 過冷却融液
2 過冷却融液供給機
3 挟持ロール
Claims (10)
- 高分子ナノ配向結晶体材料を加熱してモバイル相、または高密度絡み合いネットワーク構造を有する融液にする加熱工程;
前記加熱工程によってモバイル相、または高密度絡み合いネットワーク構造を有する融液になった高分子ナノ配向結晶体材料を成型する成型工程;および
前記成型工程後の高分子ナノ配向結晶体材料をオーダー相に相転移するまで冷却する冷却工程;を含むことを特徴とする、高分子ナノ配向結晶体材料の二次成型方法。 - 上記高分子ナノ配向結晶体材料は、結晶サイズdが300nm以下であり、結晶内高分子鎖の配向度を示す配向関数fcが0.7以上である高分子ナノ配向結晶体からなる、請求項1に記載の高分子ナノ配向結晶体材料の二次成型方法。
- 上記高分子ナノ配向結晶体材料は、棒状高次構造を含み、
当該棒状高次構造は、ナノ配向結晶体粒子が数珠状に連結してなる数珠状体が束となった構造である、請求項1または2に記載の高分子ナノ配向結晶体材料の二次成型方法。 - 上記高分子ナノ配向結晶体材料は、ポリオレフィンからなる、請求項1ないし3のいずれか1項に記載の高分子ナノ配向結晶体材料の二次成型方法。
- 上記高分子ナノ配向結晶体材料は、ポリプロピレンからなる、請求項1ないし4のいずれか1項に記載の高分子ナノ配向結晶体材料の二次成型方法。
- 上記成型工程は、複数の高分子ナノ配向結晶体材料同士を融着する工程である、請求項1ないし5のいずれか1項に記載の高分子ナノ配向結晶体材料の二次成型方法。
- 上記成型工程は、複数のシート状の高分子ナノ配向結晶体材料同士を積層し融着する工程である、請求項1ないし5のいずれか1項に記載の高分子ナノ配向結晶体材料の二次成型方法。
- 上記成型工程は、高分子ナノ配向結晶体材料をプレス成型、延伸成型、圧延成型、絞り加工成型、圧接成型、融着成型、真空成型のいずれかの工程である、請求項1ないし5のいずれか1項に記載の高分子ナノ配向結晶体材料の二次成型方法。
- 請求項1ないし7のいずれか1項に記載の高分子ナノ配向結晶体材料の二次成型方法によって得られ、
複数の高分子ナノ配向結晶体材料同士が融着してなる二次成型品。 - 複数のシート状の高分子ナノ配向結晶体材料同士が積層されてなる積層体である、請求項9に記載の二次成型品。
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