WO2020032109A1 - Objet en résine moulée, procédé de production d'objet en résine moulée, et procédé de stérilisation - Google Patents

Objet en résine moulée, procédé de production d'objet en résine moulée, et procédé de stérilisation Download PDF

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WO2020032109A1
WO2020032109A1 PCT/JP2019/031144 JP2019031144W WO2020032109A1 WO 2020032109 A1 WO2020032109 A1 WO 2020032109A1 JP 2019031144 W JP2019031144 W JP 2019031144W WO 2020032109 A1 WO2020032109 A1 WO 2020032109A1
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Prior art keywords
resin
resin molded
laser
molded article
atomic oxygen
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PCT/JP2019/031144
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English (en)
Japanese (ja)
Inventor
清水　和彦
俊輔 阿部
香代子 鬼澤
亜希 後藤
恵一 柳瀬
宮崎　英治
岳志 神谷
香菜恵 清水
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株式会社クレハ
国立研究開発法人宇宙航空研究開発機構
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Priority to JP2020535838A priority Critical patent/JP7205022B2/ja
Publication of WO2020032109A1 publication Critical patent/WO2020032109A1/fr

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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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances

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  • the present invention relates to a resin molded product, a method for producing the resin molded product, and a sterilization method.
  • Patent Documents 1 to 3 disclose a method of forming a plurality of nano-sized protrusions on the surface of a resin composition to impart antibacterial properties to the surface. According to the methods described in these documents, it is considered that the bacteria that have come into contact with the projection probably die by sticking into the projection, thereby exhibiting antibacterial properties.
  • Patent Literature 1 discloses a needle in which the distance between the protrusions is sufficiently smaller than the size of the bacterium to facilitate contact with cells, and the protrusion has a large aspect ratio and can be pierced by bacteria.
  • An antimicrobial article that exhibits antimicrobial performance by being shaped like a letter is described. Note that, in Patent Document 1, when the static contact angle of pure water on the surface of the antimicrobial article is 30 ° or less, the surface becomes hydrophilic, and the bacteria easily penetrate the microprojections. Is said to improve.
  • the antimicrobial article is manufactured by a method of curing a liquid resin composition while pressing an original plate having a desired uneven shape against the surface of the liquid resin composition. Can be.
  • Patent Document 2 describes a synthetic sterilization surface in which an array of nanospikes having a height of about 100 nm to about 600 nm is formed on a surface of black silicon or the like. According to Patent Literature 2, the nanospike perforates a cell membrane and is thus lethal to cells. According to Patent Literature 2, the array of nanospikes can be manufactured by a method such as reactive ion beam etching.
  • Patent Document 3 discloses a synthetic polymer film having a plurality of convex portions, and the two-dimensional size of the plurality of convex portions is 20 nm when viewed from the normal direction of the synthetic polymer film. Synthetic polymer membranes in the range ⁇ 500 nm are described. In Patent Document 3, sterilization is good when the contact angle of the surface of the synthetic polymer membrane with hexadecane is 51 ° or less, but the contact angle of water (hydrophilicity) is directly Is not relevant. According to Patent Literature 3, the synthetic polymer film can be manufactured by a method of curing the ultraviolet curable resin while pressing the surface of the ultraviolet curable resin using the anodized porous alumina layer as a mold.
  • Patent Document 4 the surface of a tetrafluoroethylene / hexafluoropropylene copolymer resin (FEP) is irradiated with an atomic oxygen beam obtained by a laser detonation method (the irradiation amount is 6.0 ⁇ 10 4 at the maximum). It is described that by performing 19 atoms / cm 2 ), a cell-adhesive property is imparted to the surface by forming an uneven structure having a height of about 10 nm. Patent Document 4 describes that even when the surface of low-density polyethylene (LDPE) is irradiated with an atomic oxygen beam under the same conditions, a similar uneven structure is not formed and no change in cell adhesion is observed. I have.
  • LDPE low-density polyethylene
  • Patent Document 4 performed an experiment by setting the laser energy in the laser detonation method to 5 J / Pulse to 7 J / Pulse and setting the number of repetitions (pulse rate) of the laser per second to about 1 Hz. (Non-Patent Document 1 and Non-Patent Document 2).
  • a resin molded article having a plurality of nano-sized protrusions formed on the surface of a molded article of a resin composition is obtained by applying an antimicrobial agent to the surface of the molded article.
  • the antibacterial agent is expected to be able to maintain its antibacterial performance for a longer period of time because the antibacterial agent is less likely to be degraded due to peeling and falling off of the antibacterial agent.
  • the methods described in Patent Literature 1 and Patent Literature 3 can form an antibacterial projection only on a curable resin, so that there are limitations on applicable materials and antibacterial properties can be imparted.
  • the shape of the molded article was almost limited to a film shape.
  • Patent Document 2 does not disclose a method for producing the nanospike array other than black silicon produced by reactive ion beam etching. On the other hand, the production of the nanospike array has been confirmed. Black silicon is hard, brittle, and has low shape workability, so its use is limited, and it is difficult to apply it to sterilization treatment in various situations.
  • the present invention has been made in view of the above-described problems, and can expand the selectivity of materials and shapes of molded articles, a resin molded article having antibacterial properties on a surface, and a method of manufacturing the resin molded article. It is an object of the present invention to provide a sterilization method using the resin molded body.
  • the resin composition molded article according to one embodiment of the present invention for solving the above-described problem has, on its surface, a region provided with antimicrobial properties by irradiation with an atomic oxygen beam.
  • a method for producing a resin molded article having a surface provided with antibacterial properties includes a step of preparing a molded article of a resin composition, and a step of preparing an atomic oxygen beam. Imparting antibacterial properties to the surface of the molded article by irradiation.
  • a sterilization method for solving the above-described problems, a step of preparing the resin molded body, and a step of contacting the resin molded body with a liquid containing bacteria, a solid or a gas, including.
  • a resin molded article having antibacterial properties on the surface a method for producing the resin molded article, and sterilization using the resin molded article can expand the selectivity of the shape of the material and the molded article.
  • a method is provided.
  • FIG. 1A is a schematic side view showing a protrusion having a slope having a shape recessed toward the inside of a molded article of a resin composition according to an embodiment of the present invention
  • FIG. It is a typical side view which shows the protrusion which has the slope of a convex shape toward it.
  • FIG. 2A is a graph obtained by plotting ⁇ log with respect to each bacterial species and the contact angle with pure water on the vertical axis of each of the evaluation sample and the comparative sample in the example
  • FIG. 2B is a graph obtained by plotting ⁇ log with respect to each bacterial species and the contact angle with diiodomethane on the vertical axis of each evaluation sample and comparative sample in the example
  • FIG. 3A shows the total value (A + B) of the value of the dispersion component (A) and the value of the hydrogen bond component (B) on the abscissa axis of ⁇ log of each of the evaluation sample and the comparison sample in the example with respect to each bacterial species.
  • 3B is a graph obtained by plotting on the vertical axis, and FIG.
  • FIG. 3B shows ⁇ log for each bacterial species of each of the evaluation sample and the comparative sample in the examples on the horizontal axis, and the value of the dispersion component (A) on the horizontal axis.
  • FIG. 3C is a graph obtained by plotting the ratio (B / A) of the value of the hydrogen bonding component (B) on the vertical axis, and FIG. 3C shows the bacterial species of each of the evaluation sample and the comparison sample in Examples. Is a graph obtained by plotting ⁇ log with respect to the horizontal axis, and plotting the ratio (B / (A + B)) of the value of the hydrogen bond component (B) to the total value with the vertical axis.
  • FIG. 4A shows the total value (A + C) of the value of the variance component (A) and the value of the polar component (C) on the horizontal axis of ⁇ log of each of the evaluation sample and the comparison sample in the example with respect to each bacterial species.
  • FIG. 4B is a graph obtained by plotting on the vertical axis, and FIG. 4B shows the polarities of the respective evaluation samples and comparative samples in Examples in terms of ⁇ log with respect to each bacterial species on the horizontal axis and the value of the dispersion component (A).
  • FIG. 4C is a graph obtained by plotting the ratio (C / A) of the value of the component (C) on the vertical axis, and FIG.
  • 4C shows ⁇ log of each evaluation sample and comparison sample in Examples with respect to each bacterial species. Is a graph obtained by plotting on the horizontal axis and the ratio (C / (A + C)) of the value of the polar component (C) to the total value on the vertical axis.
  • the present inventors have developed a method of irradiating the surface of a molded article of a resin composition with an atomic oxygen beam to impart antibacterial properties to the surface. According to this method, it is possible to impart antibacterial properties to a molded article of a resin composition containing a wide variety of resins. Further, according to the method, after a molded article having a desired shape is produced, the surface of the molded article may be irradiated with an atomic oxygen beam, so that the present invention can be applied to molded articles having various shapes.
  • One embodiment of the present invention relates to a molded article of a resin composition, the surface of which has a region provided with antibacterial properties by irradiation with an atomic oxygen beam.
  • the region provided with the antibacterial property has a plurality of nano-sized protrusions formed by irradiation with an atomic oxygen beam.
  • the plurality of protrusions protrude in a direction substantially perpendicular to the surface, and it is considered that the bacteria are killed by the protrusions piercing the bacteria in contact with the region.
  • the plurality of protrusions have inclined surfaces that are concave toward the inside of the protrusions.
  • FIG. 1A is a schematic side view showing a projection having a slope having a shape concave toward the inside thereof
  • FIG. 1B is a schematic side view showing a projection having a slope having a shape convex toward the outside thereof.
  • FIG. 1A it is preferable that eight or more of the arbitrarily selected ten protrusions have a shape such that the width of the protrusion monotonically decreases in the height direction.
  • the plurality of protrusions have a slope having a shape convex toward the outside thereof.
  • the antibacterial property of the resin molded article is remarkably increased as compared with when the resin molded article has (see FIG. 1B). It is considered that this is because the plurality of protrusions became more sharp needle-like, and the protrusions were more likely to pierce the bacteria in contact with the region provided with the antibacterial property.
  • the shape of the protrusion can be determined based on the protrusion curvature index calculated by the following method.
  • a cross section of each evaluation sample is imaged with a scanning electron microscope (SEM), and ten projection shapes are arbitrarily selected from the obtained SEM images.
  • the two oblique sides (a total of 20) constituting the selected projection shape are converted into actual size XY coordinate data converted to 0.0099 ⁇ m per pixel.
  • For one hypotenuse, of the converted XY coordinate data data for 5 pixels in the X-axis direction is extracted as one unit, and the extracted XY coordinate data is a two-dimensional polynomial least-squares approximation formula (ax 2 + bx + c Expression), and the value of a in the expression is determined.
  • This calculation is shifted by one pixel from the X coordinate, and the value of a is calculated for all the coordinate data of the slope.
  • the average value of all the obtained values of a is obtained and set as the hypotenuse average value.
  • the average of the hypotenuses is calculated for all of the 20 hypotenuses, and the average of the calculated averages of the 20 hypotenuses is used as the projection curvature index for the evaluation sample.
  • the projection included in the evaluation sample has a slope that is concave toward the inside of the projection (see FIG. 1A).
  • the projection curvature index is a negative value
  • the projection included in the evaluation sample has a slope having a convex shape toward the outside of the projection.
  • the projection curvature index may be any positive value, but is preferably 2.00 or more, more preferably 3.00 or more, and even more preferably 3.50 or more. If the protrusion curvature index is 2.00 or more, the antibacterial properties can be further improved, because the protrusions are more likely to penetrate bacteria.
  • the upper limit of the protrusion curvature index is not particularly limited, but if the value exceeds a certain value, the effect seems to reach a plateau, so that it can be set to, for example, 6.00.
  • the average height of the plurality of protrusions is not particularly limited, but is preferably 100 nm or more, more preferably 200 nm or more, and even more preferably 400 nm or more. If the average height is 200 nm or more, the antibacterial property is considered to be more likely because the projections are more likely to pierce the bacteria in contact with the region provided with the antibacterial property.
  • the upper limit of the average height of the projections is not particularly limited, but if the average value exceeds a certain value, the effect seems to reach a plateau, so that the average height can be, for example, 1700 nm.
  • the average value of the widths of the protrusions included in the plurality of protrusions is not particularly limited, but is preferably from 80 nm to 400 nm, more preferably from 130 nm to 400 nm. If the average value of the width of the protrusions is 130 nm or more and 400 nm or less, it is considered that the protrusions are more likely to pierce the bacteria that have contacted the region provided with the antibacterial property, and thus the antibacterial property is further enhanced.
  • the average value of the interval between the protrusions included in the plurality of protrusions is not particularly limited, but is preferably 220 nm or more and 770 nm or less, and more preferably 350 nm or more and 770 nm or less. If the average value of the intervals between the protrusions is 350 nm or more and 770 nm or less, it is considered that the protrusions are likely to pierce the bacteria that have contacted the region provided with the antibacterial property, and thus the antibacterial property is further enhanced.
  • the average height of the projections, the average value of the width of the projections, and the average value of the distance between the projections are measured by SEM image analysis obtained by imaging a cross section of the sample for evaluation with a SEM, and the surface is measured by a confocal laser microscope. It can be a value measured by analyzing the obtained cross-sectional curve. Specifically, a broken line that traces the contour of the protrusion is drawn by visual observation or some automated means.
  • any one vertex on the open line at the protrusion of a certain projection and any two vertices on the open line at the bottom side Is defined as the protrusion height of the protrusion having the largest height from the side connecting the two bottom vertices (called the base), and the base of the triangle is defined as the height of the protrusion.
  • the protrusion width of the protrusion is defined as a distance between vertices between vertices of the protrusions in the triangle having the largest height formed as described above for each of the adjacent protrusions.
  • the arithmetic average of the projection heights of all analyzed projections is defined as the average height of the projections
  • the arithmetic average of the projection width is defined as the average value of the width of the projections
  • the arithmetic average of the spacing between the projections is defined as the average value of the spacing between the projections.
  • the region provided with the antibacterial properties has antibacterial properties against various kinds of bacteria.
  • the region has antibacterial activity against at least one of Escherichia coli, Staphylococcus aureus, lactic acid bacteria, and Pseudomonas aeruginosa, and preferably has antibacterial activity against at least one of Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa.
  • sterilization is intended to both kill bacteria present in the medium and inactivate bacteria to suppress growth.
  • having antibacterial activity is determined by inoculating a bacterium, measuring the number of viable bacteria immediately after the inoculation and 24 hours after the inoculation according to the method described in JIS Z2801 (2012).
  • ⁇ log bacteria count logarithmic value of viable bacteria count after 24 hours of sample not irradiated with atomic oxygen beam ⁇ logarithmic value of viable bacteria count of evaluation sample irradiated with atomic oxygen beam after 24 hours) is 2 0.0 or more.
  • the resin composition may be any composition containing a resin.
  • the content of the resin in the resin composition is 20% by mass or more based on the total mass.
  • the resin composition may optionally contain an additive for adjusting its properties according to the use of the resin molded article.
  • the above additives include known fillers (fillers), lubricants, plasticizers, ultraviolet stabilizers, coloring inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic materials, antioxidants. Agents, coloring agents (dye, pigment) and the like. These additives may be selected and used in an optimal combination as long as the effects of the present invention are not impaired.
  • an organic substance may be another polymer
  • an inorganic substance such as metal nanoparticles may be used as other additives.
  • the type of the resin can be arbitrarily selected according to the use of the resin molded article and the like.
  • the resin may be a thermoplastic resin or a thermosetting resin. Further, the resin may be a crystalline resin or a non-crystalline resin. Further, the resin may be rubber such as synthetic rubber and natural rubber. According to the findings of the present inventors, a molded article of a resin composition having a non-aromatic resin having no aromatic ring in the repeating unit constituting the resin has an aromatic ring in the repeating unit constituting the resin. Antimicrobial properties are more likely to be imparted than molded articles of a resin composition containing an aromatic resin containing. However, even a molded article of a resin composition containing an aromatic resin can sufficiently impart antibacterial properties by appropriately adjusting the irradiation conditions of the atomic oxygen beam and the like.
  • non-aromatic resin examples include polyethylene (including linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and high-density polyethylene (HDPE)), polypropylene, and other polyolefin-based resins.
  • polyethylene including linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and high-density polyethylene (HDPE)
  • LLDPE linear low-density polyethylene
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • polypropylene examples include polypropylene, and other polyolefin-based resins.
  • PTFE polytetrafluoroethylene
  • PFA perfluoroalkoxy alkane
  • FEP perfluoroethylene propene copolymer
  • PVDF polyvinylidene fluoride
  • PVDC polyvinylidene chloride
  • non-aromatic polyamide nylon 6, nylon 66, nylon 12, etc.
  • POM polyacetal
  • POM polyurethane
  • EVOH ethylene-vinyl alcohol copolymer
  • PVC polyvinyl chloride
  • EVA ethylene-vinyl acetate Coalescence
  • PLA polylactic acid
  • PCL polycaprolactone
  • PGA polyglycolic acid
  • aromatic resin examples include polystyrene (PS), polyester (including polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polybutylene naphthalate (PBN)), and polyphenylene sulfide (PPS).
  • PS polystyrene
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PBN polybutylene naphthalate
  • PPS polyphenylene sulfide
  • Polyetheretherketone PEEK
  • semi-aromatic polyamide wholly aromatic polyamide
  • semi-aromatic polyimide wholly aromatic polyimide
  • polystyrene PS
  • acrylonitrile-styrene copolymer AS
  • ABS acrylonitrile-butadiene
  • ABS polycarbonate
  • PAR polyarylate
  • PPE polyphenylene ether
  • polyphenol-based resin and aromatic epoxy resin.
  • Examples of the synthetic rubber include isoprene rubber (IR), butadiene rubber (BR), styrene / butadiene rubber (SBR), nitrile rubber (NBR), ethylene / propylene rubber (EPM), and other thermoplastic elastomers (SEBS) , SBS, and SEPS, etc.).
  • IR isoprene rubber
  • BR butadiene rubber
  • SBR styrene / butadiene rubber
  • NBR nitrile rubber
  • EPM ethylene / propylene rubber
  • SEBS thermoplastic elastomers
  • the molded article is obtained by molding the resin composition into a two-dimensional shape or a three-dimensional shape to give a shape.
  • the shape of the molded article is not particularly limited, and can be arbitrarily selected according to the use of the resin molded article.
  • the molded body can have a shape such as a film shape, a sheet shape, a plate shape, a bag shape, a tubular shape, a fiber shape, a mesh shape, a predetermined shape, or an amorphous solid shape.
  • These molded bodies may be provided with antimicrobial properties by irradiating an atomic oxygen beam on at least a part of their surfaces, but the entire surface is imparted with antibacterial properties by irradiating an atomic oxygen beam. May be.
  • an atomic oxygen beam On at least a part of their surfaces, but the entire surface is imparted with antibacterial properties by irradiating an atomic oxygen beam. May be.
  • at least the part may be provided with antibacterial properties.
  • These molded articles may be provided with antibacterial properties on their outer surfaces, or when they have a bag-like or tubular shape, their inner surfaces may be provided with antibacterial properties.
  • the resin molded article can be used for a wide variety of applications, including packaging, building equipment, home appliances, electronic devices and peripheral devices, automotive parts, various coatings, medical devices, agricultural supplies, stationery, body accessories, and the like. is there.
  • Examples of the above-mentioned building equipment include toilet and toilet seats, vanities, plumbing, water and water plumbing, foot wipe mats, interior materials, and doors, etc. Articles are included.
  • Examples of the above home appliances include rice cookers, microwave ovens, refrigerators, irons, hair dryers, air conditioners and air purifiers.
  • Examples of the electronic device and its peripheral devices include a notebook computer, a smartphone, a tablet, a digital camera, a medical electronic device, a POS system, a printer, a television, a mouse, a keyboard, and the like.
  • Examples of the automotive parts include a steering wheel, a seat, a shift lever, and various pipes.
  • Examples of the above packaging include packaging for pharmaceuticals and foods.
  • coatings examples include coatings on walls, floors and ceilings such as factories, operating rooms, storage and shipping containers.
  • Examples of the medical device include forceps, syringes, stents, artificial blood vessels, catheters, wound dressings, scaffolds for regenerative medicine, and adhesion prevention materials.
  • Examples of the agricultural supplies include stretch films for agricultural houses.
  • Examples of the above body accessories include clothing, including outerwear and underwear, hats, shoes, gloves, diapers, and napkins and their storage bags.
  • the resin molded article can be used for contacting building equipment, body accessories, tableware, beverages, foodstuffs, and the like to sterilize bacteria contained therein.
  • the resin molded article having a surface provided with the antibacterial property can be formed by irradiating a molded article of the resin composition with an atomic oxygen beam.
  • a molded article of a resin composition to be provided with antibacterial properties on its surface is prepared.
  • the type of the resin composition and the shape of the molded article are as described above.
  • the irradiation with the atomic oxygen beam is performed on a region of the surface of the molded body to which antibacterial property is to be imparted.
  • the generation of the atomic oxygen beam can be performed by a known method such as a method utilizing gas dynamic expansion, an ion neutralization method, an electron stimulated desorption (ESD) method, and a laser detonation method.
  • a known method such as a method utilizing gas dynamic expansion, an ion neutralization method, an electron stimulated desorption (ESD) method, and a laser detonation method.
  • the laser detonation method is preferable because an atomic oxygen beam having a high kinetic energy can be efficiently generated.
  • an oxygen molecular gas and a laser are both emitted in a pulse form, and the oxygen molecular gas is turned into plasma by laser irradiation on the oxygen molecular gas.
  • the plasma is further irradiated with the laser to generate bombardment waves (detonation)
  • the thermal energy of the plasma is converted into kinetic energy, and at the same time, the ions and electrons in the plasma recombine to form a beam of atomic oxygen. Occurs.
  • the energy of the laser to be introduced is preferably 8 J / Pulse or more, more preferably 10 J / Pulse or more.
  • the energy of the laser is 8 J / Pulse or more, antibacterial properties can be efficiently imparted to molded articles of a wide variety of resin compositions.
  • the upper limit of the energy of the laser is not particularly limited, it is more preferably 20 J / Pulse or less.
  • the repetition rate (pulse rate) of the laser to be introduced per second is preferably 5 Hz or more, and more preferably 12 Hz or more.
  • the pulse rate of the laser is 12 Hz or more, antibacterial properties can be efficiently imparted to molded articles of a wide variety of resin compositions.
  • the upper limit of the pulse rate of the laser is not particularly limited, it is more preferably 20 Hz or less.
  • the translational energy of the atomic oxygen beam is preferably 1 eV or more and 20 eV or less, more preferably 2 eV or more and 15 eV or less, and still more preferably 3 eV or more and 10 eV or less.
  • the speed of the atomic oxygen beam is preferably 5 km / s or more and 13 km / s or less, and more preferably 6 km / s or more and 10 km / s or less.
  • the integrated irradiation amount of the atomic oxygen beam is preferably 1.0 ⁇ 10 17 atoms / cm 2 or more, more preferably 1.0 ⁇ 10 19 atoms / cm 2 or more, and more preferably 1.0 ⁇ 10 19 atoms / cm 2 or more. More preferably, it is at least 10 20 atoms / cm 2 .
  • the integrated irradiation amount is 1.0 ⁇ 10 20 atoms / cm 2 or more, antibacterial properties can be efficiently imparted to a wide variety of resin molded articles.
  • the upper limit of the integrated irradiation amount is not particularly limited, it can be set to 1.0 ⁇ 10 22 atoms / cm 2 or less.
  • the irradiation time of the atomic oxygen beam is not particularly limited, but is preferably 2 hours or more, more preferably 5 hours or more, further preferably 8 hours or more, and further preferably 10 hours or more. Especially good. Although the upper limit of the irradiation time is not particularly limited, the effect is expected to reach a plateau when the irradiation time exceeds a certain time.
  • the irradiation conditions of these atomic oxygen beams may be adjusted to the conditions under which antibacterial properties are imparted, depending on the type and various physical properties of the resin composition.
  • the irradiation conditions of these atomic oxygen beams are determined by measuring in advance, the type of the resin composition, and the irradiation conditions of the atomic oxygen beam, by referring to a correspondence table showing the relationship, Can be determined.
  • the irradiation conditions of the atomic oxygen beam are determined by causing a processing apparatus that has performed machine learning or the like to calculate the relationship between the type of the resin composition and the irradiation condition of the atomic oxygen beam. be able to.
  • the resin molded body may be further molded after being provided with antimicrobial properties by irradiation with an atomic oxygen beam.
  • the surface of a film-shaped or sheet-shaped molded body is irradiated with an atomic oxygen beam to impart antibacterial properties to the surface, and then further molded into a bag-like shape or a tubular shape, thereby imparting antibacterial properties to the inner surface thereof.
  • It can be a molded article such as a bag-shaped or tubular shape provided.
  • the resin molded article having a surface provided with the antibacterial property can be used for various sterilization methods.
  • the bacteria contained in the contacted liquid, the solid surface or the gas are killed, and the liquid, the solid or the gas is removed. Can be sterilized.
  • the contact may be performed by a known method.
  • the contact with a liquid is performed by immersing the resin molded body in the flowing or stationary liquid, spraying or spraying the liquid on the resin molded body, and applying or dropping the liquid on the resin molded body. It can be performed by such a method.
  • the contact with the solid can be performed by a method such as contacting or pressing the stationary or sliding resin molded body against the surface of the stationary or sliding solid.
  • the contact with the gas can be performed by a method such as allowing the resin molded body to stand still in a flowing or stationary atmosphere containing the gas, and injecting the gas into the resin molded body.
  • Laser type CO 2 laser Laser wavelength: 10.6 ⁇ m (Irradiation condition of atomic oxygen beam) Average oxygen content: about 120sccm / 12Hz Laser energy: 10J / Pulse Laser pulse rate: 12Hz Beam speed: 8.11 km / s Irradiation time: 6 hours or 12 hours Irradiation amount: 7.765 ⁇ 10 19 atoms / cm 2 (6 hours irradiation) 1.553 ⁇ 10 20 atoms / cm 2 (when irradiated for 12 hours) Irradiation temperature: room temperature
  • the used base films are as follows. Each base film had a 50 mm ⁇ 50 mm square shape.
  • PET Polyethylene terephthalate
  • PVDF Polyvinylidene fluoride
  • PVDC Kureha Co., Ltd., thickness 45 ⁇ m
  • Evaluation 2-1 Antibacterial property The antibacterial property against Escherichia coli or Staphylococcus aureus of the evaluation sample and the comparative sample was evaluated according to the method described in JIS Z 2801 (2012). Lactic acid bacteria and Pseudomonas aeruginosa were also evaluated in the same manner as Escherichia coli and Staphylococcus aureus. Specifically, the following Escherichia coli, Staphylococcus aureus, lactic acid bacteria or Pseudomonas aeruginosa were inoculated and cultured for 24 hours under the following conditions. (Species) E. coli: Escherichia coli, NBRC No.
  • Staphylococcus aureus Staphylococcus aureus
  • NBRC No. 12732 Lactic acid bacteria: Lactobacillus casei
  • NBRC No. 15883 Pseudomonas aeruginosa: Pseudomonas aeruginosa
  • NBRC No. 12689 Temperature: Escherichia coli, Staphylococcus aureus, Lactic acid bacteria 35 °C ⁇ 1 °C, Pseudomonas aeruginosa 30 °C ⁇ 1 °C (Measurement of viable cell count)
  • the viable cell count was measured according to the method described in JIS Z 2801 (2012), and the ⁇ log cell count (logarithmic value of the viable cell count 24 hours after the comparison sample-evaluation) Logarithmic value of the number of viable bacteria 24 hours after the test sample).
  • the ⁇ log bacteria count was 2.0 or more, the sample for evaluation was evaluated as having sufficient antibacterial properties.
  • Table 1 shows the ⁇ log and antibacterial evaluation results of each evaluation sample (“O” indicates sufficient antibacterial activity, and “X” indicates insufficient antibacterial activity). Is shown.
  • the irradiation time of the atomic oxygen beam is 12 hours (irradiation amount: 1.553 ⁇ 10 20 atoms / cm 2 ), the irradiation time is 6 hours (irradiation amount: 7.765 ⁇ 10 19 atoms / cm 2). 2 ) The antibacterial property was easily imparted as compared with the case of 2 ).
  • non-aromatic resins (LLDPE, PVDC and PVDF) were more likely to be provided with antibacterial properties than aromatic resins (PET), and LLDPE was particularly easy to be provided with antibacterial properties.
  • the projection included in the evaluation sample has a slope that is concave toward the inside of the projection (see FIG. 1A).
  • the projection curvature index is a negative value
  • the projection included in the evaluation sample has a slope having a convex shape toward the outside of the projection (see FIG. 1B).
  • Table 2 shows the projection curvature index and antibacterial evaluation result of each evaluation sample.
  • the evaluation sample having a positive protrusion curvature index had antibacterial properties, whereas the evaluation sample having a negative protrusion curvature index had no antibacterial properties.
  • Table 3 shows the contact angles of the respective evaluation samples and comparative samples.
  • those in which the "atomic oxygen beam irradiation time" is 0 indicate comparative samples to which the atomic oxygen beam was not irradiated.
  • FIG. 2A, FIG. 2B and FIG. 2C show the relationship between the contact angle and the evaluation result of the antibacterial property.
  • FIG. 2A is a graph obtained by plotting ⁇ log with respect to each bacterial species and the contact angle with pure water on the vertical axis of each of the evaluation sample and the comparative sample
  • FIG. 2C is a graph obtained by plotting ⁇ log with respect to each bacterial species and the contact angle with diiodomethane on the vertical axis of the evaluation sample and the comparison sample for each bacterial species
  • FIG. 2C shows the respective evaluation samples and comparison samples.
  • FIG. 4 is a graph obtained by plotting ⁇ log of each sample for each bacterial species on the horizontal axis and the contact angle with n-hexadecane on the vertical axis.
  • a boundary where ⁇ log 2, which is an index for evaluating antibacterial activity, is indicated by a dotted line.
  • the surface free energy was calculated by the Owen and Wendt method using two contact angles of the contact angle with pure water and the contact angle with diiodomethane, and the contact angle with pure water and the contact angle with n-hexadecane were calculated.
  • the surface free energy was calculated by the Kaelble-Uy method using the two contact angles.
  • Table 4 shows the surface free energies (dispersion component (A) value, hydrogen bonding component (B) value, (A) and (B)) of each evaluation sample and comparison sample calculated by the Owen and Wendt method. , The ratio of the value of the hydrogen bonding component (B) to the value of the dispersion component (A), and the ratio of the value of the hydrogen bonding component (B) to the total value).
  • those in which the "atomic oxygen beam irradiation time" is 0 indicate comparative samples to which the atomic oxygen beam was not irradiated.
  • FIGS. 3A, 3B and 3C show the relationship between the surface free energy calculated by the ⁇ Owen ⁇ and ⁇ Wendt ⁇ method and the antibacterial evaluation result.
  • FIG. 3A shows ⁇ log for each bacterial species of each evaluation sample and comparison sample on the horizontal axis, and the total value (A + B) of the values of the dispersion component (A) and the hydrogen bonding component (B) on the vertical axis.
  • FIG. 3B is a graph obtained by plotting, and FIG. 3B shows the hydrogen bond component (B) with respect to the value of the dispersion component (A) on the abscissa axis of ⁇ log of each evaluation sample and the comparison sample with respect to each bacterial species.
  • FIG. 3A shows ⁇ log for each bacterial species of each evaluation sample and comparison sample on the horizontal axis, and the total value (A + B) of the values of the dispersion component (A) and the hydrogen bonding component (B) on the vertical axis.
  • FIG. 3B
  • 3C is a graph obtained by plotting the ratio of values (B / A) on the vertical axis and ⁇ log for each bacterial species of each evaluation sample and comparative sample on the horizontal axis.
  • 5 is a graph obtained by plotting the ratio (B / (A + B)) of the value of the hydrogen bonding component (B) to the vertical axis on the vertical axis.
  • ⁇ log 2 which is an index for evaluating antibacterial activity
  • Table 5 shows the surface free energies (dispersion component (A) values, polar component (C) values, (A) and (C) values) of the respective evaluation samples and comparative samples calculated by the Kaelble-Uy method.
  • the total value, the ratio of the value of the polar component (C) to the value of the variance component (A), and the ratio of the value of the polar component (C) to the total value) are shown.
  • those in which the "atomic oxygen beam irradiation time" is 0 indicate comparative samples to which the atomic oxygen beam was not irradiated.
  • FIGS. 4A, 4B and 4C show the relationship between the surface free energy calculated by the ⁇ Kaelble-Uy ⁇ method and the antibacterial evaluation result.
  • FIG. 4A shows ⁇ log for each bacterial species of each evaluation sample and comparative sample on the horizontal axis, and the total value (A + C) of the values of the dispersion component (A) and the polar component (C) on the vertical axis.
  • FIG. 4B is a graph obtained by plotting, and FIG. 4B shows the value of the polar component (C) with respect to the value of the dispersion component (A) on the abscissa axis of ⁇ log of each evaluation sample and the comparison sample with respect to each bacterial species.
  • FIG. 4C is a graph obtained by plotting the ratio (C / A) on the vertical axis, and FIG. 4C shows ⁇ log for each bacterial species of each evaluation sample and comparative sample on the horizontal axis, and the polarity with respect to the total value. It is a graph obtained by plotting the ratio (C / (A + C)) of the value of the component (C) on the vertical axis.
  • a boundary where ⁇ log 2, which is an index for evaluating antibacterial activity, is indicated by a dotted line.
  • the resin molded article of the present invention can be used for various sterilization and antibacterial applications.

Abstract

La présente invention a pour objet de fournir : un objet en résine moulée qui permet d'atteindre un choix plus large de matériaux et de formes d'objet moulé et qui comprend une surface à laquelle sont conférées des propriétés antibactériennes ; et un procédé de production de l'objet en résine moulée. L'objectif est atteint avec un objet moulé en résine qui est un objet moulé d'une composition de résine et qui comprend une surface ayant une région à laquelle ont été conférées des propriétés antibactériennes par exposition à des faisceaux d'oxygène atomique. L'objet en résine moulée peut être produit par un procédé comprenant : une étape dans laquelle un objet moulé d'une composition de résine est préparé ; et une étape dans laquelle des propriétés antibactériennes sont conférées à une surface de l'objet moulé par exposition à des faisceaux d'oxygène atomique.
PCT/JP2019/031144 2018-08-08 2019-08-07 Objet en résine moulée, procédé de production d'objet en résine moulée, et procédé de stérilisation WO2020032109A1 (fr)

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