WO2018016561A1 - 医療用フィルム及びその製造方法、医療用コーティング組成物、医療用具及びその製造方法 - Google Patents
医療用フィルム及びその製造方法、医療用コーティング組成物、医療用具及びその製造方法 Download PDFInfo
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- WO2018016561A1 WO2018016561A1 PCT/JP2017/026208 JP2017026208W WO2018016561A1 WO 2018016561 A1 WO2018016561 A1 WO 2018016561A1 JP 2017026208 W JP2017026208 W JP 2017026208W WO 2018016561 A1 WO2018016561 A1 WO 2018016561A1
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- acid dianhydride
- medical film
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- 0 CC(C)*CNC(*(C(O)=O)C(O)=O)=O Chemical compound CC(C)*CNC(*(C(O)=O)C(O)=O)=O 0.000 description 1
- FILVHGGOUFZULB-UHFFFAOYSA-N CCC(C)NC(C)=O Chemical compound CCC(C)NC(C)=O FILVHGGOUFZULB-UHFFFAOYSA-N 0.000 description 1
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Definitions
- the present invention relates to a medical film and a method of manufacturing the same, a coating composition for medical use, a medical device and a method of manufacturing the same.
- Medical devices such as medical containers filled with a drug solution, blood, etc. are required to have transparency that facilitates visual recognition of contents in order to be able to confirm the contamination due to foreign substances and the change due to the mixing of drugs. Furthermore, heat resistance, chemical resistance, and solvent resistance that can withstand heat sterilization and the like are also required.
- glass containers have been used as medical containers satisfying such performance.
- care must be taken in handling such as cracking due to impact or falling, heavy, elution of alkali ions, and the like.
- it is difficult to make it disposable for example, it is difficult to incinerate it, and it is dangerous to dispose of fragments.
- resin materials such as polypropylene resin, polyethylene resin, vinyl chloride resin, ethylene-vinyl acetate copolymer resin, polystyrene resin and polycarbonate resin are used as alternatives to glass. These resin materials are used in disposable plastic medical containers, particularly in consideration of hygiene. However, these general-purpose resins are inferior in heat resistance and not only can not be steam-sterilized, but also inferior in solvent resistance, so there is a risk that low-molecular organic components and halogen components may be eluted.
- Such medical devices are often sterilized with alcohol or the like because they must be sterilized because sterility is essential.
- the medical device is composed of a base material having poor chemical resistance, there has been a problem that solvents and cracks easily occur, and the transparency may be impaired.
- the medical device is composed of a base material having poor heat resistance, it may be deformed by heat during heat sterilization such as steam sterilization, autoclave sterilization, dry sterilization, etc., and the transparency may be impaired due to the effect. .
- sterilization methods include ethylene oxide gas sterilization and gamma ray sterilization.
- medical containers have problems such as cracking and crazing due to ethylene oxide sterilization temperature (40 to 60 ° C) and humidity, material changes due to deformation, and material changes due to ⁇ rays, etc., making it difficult to use in the medical field May be
- polyimide resins generally have high heat resistance and mechanical strength, and may be applied as a substrate used for medical devices.
- a medical device including a conductor and an insulating layer covering the conductor and containing an aromatic polyimide is known (see, for example, Patent Document 1).
- a bag-shaped material for heat treatment comprising a laminated film of a commercially available aromatic polyimide film and an adhesive fluororesin layer is known (see, for example, Patent Document 2).
- a medical device having a coating layer comprising a cured product of a photocurable polyimide resin composition comprising (a) soluble polyimide, (b) carbon cluster and / or a derivative thereof, and (c) a heterocycle-containing compound is known. (See, for example, Patent Document 3).
- This invention is made in view of the said situation, and it aims at obtaining the medical film excellent in transparency, heat resistance, and solvent resistance.
- a medical film having a b * value of 10 or less in the L * a * b * color system is 5 or less.
- Medical film described in. [8] A method for producing the medical use film according to any one of [1] to [7], which is a polyamide acid composition containing a polyamide acid containing an amic acid unit represented by the following general formula (2): The process of obtaining (In the general formula (2), R 1 is a group derived from an alicyclic diamine, R 2 is a group derived from aromatic tetracarboxylic acid dianhydride) After the polyamic acid composition is coated on a support, the composition is heated to a maximum temperature at an average temperature rising rate of 1 to 10 ° C./min at an oxygen concentration of 5% or less, and then imidized at the maximum temperature.
- a medical device comprising the medical film according to any one of [1] to [7].
- a medical coating composition comprising a polyamic acid, wherein the total light transmittance of a 10 ⁇ m thick film made of a cured product of the medical coating composition is 80% or more, and L * a * b * Medical coating composition whose b * value in a color system is 10 or less.
- R 1 is a group derived from an alicyclic diamine
- R 2 is a group derived from aromatic tetracarboxylic acid dianhydride
- the group derived from the alicyclic diamine is a group selected from the group consisting of 1,4-bis (aminomethyl) cyclohexane, trans-1,4-cyclohexyldiamine, and norbornane diamine
- Groups derived from carboxylic acid dianhydrides are selected from pyromellitic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride
- the medical coating composition according to [12] which is a group derived from an aromatic tetracarboxylic acid dianhydride selected from the group consisting of [14]
- a medical device comprising: a medical member; and a coating layer comprising a cured product of the medical coating composition according to any of [11] to [14].
- the medical film excellent in transparency, heat resistance, and solvent resistance can be provided.
- a film obtained by molding 1) using a polyimide containing a structural unit derived from an alicyclic diamine and 2) molding under a specific molding condition has high colorless transparency (high overall transparency). It was found to have light transmittance and low b * value).
- the film can maintain very little color change, deformation, and the like, and can maintain high colorless transparency and shape retention.
- Such a film is suitable, for example, as a base material (a packaging material or a coating material) constituting a medical device that is required to have heat resistance that withstands heat sterilization and the like and transparency with which the contents can be viewed.
- the film is also excellent in resistance to load and deformation such as repeated bending, it is more suitable as a base material (packaging material or coating material) constituting a medical device.
- the present invention has been made based on these findings.
- the medical film of the present invention contains a heat resistant resin having a glass transition temperature of 190 ° C. or higher.
- composition (heat-resistant resin)
- the medical film contains a heat resistant resin having a glass transition temperature of 190 ° C. or higher.
- a heat resistant resin having a high glass transition temperature of 190 ° C. or higher is considered to have not only high heat resistance but also high solvent resistance because the interaction between polymer molecules is also high.
- the heat resistant resin may be a thermoplastic resin.
- the glass transition temperature of the heat resistant resin is preferably 200 ° C. or more, and more preferably 205 ° C. or more.
- Glass transition temperature is the temperature measured by thermomechanical analysis (TMA). Specific measurement conditions are the same as in the examples described later.
- the heat-resistant resin having a glass transition temperature of 190 ° C. or higher is preferably polyimide, from the viewpoint of having good heat resistance and solvent resistance.
- the polyimide contains a structural unit derived from a diamine and a structural unit derived from tetracarboxylic acid dianhydride.
- the structural unit derived from tetracarboxylic acid dianhydride contains a structural unit derived from alicyclic tetracarboxylic acid, or the structural unit derived from diamine is alicyclic from the viewpoint of enhancing the transparency of the polyimide and making it difficult to cause coloring
- a structural unit derived from a diamine is included, and from the viewpoint of enhancing transparency and making coloring less likely to occur, the structural unit derived from a diamine preferably includes at least a structural unit derived from an alicyclic diamine. That is, the polyimide preferably contains an imide unit represented by the general formula (1).
- R 1 in the general formula (1) is a group derived from an alicyclic diamine.
- alicyclic diamines include cyclobutanediamine, cyclohexyldiamine (including 1,4-cyclohexyldiamine), bis (aminomethyl) cyclohexane (including 1,4-bis (aminomethyl) cyclohexane), diaminobicycloheptane, Diaminomethyl bicycloheptane (including norbornane diamines such as norbornane diamine), diaminooxy bicycloheptane, diaminomethyl oxy bicycloheptane (including oxa norbornane diamine), isophorone diamine, diaminotricyclodecane, diaminomethyl tricyclodecane, bis ( Aminocyclohexyl) methane [or methylene bis (cyclohexylamine)], and bis (aminocyclohexyl) is
- 1,4-bis (aminomethyl) cyclohexane, 1,4-cyclohexyldiamine, and norbornane diamine are preferable from the viewpoint of easily increasing the transparency of the film containing the polyimide and causing less coloration.
- the structural unit (X) derived from 1,4-bis (aminomethyl) cyclohexane can adopt any of the following two geometric isomers (cis / trans).
- the structural unit derived from trans is represented by formula (X1)
- the structural unit derived from cis is represented by formula (X2).
- the ratio (X2 / X1) of the cis form (X2) to the trans form (X1) of the structural unit derived from 1,4-bis (aminomethyl) cyclohexane is 40/60 to 0 in view of increasing the glass transition temperature of the polyimide. It is preferably / 100 (molar ratio), and more preferably 20/80 to 0/100 (molar ratio).
- the trans form (X1) + the cis form (X2) 100 mol%.
- the glass transition temperature of the polyimide is adjusted, for example, by the ratio of the cis form (X2) to the trans form (X1) (X2 / X1), the structure of the structural unit derived from diamine, and the structure of the structural unit derived from tetracarboxylic acid dianhydride sell.
- the proportion of trans isomer (X1) may be increased, the content ratio of structural units derived from alicyclic diamine may be increased, or an aromatic skeleton may be used.
- the content ratio of structural units derived from tetracarboxylic acid dianhydride having a typical structure may be increased.
- the structural unit (Y) derived from 1,4-cyclohexyldiamine can take any of the following two geometric isomers (cis / trans).
- the structural unit derived from the trans form is represented by formula (Y1)
- the structural unit derived from the cis form is represented by formula (Y2).
- the ratio (Y2 / Y1) of the cis form (Y2) to the trans form (Y1) of the structural unit derived from 1,4-cyclohexyldiamine is 50/50 to 0/100 (molar) in that the glass transition temperature of the polyimide is increased.
- the ratio is 30/70 to 0/100 (molar ratio).
- the structural unit derived from an alicyclic diamine may be contained by only one kind, or two or more kinds may be contained.
- the content ratio of structural units derived from alicyclic diamines is preferably 70 mol% or more based on 100 mol% in total of structural units derived from diamines in terms of enhancing the heat resistance and colorless transparency of the obtained film. More preferably, it is 80 mol% or more, and it may be 100 mol%.
- the structural unit derived from the diamine which comprises a polyimide may further contain the structural unit derived from other diamine other than an alicyclic diamine.
- the first to third of the other diamines correspond to aromatic diamines, and the fourth to sixth correspond to aliphatic diamines.
- the first example of other diamines in structural units derived from other diamines is a diamine having a benzene ring.
- diamines having a benzene ring are ⁇ 1> p-phenylenediamine, m-phenylenediamine, p-xylylene diamine, diamine having one benzene ring such as m-xylylene diamine; ⁇ 2> 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′- Diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-dia
- a second example of other diamines is 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino- Included are diamines having aromatic substituents such as 4-phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone and the like.
- diamines include 6,6'-bis (3-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis Included are diamines having a spirobiindane ring such as (4-aminophenoxy) -3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane.
- diamines include 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, ⁇ , ⁇ -bis (3) Included are siloxane diamines such as -aminopropyl) polydimethylsiloxane, ⁇ , ⁇ -bis (3-aminobutyl) polydimethylsiloxane and the like.
- diamines include bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [2 -(2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3- Included are ethylene glycol diamines such as aminopropyl) ether and triethylene glycol bis (3-aminopropyl) ether.
- diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,1 Included are alkylene diamines such as 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like.
- R 2 in the general formula (1) is a group derived from tetracarboxylic acid dianhydride.
- the tetracarboxylic acid dianhydride is not particularly limited, and examples thereof include aromatic tetracarboxylic acid dianhydride and alicyclic tetracarboxylic acid dianhydride.
- aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetra Carboxylic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride , Bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl)- 1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4
- cycloaliphatic tetracarboxylic acid dianhydride examples include cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid Acid dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5, 6-tetracarboxylic acid dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, bicyclo [2] 2.2.1] Heptane-2,3,5-tricarboxylic acid-6-acetic acid dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,
- tetracarboxylic acid dianhydride contains an aromatic ring such as a benzene ring
- some or all of the hydrogen atoms on the aromatic ring are selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group and a trifluoromethoxy group It may be substituted by a selected group.
- tetracarboxylic acid dianhydride is selected from ethynyl group, benzocyclobutene-4'-yl group, vinyl group, allyl group, cyano group, isocyanate group, nitrilo group, and isopropenyl group according to the purpose.
- the tetracarboxylic acid dianhydride may further have a group serving as a crosslinking point such as vinylene group, vinylidene group, and ethynylidene group in the main chain skeleton as long as the molding processability is not impaired.
- the tetracarboxylic acid dianhydride is preferably an aromatic tetracarboxylic acid dianhydride from the viewpoint that the glass transition temperature of the polyimide can be easily raised from the viewpoint that the heat resistance is hardly impaired; From the viewpoint of being easy to increase, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and bis (3,4-dicarboxyphenyl) ether dianhydride are more preferable.
- the structural unit derived from aromatic tetracarboxylic acid dianhydride may be contained alone or in combination of two or more.
- the structural unit derived from tetracarboxylic acid dianhydride constituting the polyimide may further include structural units derived from other tetracarboxylic acid dianhydride other than the above-mentioned aromatic tetracarboxylic acid dianhydride.
- the content ratio of structural units derived from aromatic tetracarboxylic acid dianhydride is 70 mol% or more with respect to the total 100 mol% of structural units derived from tetracarboxylic acid dianhydride in terms of enhancing the heat resistance of the obtained film Is preferably 80 mol% or more, and may be 100 mol%.
- the polyimide having an imide unit represented by the general formula (1) may be a homopolymer of one kind of imide unit, or a random copolymer or block copolymer of two or more kinds of imide units. May be
- the block copolymer is not particularly limited, but, for convenience of the polymerization method, a multiblock in which a plurality of blocks are linked in one polymer molecule is usually used, as in ABABAA. It can be a body.
- Examples of the polyimide having an imide unit represented by the general formula (1) include those represented by the following formulas (1A) to (1F).
- N in the formulas (1A) to (1E) is the number of repetitions, and is an integer of 2 or more.
- Ratio in R 1 and R 2, R 1 of formula (1E) of the formula (1C) shows a molar ratio.
- a film comprising a block polyimide having an average value of m and an average value of n in the above range may have good transparency and folding resistance.
- the average value of m means "the total number of structural units represented by the formula (1F-1) contained in the polyimide” or “the total number of blocks composed of structural units represented by the formula (1F-1) It is the value divided by ".
- the average value of n means "the total number of structural units represented by the formula (1F-2) contained in the polyimide” or “the total number of blocks composed of structural units represented by the formula (1F-2) It is the value divided by ".
- the ratio of the number of repetitions m of the structural unit represented by the formula (1F-1) is a predetermined value or more, the thermal expansion coefficient of the polyimide decreases. Moreover, the visible light transmittance
- 1,4-cyclohexyldiamine is generally expensive, cost reduction can be achieved by reducing the ratio of the number m of repeating structural units represented by Formula (1F-1).
- the content of the heat resistant resin (preferably polyimide) is preferably 70 to 100% by mass with respect to the total mass of the medical film.
- the content of the polyimide is 70% by mass or more, the heat resistance and the transparency of the medical film can be easily enhanced.
- the content of the polyimide is more preferably 80 to 100% by mass with respect to the total mass of the medical film.
- the medical film may further contain other components as needed.
- other components include wear resistance improvers such as graphite, graphene, carbon nanotube, carborundum, molybdenum disulfide, fluorine resin and the like, clay, mica, kaolin and the like, as long as the physical properties described above are not impaired.
- tracking improvers such as asbestos, silica and graphite, acid resistance improvers such as silica and calcium metasilicate, thermal conductivity improvers such as iron powder, zinc powder and aluminum powder, other glass beads, Additives such as glass spheres, glass fibers, talc, diatomaceous earth, alumina, hydrated alumina, titania, shirasu balloon, fluorescence quenching agent and the like are included.
- the medical film may be a single layer film or a laminated film.
- the number of layers constituting the laminated film is not particularly limited, and is 2 or more. Two or more layers constituting the laminated film may have different compositions or physical properties as long as the effects of the present invention are not impaired. Further, when the laminated film is viewed in plan, the laminated portion may be the entire surface of the film or may be only a part.
- the medical film of the present invention when used as a bag-like substrate, it not only has high heat resistance but also has further properties (eg heat sealability) that can be sealed without using an adhesive. desired.
- the medical film is a laminated film of two or more layers having different glass transition temperatures; for example, a layer including a heat resistant resin having a relatively high glass transition temperature (high Tg layer) and a glass transition temperature It can be set as the laminated film of the layer (low Tg layer) containing relatively low heat resistant resin.
- the low Tg layer may be provided only on the portion requiring sealing on the high Tg layer.
- the heat resistant resin contained in the low Tg layer and the heat resistant resin contained in the high Tg layer may be heat resistant resins having a glass transition temperature of 190 ° C. or higher at least on one side, and they are the same kind of resin. Although it may be a different kind of resin, it is preferably the above-mentioned polyimide from the viewpoint of securing the formability and interlayer adhesion of the laminated film.
- the content ratio of the aliphatic diamine-derived structural unit of the polyimide contained in the low Tg layer is more preferably higher than the content ratio of the aliphatic diamine-derived structural unit of the polyimide contained in the high Tg layer.
- the polyimide contained in the low Tg layer preferably contains a structural unit derived from an alicyclic diamine and a structural unit derived from an aliphatic diamine.
- Tg tends to be low.
- the Tg of the heat resistant resin constituting the low Tg layer is preferably 190 to 240 ° C .; the Tg of the heat resistant resin constituting the high Tg layer is preferably 250 to 300 ° C.
- the difference in Tg between the heat-resistant resin forming the low Tg layer and the heat-resistant resin forming the high Tg layer may be, for example, 30 to 110.degree.
- the ratio is 0.02 or more, the heat sealability tends to increase as long as the heat resistance is not impaired; when the ratio is 2 or less, the heat resistance can be enhanced as long as the heat sealability is not impaired.
- the thickness of the low Tg layer means the sum of the thicknesses of the plurality of low Tg layers; the thickness of the high Tg layer is the thickness of the plurality of high Tg layers Means the sum of
- the difference in CTE between one adjacent layer and the other layer of the two or more layers constituting the laminated film is preferably small.
- the difference in CTE between one layer and the other layer is preferably 40 ppm / K or less.
- the heat ray expansion coefficient (CTE) of the medical film can be measured by the following method. That is, the medical film is cut into a predetermined size to obtain a test piece. The elongation of the obtained test piece is measured using TMA-50 manufactured by Shimadzu Corporation; CTE is calculated from the slope of the temperature-elongation curve in the range of 100 to 200 ° C.
- Examples of the layer configuration of such a laminated film include the following. High Tg Layer / Low Tg Layer Low Tg Layer / High Tg Layer / Low Tg Layer Low Tg Layer / Medium Tg Layer / High Tg Layer / Medium Tg Layer / Low Tg Layer / Low Tg Layer
- FIG. 1 is a view showing an example of the medical film of the present invention.
- the medical film 10 includes a high Tg layer 11A and a low Tg layer 11B.
- the high Tg layer 11A can be, for example, a layer including a polyimide in which a structural unit derived from a diamine consists only of a structural unit derived from an alicyclic diamine.
- the low Tg layer 11B can be, for example, a layer including a polyimide in which structural units derived from diamines include structural units derived from alicyclic diamines and structural units derived from aliphatic diamines.
- the medical film 10 may be used such that the low Tg layer 11B is a sealing surface.
- the medical film which has such a structure can be sealed by heat lamination by using the low Tg layer 1B, for example so that it may become an inner surface of a bag.
- the total light transmittance of the medical film of the present invention at a thickness of 10 ⁇ m is preferably 80% or more.
- the total light transmittance of the medical film at a thickness of 10 ⁇ m is more preferably 85% or more.
- the haze of the medical film is preferably 2% or less, more preferably 1% or less. When the haze of the medical film is 2% or less, good transparency is easily obtained.
- the total light transmittance and the haze of the medical film can be measured by the following procedure. That is, the total light transmittance at the actual film thickness of the medical film is measured according to JIS-K7136 using a Haze Meter NDH 2000 type manufactured by Nippon Denshoku Kogyo. Then, the total light transmittance converted into a thickness of 10 ⁇ m is obtained from Lambert's law. On the other hand, for haze, a medical film is sliced to a thickness of 10 ⁇ m to obtain a sample piece. The haze of the obtained test piece is measured according to JIS-K7136 using Haze Meter NDH 2000 type manufactured by Nippon Denshoku Kogyo.
- the total light transmittance and the haze of the medical film can be adjusted by the polyimide composition (type and ratio of constituent units) and film forming conditions.
- the polyimide composition type and ratio of constituent units
- film forming conditions for example, in order to increase the total light transmittance of the medical film and lower the haze (increase the transparency), for example, the content ratio of the alicyclic diamine derived structural unit in the diamine derived structural unit constituting the polyimide Among them, it is preferable to select H-XDA and NBDA among alicyclic diamines.
- the oxygen concentration in the environmental atmosphere at the time of imidization is reduced to 5% or less (preferably 0.1% or less), the maximum temperature reached at the time of imidization is increased, or glass transition of polyimide It is preferable to lower the temperature) and the average heating rate.
- the light transmittance at a wavelength of 450 nm can be measured by the following method. That is, the light transmittance at a wavelength of 450 nm at the actual film thickness of the medical film is measured using an ultraviolet-visible spectrophotometer (for example, MultiSpec-1500 (manufactured by Shimadzu Corporation)). Then, from the Lambert's law, the light transmittance at 450 nm, which is converted to a thickness of 10 ⁇ m, is determined.
- an ultraviolet-visible spectrophotometer for example, MultiSpec-1500 (manufactured by Shimadzu Corporation)
- the b * value of the medical film of the present invention measured in the L * a * b * color system at a thickness of 10 ⁇ m is preferably 10 or less. Since the medical film whose b * value is in the above range is not colored (colorless and transparent), for example, when it is formed into a bag-like material, the color of the contents can be accurately recognized. Moreover, the medical film which is colorless and transparent can be applied to the apparatus which combined the light source and the light detector especially in measurement of biological information.
- the b * value of the medical film of the present invention measured in the L * a * b * colorimetric system at a thickness of 10 ⁇ m is 5 or less.
- the b * value of the medical film can be measured by the following method. That is, the medical film is sliced to a thickness of 10 ⁇ m to obtain a sample piece. The b * value of the obtained test piece is calibrated with a white standard plate, and then measured using a Suga Test Instruments Color Cute i-type in transmission mode, photometric method 8 ° di.
- the light transmittance and the b * value at a wavelength of 450 nm of the medical film can be adjusted by the polyimide composition (type and ratio of constituent units) and film forming conditions.
- the polyimide composition type and ratio of constituent units
- film forming conditions for example, in order to increase the light transmittance at a wavelength of 450 nm of the medical film and decrease the b * value (make it colorless and transparent), for example, alicyclic diamine in the structural unit derived from diamine constituting polyimide is used. It is preferable to increase the content ratio of structural units; to select H-XDA or NBDA among alicyclic diamines; to select PMDA or BPDA from tetracarboxylic acid dianhydrides, and the like.
- the oxygen concentration in the environmental atmosphere at the time of imidization is lowered to 5% or less (preferably 0.1% or less, more preferably 0.01% or less), or the maximum reaching temperature at the time of imidization It is preferable to increase the average heating rate or slow the average heating rate.
- the coefficient of thermal expansion (CTE) of the medical film of the present invention is preferably 5 to 60 ppm / K. If the coefficient of thermal expansion (CTE) of the medical film is 60 ppm / K or less, the coefficient of thermal expansion is not too large, which may cause peeling from adjacent layers or peeling from an adherend, for example, in a laminated film. Few. In addition, in order not to impair the adhesion between the medical film and a member (member to be adhered) to which the film is adhered at the time of use, the difference in thermal expansion coefficient (CTE) of the member to be adhered is small. preferable.
- the heat ray expansion coefficient (CTE) of the medical film can be measured by the following method. That is, the medical film is sliced to a thickness of 10 ⁇ m to obtain a sample piece. The elongation of the obtained test piece is measured using TMA-50 manufactured by Shimadzu Corporation; CTE is calculated from the slope of the temperature-elongation curve in the range of 100 to 200 ° C.
- the tensile strength of the medical film of the present invention is preferably 80 to 400 MPa. When the tensile strength is 80 MPa or more, sufficient mechanical strength can be easily obtained. The tensile strength of the medical film of the present invention is more preferably 100 to 350 MPa.
- the tensile strength of the medical film can be measured by a tensile test.
- the test pieces used and the measurement conditions are the same as in the examples described later.
- the CTE and tensile strength of the medical film can be adjusted by the polyimide composition (type and ratio of constituent units) and film forming conditions.
- the polyimide composition type and ratio of constituent units
- film forming conditions for example, an acid dianhydride having an aromatic skeleton is used, a diamine having a rigid and symmetrical structure, or / and an acid dianhydride
- a polyimide containing a structural unit derived from; as a film forming condition for example, to lower an average temperature rising rate at the time of imidization.
- the number of times of folding in the MIT folding endurance test of the medical film of the present invention is 1,000 or more.
- the number of folding times of the medical film is 1,000 or more, the flexibility of the medical film is sufficient, so that problems such as cutting of the film during actual use hardly occur.
- the number of times of folding in the MIT folding resistance test of the medical film is more preferably 3,000 or more, and still more preferably 10,000 or more.
- the number of folds of the medical film can be measured by the MIT fold resistance test.
- the test pieces used and the measurement conditions are the same as in the examples described later.
- the bending resistance of the medical film can be adjusted by the polyimide composition (type and ratio of the structural unit) and the film forming conditions.
- a structural unit derived from an acid dianhydride having an aromatic ring or a structural unit derived from a diamine and / or an acid dianhydride having a symmetrical structure for example, a structural unit derived from an acid dianhydride having an aromatic ring or a structural unit derived from a diamine and / or an acid dianhydride having a symmetrical structure, and It is preferable to contain a structural unit having a relatively flexible structure (eg, a structural unit derived from an alicyclic diamine such as H-XDA, a structural unit derived from an aliphatic diamine, etc.).
- film forming conditions for example, it is preferable to lower the average temperature rising rate at the time of imidization.
- the medical film of the present invention includes ketones such as acetone, alcohols such as methanol and ethanol, phenols such as cresol, dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc) ), Chloroform and the like, and in particular, it can have good solvent resistance to alcohols such as methanol and ethanol.
- the weight loss before and after immersion when the film is immersed at room temperature (22 ° C.) for 24 hours is preferably 5% by mass or less of the film before immersion, and is 3% by mass or less Is more preferable, and 0 mass% (without dissolution) is more preferable.
- the solvent resistance of the medical film can be adjusted by the polyimide composition (type and ratio of constituent units).
- 1,4-bis (aminomethyl) cyclohexane, trans-1,4-cyclohexyldiamine, or norbornane diamine is selected as an alicyclic diamine, and tetracarboxylic acid is selected.
- Selecting pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, or bis (3,4-dicarboxyphenyl) ether dianhydride as the acid dianhydride Is preferred.
- the thickness of the medical film varies depending on the application of the medical film, but is preferably 0.5 to 200 ⁇ m. When the thickness of the medical film is 0.5 ⁇ m or more, sufficient mechanical strength can be easily secured, and when it is 200 ⁇ m or less, the transparency and the flexibility are hardly impaired.
- the thickness of the medical film is more preferably 1 to 100 ⁇ m.
- the medical film of the present invention has high heat resistance and transparency as described above. Therefore, it is preferably used as a substrate of various medical devices that require such heat resistance and transparency.
- medical devices include bags such as infusion bags, covers (packaging materials) such as catheters, medical containers such as culture dishes and culture containers, medical devices (diagnostic / examination / treatment devices) and medical treatment.
- the components of the wearable device are included.
- a coating layer having a predetermined function may be further laminated on the surface of the medical film of the present invention to form a medical laminate.
- a medical laminate can also be preferably used as a substrate of a medical device, as described above.
- the surface coating layer in the medical laminate examples include a hydrophilicity enhancement coating layer, a bioreactive stealth coating layer, a hardness enhancement coating layer, a water vapor permeation barrier coating layer, an oxygen permeation barrier coating and the like.
- the thickness of the surface coating layer is preferably very thin (for example, 20% or less of the thickness of the medical film) with respect to the thickness of the medical film.
- the medical film of the present invention is, for example, 1) a step of obtaining a precursor solution (polyamic acid composition) of the above-mentioned polyimide, 2) after applying the polyamic acid composition on a support, It can be obtained through the steps of drying and heat curing (imidization), and 3) peeling the cured product of the polyamic acid composition from the support to obtain a medical film made of a polyimide film.
- the polyamic-acid composition containing a polyamic acid is prepared.
- the polyamic acid contained in the polyamic acid composition has an amic acid unit represented by the general formula (2).
- R 1 and R 2 in general formula (2) is R 1 and R 2 in the general formula (1) respectively the same.
- the polyamic acid may further contain other polyamic acid units other than the amic acid unit represented by General Formula (2).
- Other amic acid units may be similar to other imide units contained in the polyimide except that the imide skeleton is changed to an amic acid skeleton.
- Examples of the polyamic acid containing an amic acid unit represented by the general formula (2) include the following formulas (2A) to (2F).
- N in the formulas (2A) to (2E) has the same meaning as n in the formulas (1A) to (1E).
- Ratio in R 1 and R 2, R 1 of formula (2E) of the formula (2C) indicates the molar ratio.
- the average value of m, the average value of n, R, R ′ and R ′ ′ in formula (2F) are the average value of m in formula (1F), the average value of n, R, R ′ and R ′ ′, respectively. It is synonymous.
- the block polyamic acid imide represented by the formula (2F) is, for example, a diamine-terminated amic acid oligomer composed of a structural unit represented by the following formula (2F′-1), and a compound of the formula (2F′-2) It can be obtained by imidization after reaction in a solvent with a tetracarboxylic acid dianhydride-terminated imide oligomer composed of the structural units represented.
- the polyamic acid composition may further contain a solvent, as required.
- aprotic polar solvents include N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphoraamide, etc .; ether compounds; Methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol Glycol, triethylene glycol monoethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dip Examples thereof include glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropy
- water-soluble alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, tert-butyl alcohol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol , 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-butene-1,4-diol, 2-methyl-2,4-pentanediol, 1,2,6-hexane It contains triol, diacetone alcohol and the like.
- solvents can be used alone or in combination of two or more.
- preferred examples of the solvent include N, N-dimethylacetamide, N-methylpyrrolidone or a combination thereof.
- the concentration of the polyamic acid is not particularly limited, but can be, for example, 15% by mass or more based on the total mass of the polyamic acid composition in terms of facilitating the removal of the solvent by drying; In terms of point, for example, it can be 50% by mass or less based on the total mass of the polyamic acid composition.
- the intrinsic logarithmic viscosity at 35 ° C. of the polyamic acid composition (concentration 0.5 g / dl) when N-methyl-2-pyrrolidone is a solvent is preferably 0.1 to 3.0 dl / g. . It is because application of a polyamic-acid composition becomes easy.
- the polyamic acid composition can be obtained, for example, by polymerizing the aforementioned alicyclic diamine and tetracarboxylic acid dianhydride in an aprotic polar solvent or a water-soluble alcohol solvent.
- a container equipped with a stirrer and a nitrogen introduction pipe is prepared.
- the above-mentioned solvent is placed in a nitrogen-substituted container, and a diamine is added so that the solid content concentration of the polyimide becomes 30% by weight, and the temperature is adjusted to stir and dissolve.
- a tetracarboxylic acid dianhydride is added to this solution so that the molar ratio is about 1, for example, 0.95 to 1.05 with respect to the diamine compound, and the temperature is adjusted and stirring is performed for about 1 to 50 hours.
- a polyamide acid composition can be obtained.
- Step 2) After the above-described polyamic acid composition is applied onto a support, it is heated and dried (imidized) under an inert gas atmosphere to obtain the above-mentioned polyimide film.
- a conventional heating and drying furnace can be used.
- the atmosphere of the drying furnace air, inert gas (nitrogen, argon) or the like can be used, but an inert gas atmosphere having an oxygen concentration of 5% or less is preferable.
- the oxygen concentration in the environmental atmosphere of the inert gas is more preferably 0.1% or less.
- the average heating rate during heating and drying of the coating is in the range of 50 to 300 ° C., for example, 0.25 to 50 ° C./minute, preferably 1 to 10 ° C./minute, more preferably 2 to 5 ° C./minute It can be.
- the heating rate may be constant or may be changed in two or more stages. When changing to two or more steps, it is preferable to set each heating rate to 0.25 to 50 ° C./minute. Not only the obtained film is difficult to be colored and the total light transmittance is not easily reduced, but also the tensile strength and the folding resistance are easily increased.
- the temperature rise may be continuous or stepwise (sequential), it is preferable to set it continuous because it can suppress the appearance defect of the obtained film and whitening accompanying the imidization reaction.
- the coating film does not necessarily have to be heated to 300.degree.
- the temperature rise finish temperature is less than 300 ° C., it is preferable to set the average temperature rise rate in the range from 150 ° C. to the temperature rise finish temperature to 0.25 to 50 ° C./minute.
- the temperature rise finish (maximum reached) temperature is usually (Tg ⁇ 75) ° C., more preferably (Tg ⁇ 10) ° C., where Tg is a higher temperature, specifically the glass transition temperature of the selected resin. More preferably, when the temperature is (Tg + 10) ° C. or higher, the residual solvent contained in the coating film can be easily removed. In addition, the resulting film is difficult to color, and the total light transmittance is unlikely to be reduced.
- the heating end temperature (maximum temperature) is, for example, preferably 200 to 300 ° C., more preferably 250 to 290 ° C., and still more preferably 270 to 290 ° C.
- the heating time after the end of the heating can be, for example, about 1 second to 10 hours.
- the total light transmittance and b * value of the obtained medical film can be adjusted by the oxygen concentration in the environmental atmosphere at the time of imidization, the average temperature rising rate and the final temperature reached. For example, to increase the total light transmittance of the resulting medical film and lower the b * value, for example, after applying the polyamic acid composition to a substrate, the oxygen concentration in the environmental atmosphere at the time of imidization is lowered. (Preferably having an oxygen concentration of 5% or less, more preferably 0.1% or less, still more preferably 0.01% or less); it is preferable to increase the final temperature reached; to lower the average temperature increase rate.
- the means for applying the polyamic acid composition is not particularly limited.
- known means such as spin coater, slit coater, die coater, comma coater, roll coater, gravure coater, curtain coater, spray coater and lip coater can be used.
- the other layer may be coated and formed on one polyimide film obtained as described above, and then it may be obtained by imidization; one layer and the other layer And may be obtained by imidization after co-casting.
- Step 3 Thereafter, the cured product can be peeled off from the support to obtain a polyimide film (medical film).
- the polyamic acid composition used in the step 1) of the method for producing a medical film can be preferably used as a medical coating composition because the cured product has high heat resistance and transparency.
- the medical coating composition can be used as a transparent coating material of a medical member.
- medical members include scalpels, scissors, forceps, forceps, needles, etc., medical fibers / optical fibers, optical sensors etc.
- the medical device of the present invention comprises a cured product of a medical film or a medical coating composition.
- the medical film is as described in 1. above.
- Medical film and the medical coating composition are the same as those described in 3. above. It may be a medical coating composition.
- the medical device according to the first embodiment of the present invention includes a medical film.
- medical devices include various bags such as infusion bags; various covers (packaging materials) such as catheters; medical containers such as culture dishes and culture containers; medical equipment (diagnostic / inspection / treatment equipment) And components of a medical wearable device.
- the medical device and the medical wearable device include a biosignal detection sensor, an electroencephalogram sensor, a device in which a pressure sensor is integrated in a medical catheter, and an artificial skin provided with a pressure / temperature sensor.
- components of medical devices and medical wearable devices include a member having a structure in which a protective layer, an organic transistor (OTFT) layer and a substrate (medical film) are laminated in this order.
- OTFT organic transistor
- the pouch may be a pouch having at least one opening.
- the bag-like material in the present invention is not limited to a bag-like material having one opening, but includes partially sealed materials such as a cylindrical material having two openings.
- Such a bag-like product is 1-1) bending one medical film or laminating two or more medical films to obtain a laminate; 1-2) medical film of the laminate Manufacturing at least a part of the overlapping portion of the bag to obtain a bag-like medical device.
- the sealing in the step 1-2) may be performed via an adhesive or may be performed by thermocompression bonding.
- the medical film is a laminated film including the low Tg layer described above, it can be well sealed by thermocompression bonding.
- the medical device according to the second embodiment of the present invention includes a medical member and a coating layer made of a cured product of the medical coating composition.
- Examples of medical members include scalpels, scissors, forceps, forceps, needles and the like; medical fibers, optical fibers, optical sensors and the like.
- the coating layer is a layer comprising a cured product of a medical coating composition.
- the covering layer may cover at least a part of the surface of the medical member.
- the thickness of the covering layer may be, for example, about 0.1 to 50 ⁇ m although it varies depending on the type and purpose of the medical member.
- Such a medical device comprises the steps of: 2-1) coating the surface of a medical member with a medical coating composition; 2-2) heating a coating of the medical coating composition under an inert gas atmosphere
- the method is manufactured through the process of obtaining a medical device in which the surface of the medical member is coated with the cured product of the medical coating composition.
- the coating means in the step 2-1) is not particularly limited, and may be, for example, a spray coating method or a dip coating method.
- the imidation conditions (imidation temperature, average temperature rising rate, oxygen concentration, etc.) in the step 2-2) depend on the type and material of the medical member, but the above-mentioned 2.
- the imidation conditions (imidation temperature, average temperature rising rate, oxygen concentration, etc.) in the step 2) of the method for producing a medical film may be the same.
- H-XDA 1,4-bis (aminomethyl) cyclohexane (trans 85 mol%, cis 15 mol%)
- NBDA norbornane diamine
- CHDA trans-1,4-cyclohexyldiamine
- HMDA 1,6-hexamethylenediamine
- ODA 4,4'-diaminodiphenyl ether [4,4'-oxydianiline]
- APB 1,3-bis (3-aminophenoxy) benzene
- NMP N-methylpyrrolidone
- DMAc N, N-dimethylacetamide
- DMI 1,3-dimethyl-2-imidazolidinone
- composition example 2 153 g (0.700 mol) of PMDA and 420 g of solvent DMAc are added to a 1.5 L 5-neck separable flask (reaction vessel) equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a dropping funnel, and the reaction vessel is heated to 0 ° C. The mixture was stirred in an ice bath to form a slurry liquid. A solution containing 108 g (0.700 mol) of NBDA and 189 g of DMAc charged into the dropping funnel was dropped into the slurry liquid over 2 hours. After the addition was completed, the ice bath was removed, and the mixture was further stirred at room temperature for 18 hours to obtain a polyamic acid solution (varnish).
- composition example 3 In a 300 mL 5-neck separable flask (reaction vessel) equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 11.4 g (0.100 mol) of CHDA, 25.9 g (0.0880 mol) of BPDA, and 149 g of a solvent NMP at room temperature Added. The reaction vessel was bathed in an oil bath maintained at 90 ° C. for 1 hour. The salt was formed after about 10 minutes on the way, but dissolved rapidly and became a homogeneous solution. After removing the oil bath, the mixture was further stirred at room temperature for 18 hours to obtain an oligoamic acid solution (varnish) having an amino group derived from CHDA at its end.
- oligoamic acid solution varnish
- composition example 5 A polyamic acid solution (varnish) was obtained in the same manner as in Synthesis Example 1 except that H-XDA (0.250 mol) used in Synthesis Example 1 was changed to 28.5 g (0.250 mol) of CHDA.
- Synthesis Example 6 A polyamide acid solution (varnish) is obtained in the same manner as in Synthesis Example 2 except that 153 g (0.700 mol) of PMDA and 420 g of solvent DMAc used in Synthesis Example 2 are changed to 217 g (0.700 mol) of ODPA and 786 g of solvent DMAc.
- Synthesis Example 7 PMDA (0.700 mol) used in Synthesis Example 2 and 420 g of solvent DMAc were changed to 217 g (0.700 mol) of ODPA and 750 g of solvent NMP, respectively, and 108 g (0.700 mol) of NBDA used in Synthesis Example 2 and 189 g of solvent DMAc
- a polyamic acid solution (varnish) was obtained in the same manner as in Synthesis Example 2 except that 79.5 g (0.560 mol) of H-XDA, 16.2 g (0.140 mol) of HMDA and 189 g of a solvent were changed.
- Synthesis Example 8 Add 50.0 g (0.250 mol) of ODA and 591 g of NMP to a 1.5 L 5-neck separable flask (reaction vessel) equipped with a thermometer, a stirrer, and a nitrogen inlet tube to make a uniform solution, and make the reaction vessel 0 Stir in an ice bath.
- the homogeneous solution was charged with 54.3 g (0.249 mol) of PMDA as a powder and stirred in an ice bath for 3 hours.
- the slurry changed to a homogeneous solution while thickening. After removing the ice bath, the mixture was further stirred at room temperature for 18 hours to obtain a homogeneous polyamic acid solution (varnish).
- Synthesis Example 9 153 g (0.700 mol) of PMDA and 420 g of solvent DMAc are changed to 186 g (0.600 mol) of ODPA and 643 g of solvent NMP respectively, and 108 g (0.700 mol) of NBDA and 189 g of solvent DMAc are 59.7 g (0.420 mol) of H-XDA A polyamic acid solution (varnish) was obtained in the same manner as in Synthesis Example 2 except that HMDA was changed to 20.8 g (0.180 mol) and solvent NMP was 162 g.
- Synthesis Example 10 153 g (0.700 mol) of PMDA and 420 g of solvent DMAc were changed to 267 g (0.600 mol) of 6FDA and 643 g of solvent NMP, respectively, and 108 g (0.700 mol) of NBDA and 189 g of solvent DMAc were mixed with 42.6 g (0.300 mol of H-XDA) A polyamic acid solution (varnish) was obtained in the same manner as in Synthesis Example 2 except that CHDA was changed to 34.2 g (0.300 mol) and solvent NMP was changed to 162 g.
- Synthesis Example 11 A polyamic acid solution (varnish) was obtained in the same manner as in Synthesis Example 2 except that 153 g (0.700 mol) of PMDA was changed to 311 g (0.700 mol) of 6FDA.
- Synthesis Example 12 Change 153 g (0.700 mol) of PMDA and 420 g of solvent DMAc into 112 g (0.500 mol) of 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride (H-PMDA) and 590 g of DMAc, respectively, and Polyamide acid in the same manner as in Synthesis Example 2 except that 0.700 mol) and 189 g of solvent DMAc were changed to 146 g (0.500 mol) of 1,3-bis (3-aminophenoxy) benzene (APB) and 184 g of solvent DMAc. A solution (varnish) was obtained.
- H-PMDA 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride
- APIB 1,3-bis (3-aminophenoxy) benzene
- the inherent logarithmic viscosity of the varnish obtained in Synthesis Example 1 to 12 was measured by the following method.
- the hue of the films obtained in Examples 1 to 11 and Comparative Examples 1 to 6 and the appearance after sterilization were evaluated by visual observation.
- the sterilization treatment method and the appearance after the sterilization treatment were evaluated by the following methods.
- the film of Comparative Example 1 is not seen to change in appearance (discoloration or the like) or deformation after sterilization, and is transparent, but is colored yellow. Further, it is understood that although the films (or sheets) of Comparative Examples 2 to 6 are all colorless and transparent, appearance change (such as discoloration) and deformation after sterilization are observed.
- evaluations 1) to 7) were performed for the films of the respective examples.
- the evaluations 1) to 6) were performed on all the untreated, autoclaved and dry heat sterilized films; the evaluation of 7) was performed only on the untreated films.
- the film of Comparative Example 1 was good without any change before and after the above-mentioned sterilization treatment, but since the hue was pale yellow, the evaluations 1) to 7) were not performed.
- Light transmittance @ 450 nm (unit:%) The UV-visible spectrum of the above film was measured using MultiSpec-1500 (manufactured by Shimadzu Corporation). The light transmittance at a wavelength of 450 nm was measured at this time. The light transmittance @ 450 nm converted to a thickness of 10 ⁇ m was determined from the light transmittance at a wavelength of 450 nm (light transmittance at an actual thickness) according to Lambert's law.
- MIT-type bending tester (type 307) manufactured by Yasuda Seiki Seisakusho Co., Ltd., radius of curvature 0.38 mm, load 0.5 Kg, bending accuracy 270 degrees (right and left 135 degrees), bending speed 175 times / The number of times to break under the condition of minutes was measured.
- the test piece For the bending resistance, one end of the test piece is fixed to the above test piece using the MIT bending resistance test (type 307, manufactured by Yasuda Seiki Seisakusho), and then the other end is gripped to reciprocate the test piece, The number of times of bending until the test piece breaks is measured.
- the film of Example 7 containing a large amount of structural units derived from alicyclic diamine is found to have a higher glass transition temperature than the film of Example 8.
- the film of Example 8 has a lower b * value although the content of the structural unit derived from alicyclic diamine is smaller than that of the film of Example 7, the oxygen concentration at curing is low. It is considered to be.
- the films of Examples 1 to 11 are excellent in solvent resistance, particularly with respect to methanol and ethanol.
- a group derived from an alicyclic diamine is a group selected from the group consisting of 1,4-bis (aminomethyl) cyclohexane, trans-1,4-cyclohexyldiamine, and norbornane diamine.
- groups derived from aromatic tetracarboxylic acid dianhydride are pyromellitic acid dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic acid dianhydride, and bis (3,4-dicarboxy).
- the films of Examples 1 to 7 containing a polyimide which is a group derived from aromatic tetracarboxylic acid dianhydride selected from the group consisting of phenyl) ether dianhydrides are the films of Examples 9 to 11 containing other polyimides. It can be seen that the solvent resistance is better than that.
- Example 12 Bag made of laminated film (example of the first embodiment)
- the polyamic acid solution (varnish) prepared in Synthesis Example 6 on the polyimide film 4 (high Tg layer, thickness 21 ⁇ m, Tg: 270 ° C.) prepared above, from 50 ° C. to 280 under nitrogen stream in an inert oven.
- the temperature was raised to ° C. and held at 280 ° C. for 1 hour to form a polyimide layer (low Tg layer, 10 ⁇ m thickness, Tg: 219 ° C.) to obtain a laminated film (31 ⁇ m thickness).
- Two sheets obtained by cutting the obtained laminated film into 10 cm squares were prepared. Then, after laminating the polyimide resin layers of two laminated films, they were thermally laminated at 250 ° C., 1 hour, 10 MPa with a hand heat press machine to obtain a laminate.
- the 180 ° peel strength (peel strength) of the obtained laminate was measured at a rate of 10 mm / min using a device the same as the above tensile test, changing the jig to 1.5 kN / m. there were.
- the laminate was subjected to sterilization treatment at 121 ° C. for 20 minutes in an autoclave (under steam).
- sterilization treatment at 121 ° C. for 20 minutes in an autoclave (under steam).
- Example 13 Image Fiber Coated with Coating Layer (Example of Second Embodiment)
- a quartz-based image fiber having a diameter of 500 ⁇ m and a length of 3.5 cm used for image transmission was immersed in the varnish (polyamic acid solution) obtained in Synthesis Example 4, then pulled out from the solution at a speed of 3 cm / min and dip-coated .
- the dip-coated fiber is heated from 50 ° C. to 280 ° C. over 1.5 hours in an oven under a nitrogen stream, and then maintained at 280 ° C. for 1 hour to remove the solvent and thermal imidization.
- an image fiber coated with a coating layer consisting of a cured product of a 12 ⁇ m thick polyamic acid solution was obtained.
- the obtained image fiber was sterilized in an autoclave (under steam) at 121 ° C. for 20 minutes.
- no abnormality such as change in appearance, deformation, deterioration or the like of the image fiber was recognized before and after the sterilization treatment.
- the medical film which is excellent in transparency, heat resistance, and solvent resistance can be provided.
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Abstract
Description
[2] 前記医療用フィルムの、厚み10μmにおけるL*a*b*表色系におけるb*値が5以下である、[1]に記載の医療用フィルム。
[3] 前記耐熱性樹脂は、ポリイミドである、[1]又は[2]に記載の医療用フィルム。
[4] 前記ポリイミドは、下記一般式(1)で表されるイミドユニットを含む、[3]に記載の医療用フィルム。
R1は、脂環族ジアミン由来の基であり、
R2は、芳香族テトラカルボン酸二無水物由来の基である)
[5] 前記脂環族ジアミン由来の基が、1,4-ビス(アミノメチル)シクロヘキサン、トランス-1,4-シクロヘキシルジアミン、及びノルボルナンジアミンからなる群より選ばれる基であり、前記芳香族テトラカルボン酸二無水物由来の基が、ピロメリット酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物からなる群より選ばれる芳香族テトラカルボン酸二無水物由来の基である、[4]に記載の医療用フィルム。
[6] 前記医療用フィルムの厚みは、1~100μmである、[1]~[5]のいずれかに記載の医療用フィルム。
[7] 前記医療用フィルムは、ガラス転移温度が相対的に高いポリイミドを含む層と、ガラス転移温度が相対的に低いポリイミドを含む層の積層フィルムである、[1]~[6]のいずれかに記載の医療用フィルム。
[8] [1]~[7]のいずれかに記載の医療用フィルムの製造方法であって、下記一般式(2)で表されるアミド酸ユニットを含むポリアミド酸を含むポリアミド酸組成物を得る工程と、
R1は、脂環族ジアミン由来の基であり、
R2は、芳香族テトラカルボン酸二無水物由来の基である)
前記ポリアミド酸組成物を支持体上に塗布した後、酸素濃度5%以下で、平均昇温速度1~10℃/minで最高到達温度まで昇温した後、該最高到達温度でイミド化して、前記ポリアミド酸組成物の硬化物を得る工程と、
前記ポリアミド酸組成物の硬化物を前記支持体から剥離して、医療用フィルムを得る工程とを含む、医療用フィルムの製造方法。
[9] [1]~[7]のいずれかに記載の医療用フィルムを含む、医療用具。
[10] [1]~[7]のいずれかに記載の医療用フィルムを折り曲げるか、又は少なくとも2つの前記医療用フィルムを積層して積層体を得る工程と、前記積層体の少なくとも一部を熱圧着して、袋状物である医療用具を得る工程とを含む、医療用具の製造方法。
[12] 前記ポリアミド酸は、下記一般式(2)で表されるアミド酸ユニットを含む、[11]に記載の医療用コーティング組成物。
R1は、脂環族ジアミン由来の基であり、
R2は、芳香族テトラカルボン酸二無水物由来の基である)
[13] 前記脂環族ジアミン由来の基が、1,4-ビス(アミノメチル)シクロヘキサン、トランス-1,4-シクロヘキシルジアミン、及びノルボルナンジアミンからなる群より選ばれる基であり、前記芳香族テトラカルボン酸二無水物由来の基が、ピロメリット酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物からなる群より選ばれる芳香族テトラカルボン酸二無水物由来の基である、[12]に記載の医療用コーティング組成物。
[14] 溶媒をさらに含む、[11]~[13]のいずれかに記載の医療用コーティング組成物。
[15] 医療用部材と、[11]~[14]のいずれかに記載の医療用コーティング組成物の硬化物からなる被覆層とを含む、医療用具。
[16] 医療用部材の表面を、[11]~[14]のいずれかに記載の医療用コーティング組成物でコーティングする工程と、前記医療用コーティング組成物の塗膜を不活性ガス雰囲気下で加熱して、前記医療用部材と、その表面を覆う前記医療用コーティング組成物の硬化物からなる被覆層とを有する医療用具を得る工程とを含む、医療用具の製造方法。
本発明の医療用フィルムは、ガラス転移温度が190℃以上の耐熱性樹脂を含む。
(耐熱性樹脂)
医療用フィルムは、ガラス転移温度が190℃以上の耐熱性樹脂を含む。ガラス転移温度が190℃以上と高い耐熱性樹脂は、高い耐熱性を有するだけでなく、ポリマー分子間の相互作用も高くなるため、高い耐溶剤性も有すると考えられる。耐熱性樹脂は、熱可塑性樹脂であってもよい。耐熱性樹脂のガラス転移温度は、200℃以上であることが好ましく、205℃以上であることがより好ましい。
<1>p-フェニレンジアミン、m-フェニレンジアミン、p-キシリレンジアミン、m-キシリレンジアミン等のベンゼン環を1つ有するジアミン;
<2>3,3'-ジアミノジフェニルエーテル、3,4'-ジアミノジフェニルエーテル、4,4'-ジアミノジフェニルエーテル、3,3'-ジアミノジフェニルスルフィド、3,4'-ジアミノジフェニルスルフィド、4,4'-ジアミノジフェニルスルフィド、3,3'-ジアミノジフェニルスルホン、3,4'-ジアミノジフェニルスルホン、4,4'-ジアミノジフェニルスルホン、3,3'-ジアミノベンゾフェノン、4,4'-ジアミノベンゾフェノン、3,4'-ジアミノベンゾフェノン、3,3'-ジアミノジフェニルメタン、4,4'-ジアミノジフェニルメタン、3,4'-ジアミノジフェニルメタン、2,2-ジ(3-アミノフェニル)プロパン、2,2-ジ(4-アミノフェニル)プロパン、2-(3-アミノフェニル)-2-(4-アミノフェニル)プロパン、2,2-ジ(3-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ジ(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2-(3-アミノフェニル)-2-(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、1,1-ジ(3-アミノフェニル)-1-フェニルエタン、1,1-ジ(4-アミノフェニル)-1-フェニルエタン、1-(3-アミノフェニル)-1-(4-アミノフェニル)-1-フェニルエタン等のベンゼン環を2つ有するジアミン;
<3>1,3-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(3-アミノフェノキシ)ベンゼン、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノベンゾイル)ベンゼン、1,3-ビス(4-アミノベンゾイル)ベンゼン、1,4-ビス(3-アミノベンゾイル)ベンゼン、1,4-ビス(4-アミノベンゾイル)ベンゼン、1,3-ビス(3-アミノ-α,α-ジメチルベンジル)ベンゼン、1,3-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン、1,4-ビス(3-アミノ-α,α-ジメチルベンジル)ベンゼン、1,4-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン、1,3-ビス(3-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,3-ビス(4-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,4-ビス(3-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、1,4-ビス(4-アミノ-α,α-ジトリフルオロメチルベンジル)ベンゼン、2,6-ビス(3-アミノフェノキシ)ベンゾニトリル、2,6-ビス(3-アミノフェノキシ)ピリジン等のベンゼン環を3つ有するジアミン;
<4>4,4'-ビス(3-アミノフェノキシ)ビフェニル、4,4'-ビス(4-アミノフェノキシ)ビフェニル、ビス[4-(3-アミノフェノキシ)フェニル]ケトン、ビス[4-(4-アミノフェノキシ)フェニル]ケトン、ビス[4-(3-アミノフェノキシ)フェニル]スルフィド、ビス[4-(4-アミノフェノキシ)フェニル]スルフィド、ビス[4-(3-アミノフェノキシ)フェニル]スルホン、ビス[4-(4-アミノフェノキシ)フェニル]スルホン、ビス[4-(3-アミノフェノキシ)フェニル]エーテル、ビス[4-(4-アミノフェノキシ)フェニル]エーテル、2,2-ビス[4-(3-アミノフェノキシ)フェニル]プロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン、2,2-ビス[3-(3-アミノフェノキシ)フェニル]-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス[4-(4-アミノフェノキシ)フェニル]-1,1,1,3,3,3-ヘキサフルオロプロパン等のベンゼン環を4つ有するジアミン;
<5>1,3-ビス[4-(3-アミノフェノキシ)ベンゾイル]ベンゼン、1,3-ビス[4-(4-アミノフェノキシ)ベンゾイル]ベンゼン、1,4-ビス[4-(3-アミノフェノキシ)ベンゾイル]ベンゼン、1,4-ビス[4-(4-アミノフェノキシ)ベンゾイル]ベンゼン、1,3-ビス[4-(3-アミノフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,3-ビス[4-(4-アミノフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,4-ビス[4-(3-アミノフェノキシ)-α,α-ジメチルベンジル]ベンゼン、1,4-ビス[4-(4-アミノフェノキシ)-α,α-ジメチルベンジル]ベンゼン等のベンゼン環を5つ有するジアミン;
<6>4,4'-ビス[4-(4-アミノフェノキシ)ベンゾイル]ジフェニルエーテル、4,4'-ビス[4-(4-アミノ-α,α-ジメチルベンジル)フェノキシ]ベンゾフェノン、4,4'-ビス[4-(4-アミノ-α,α-ジメチルベンジル)フェノキシ]ジフェニルスルホン、4,4'-ビス[4-(4-アミノフェノキシ)フェノキシ]ジフェニルスルホン等のベンゼン環を6つ有するジアミンが含まれる。
医療用フィルムは、必要に応じて他の成分をさらに含んでいてもよい。他の成分の例には、前述の物性を損なわない範囲で、グラファイト、グラフェン、カーボンナノチューブ、カーボランダム、二硫化モリブデン、フッ素系樹脂等の耐磨耗性向上剤、クレー、マイカ、カオリン等の電気的特性向上剤、アスベスト、シリカ、グラファイト等の耐トラッキング向上剤、シリカ、メタ珪酸カルシウム等の耐酸性向上剤、鉄粉、亜鉛粉、アルミニウム粉等の熱伝導度向上剤、その他ガラスビーズ、ガラス球、ガラス繊維、タルク、珪藻土、アルミナ、水和アルミナ、チタニア、シラスバルーン、蛍光消光剤等の添加剤が含まれる。
医療用フィルムは、単層フィルムであってもよいし、積層フィルムであってもよい。積層フィルムを構成する層の数は、特に制限されず、2以上である。積層フィルムを構成する2以上の層は、本発明の効果を損なわない範囲で、互いに異なる組成又は物性を有し得る。また、積層フィルムを平面視したとき、積層部分は、フィルムの全面であってもよいし、一部だけであってもよい。
高Tg層/低Tg層
低Tg層/高Tg層/低Tg層
低Tg層/中Tg層/高Tg層/中Tg層/低Tg層
(全光線透過率)
本発明の医療用フィルムの、厚み10μmにおける全光線透過率は、80%以上であることが好ましい。全光線透過率が80%以上であると、例えば本発明の医療用フィルムを輸血バッグや各種容器に用いた際に、中身を十分に視認できる高い透明性を得ることができる。医療用フィルムの、厚み10μmにおける全光線透過率は、85%以上であることがより好ましい。
医療用フィルムのヘイズは、2%以下であることが好ましく、1%以下であることがより好ましい。医療用フィルムのヘイズが2%以下であると、良好な透明性が得られやすい。
即ち、医療用フィルムの実際のフィルム厚みでの全光線透過率を、日本電色工業製Haze Meter NDH2000型を用いて、JIS-K7136に準拠して測定する。そして、Lambertの法則から、10μmに厚み換算した全光線透過率を求める。
一方、ヘイズは、医療用フィルムを、厚みが10μmとなるようにスライスして、試料片を得る。得られた試験片のヘイズを、日本電色工業製Haze Meter NDH2000型を用いて、JIS-K7136に準拠して測定する。
さらに、医療用フィルムは、全波長領域で透過率が高いことが要求される。一方で、ポリイミドは、一般的には短波長側の光を吸収しやすい傾向があり、それにより医療用フィルムが黄色を呈する場合がある。本発明の医療用フィルムは、厚みが10μmであるとき、波長450nmでの光透過率が80%以上であることが好ましい。波長450nmでの光透過率が80%以上であると、短波長側の透過率も高いので、そのような黄色味を呈することなく、高い透明性が得られやすい。それにより、医療用フィルムを、ガラス代替用途等の透明フィルムとして使用することができる。医療用フィルムの、厚み10μmにおける波長450nmでの光透過率は、83%以上であることがより好ましく、85%よりも高いことがさらに好ましい。
芳香族ポリイミドを含むフィルムは、特に黄色に着色することが多いが、医療用フィルムとしては、より無色に近いことが好ましい。本発明の医療用フィルムの、厚み10μmにおけるL*a*b*表色系で測定されるb*値は、10以下であることが好ましい。b*値が上記範囲である医療用フィルムは着色していない(無色透明である)ので、例えば袋状物としたときに内容物の色を正確に視認することができる。また、無色透明性である医療用フィルムは、特に生体情報の計測において、光源と光検出器を組み合わせた装置に適用できる。さらに、測定対象となる試料が柔らかい場合(例えば皮膚や臓器等)、その変形に追従できるように、センサ自体も柔らかい(フレキシブル)である必要がある。これに対して、無色透明で、且つフレキシブル性を有する医療用フィルムは、柔らかい(フレキシブルな)生体情報計測センサとして好適に用いることができる。本発明の医療用フィルムの、厚み10μmにおけるL*a*b*表色系で測定されるb*値は、5以下であることがより好ましい。
本発明の医療用フィルムの熱線膨脹率(CTE)は、5~60ppm/Kであることが好ましい。医療用フィルムの熱線膨脹率(CTE)が60ppm/K以下であると、熱による膨張率が大きすぎないので、例えば積層フィルムにおいて隣接する層からの剥離や被着部材からの剥離を生じる虞が少ない。また、医療用フィルムは、使用時に当該フィルムが接着される部材(被接着部材)との間の密着性を損なわないためには、被接着部材の熱線膨張率(CTE)の差が小さいことが好ましい。
本発明の医療用フィルムの引張強度は、80~400MPaであることが好ましい。引張強度が80MPa以上であると、十分な機械的強度が得られやすい。本発明の医療用フィルムの引張強度は、100~350MPaであることがより好ましい。
本発明の医療用フィルムのMIT耐折性試験での耐折回数は、1000回以上であることが好ましい。医療用フィルムの耐折回数が1000回以上であると、医療用フィルムの可とう性が十分であるため、実際に使用する際にフィルムが切断してしまう等の問題が生じにくい。医療用フィルムのMIT耐折性試験での耐折回数は、3000回以上であることがより好ましく、1万回以上であることがさらに好ましい。
本発明の医療用フィルムは、アセトン等のケトン類やメタノール、エタノール等のアルコール類、クレゾール等のフェノール類、ジメチルスルホキシド(DMSO)、N-メチルピロリドン(NMP)、N,N-ジメチルアセトアミド(DMAc)、クロロホルム等の各種溶剤、特にメタノールやエタノール等のアルコール類に対して良好な耐溶剤性を有しうる。具体的には、当該フィルムを室温(22℃)で24時間浸漬させたときの浸漬前後の重量減少量が、浸漬前のフィルムの5質量%以下であることが好ましく、3質量%以下であることがより好ましく、0質量%(溶解なし)であることがさらに好ましい。
医療用フィルムの厚みは、医療用フィルムの用途によって異なるが、0.5~200μmであることが好ましい。医療用フィルムの厚みが0.5μm以上であると、十分な機械的強度を確保しやすく、200μm以下であると、透明性やフレキシブル性が損なわれにくい。医療用フィルムの厚みは、1~100μmであることがより好ましい。
本発明の医療用フィルムは、前述の通り、高い耐熱性と透明性とを有する。従って、そのような耐熱性や透明性が要求される各種医療用具の基材として好ましく用いられる。そのような医療用具の例には、輸液バック等の袋状物やカテーテル等のカバー(包装材)、培養皿や培養容器等の医療用容器、医療機器(診察・検査・治療機器)や医療用ウエアラブル・デバイスの部材等が含まれる。
本発明の医療用フィルムは、例えば1)前述のポリイミドの前駆体溶液(ポリアミド酸組成物)を得る工程、2)該ポリアミド酸組成物を支持体上に塗布した後、乾燥及び熱硬化(イミド化)させる工程、及び3)該ポリアミド酸組成物の硬化物を支持体から剥離して、ポリイミドフィルムからなる医療用フィルムを得る工程を経て得ることができる。
ηinh=ln(Tp/Tb)/c(Tp:ポリアミド酸組成物の流下時間(sec)
Tb:ブランク(溶媒のみ)の流下時間(sec)
c:ポリアミド酸組成物の濃度(g/dL))
前述のポリアミド酸組成物を支持体上に塗布した後、不活性ガス雰囲気下で、加熱及び乾燥させて(イミド化させて)、前述のポリイミドフィルムを得る。
その後、支持体から硬化物を剥離し、ポリイミドフィルム(医療用フィルム)を得ることができる。
前述の2.医療用フィルムの製造方法の1)の工程で用いたポリアミド酸組成物は、硬化物が高い耐熱性と透明性とを有することから、医療用コーティング組成物として好ましく用いることができる。
本発明の医療用具は、医療用フィルム又は医療用コーティング組成物の硬化物を含む。医療用フィルムは、前述の1.医療用フィルムとし;医療用コーティング組成物は、前述の3.医療用コーティング組成物とし得る。
本発明の第一実施形態に係る医療用具は、医療用フィルムを含む。そのような医療用具の例には、輸液バック等の各種袋状物;カテーテル等の各種カバー(包装材);培養皿や培養容器等の医療用容器;医療機器(診察・検査・治療機器)や医療用ウエアラブル・デバイスの構成部材が含まれる。医療用機器や医療用ウエアラブル・デバイスの例としては、生体信号検出センサ、脳波センサ、医療用カテーテルの内部に圧力センサを集積化したデバイス、圧力・温度センサを備えた人工皮膚等がある。医療用機器や医療用ウエアラブル・デバイスの構成部材の例には、保護層、有機トランシ゛スタ(OTFT)層及び基材(医療用フィルム)をこの順に積層した構造を有する部材が含まれる。
本発明の第二実施形態に係る医療用具は、医療用部材と、医療用コーティング組成物の硬化物からなる被覆層とを含む。
<ジアミン>
H-XDA:1,4-ビス(アミノメチル)シクロヘキサン(トランス85モル%、シス15モル%)
NBDA:ノルボルナンジアミン
CHDA:トランス-1,4-シクロヘキシルジアミン
HMDA:1,6-ヘキサメチレンジアミン
ODA:4,4’-ジアミノジフェニルエーテル〔4,4’-オキシジアニリン〕
APB:1,3-ビス(3-アミノフェノキシ)ベンゼン
PMDA:ピロメリット酸二無水物
BPDA:3,3’,4,4’-ビフェニルテトラカルボン酸二無水物
ODPA:ビス(3,4-ジカルボキシフェニル)エーテル二無水物
6FDA:2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物
H-PMDA:1,2,4,5-シクロヘキサンテトラカルボン酸二無水物
NMP:N-メチルピロリドン
DMAc:N,N-ジメチルアセトアミド
DMI:1,3-ジメチル-2-イミダゾリジノン
(合成例1)
温度計、攪拌機、窒素導入管を備えた1Lの5つ口セパラブルフラスコ(反応容器)に、H-XDA35.5g(0.250モル)、BPDA73.2g(0.249モル)、及びNMP616gを室温で加えた。該反応容器を、80℃に保持したオイルバス中に1時間間浴した。途中、5~10分で造塩したが、速やかに溶解し、均一溶液となった。オイルバスを外してから、さらに室温で18時間攪拌し、均一なポリアミド酸溶液(ワニス)を得た。
温度計、攪拌機、窒素導入管、滴下ロートを備えた1.5Lの5つ口セパラブルフラスコ(反応容器)に、PMDA153g(0.700モル)及び溶媒DMAc420gを加え、該反応容器を0℃のアイスバス中で攪拌してスラリー状液体とした。滴下ロート内に装入したNBDA108g(0.700モル)とDMAc189gを含む溶液を、該スラリー状液体に2時間かけて滴下した。滴下終了後、アイスバスを外し、更に18時間室温で攪拌し、ポリアミド酸溶液(ワニス)を得た。
温度計、攪拌機、窒素導入管を備えた300mLの5つ口セパラブルフラスコ(反応容器)に、CHDA11.4g(0.100モル)、BPDA25.9g(0.0880モル)、及び溶媒NMP149gを室温で加えた。該反応容器を、90℃に保持したオイルバス中に1時間間浴した。途中、約10分後に造塩したが、速やかに溶解し、均一溶液となった。オイルバスを外してから、更に18時間室温で攪拌し、末端にCHDA由来のアミノ基を有するオリゴアミド酸溶液(ワニス)を得た。
次いで、温度計、攪拌機、窒素導入管を備えた200mLの5つ口セパラブルフラスコ(反応容器)に、NBDA6.19g(0.0402モル)、BPDA15.3g(0.0522モル)、及び溶媒DMI64.5gを室温で加えた。該反応容器を120℃に保持したオイルバス中に5分間浴した。途中、上記同様、造塩と速やかな溶解を確認したところで、該セパラブルフラスコに冷却管とディーンスターク型濃縮器を取付け、さらに、キシレン15gを反応溶液に追加して、脱水熱イミド化反応を190℃で4時間攪拌しながら行った。最後に、キシレンを留去することで、末端にBPDA由来の酸無水物構造を有するオリゴイミド溶液(ワニス)を得た。
そして、得られたオリゴアミド酸ワニス全量と、オリゴイミドワニス全量とを混合し、さらにNMP120gを加えて15%相当まで希釈して、マルチブロック状ポリアミド酸イミドワニスを得た。
合成例1で用いたH-XDA(0.250モル)を、NBDA4.05g(0.0260モル)及びH-XDA31.8g(0.224モル)に変更し、且つ合成例1で用いたBPDA(0.249モル)を、PMDA5.70g(0.0260モル)及びBPDA65.5g(0.223モル)に変更した以外は合成例1と同様にして、ポリアミド酸溶液(ワニス)を得た。
合成例1で用いたH-XDA(0.250モル)を、CHDA28.5g(0.250モル)に変更した以外は合成例1と同様にして、ポリアミド酸溶液(ワニス)を得た。
合成例2で用いたPMDA153g(0.700モル)及び溶媒DMAc420gを、ODPA217g(0.700モル)及び溶媒DMAc786gにそれぞれ変更した以外は合成例2と同様にして、ポリアミド酸溶液(ワニス)を得た。
合成例2で用いたPMDA(0.700モル)及び溶媒DMAc420gを、ODPA217g(0.700モル)及び溶媒NMP750gにそれぞれ変更し、且つ合成例2で用いたNBDA108g(0.700モル)及び溶媒DMAc189gを、H-XDA79.5g(0.560モル)、HMDA16.2g(0.140モル)及び溶媒NMP189gに変更した以外は合成例2と同様にして、ポリアミド酸溶液(ワニス)を得た。
温度計、攪拌機、窒素導入管を備えた1.5Lの5つ口セパラブルフラスコ(反応容器)に、ODA50.0g(0.250モル)及びNMP591gを加えて均一溶液とし、該反応容器を0℃のアイスバス中で攪拌した。該均一溶液に、PMDA54.3g(0.249モル)を粉のまま装入し、アイスバス中で3時間間撹拌した。途中、増粘しながら、スラリー状から均一溶液に変化した。アイスバスを外した後、さらに室温で18時間攪拌して、均一なポリアミド酸溶液(ワニス)を得た。
PMDA153g(0.700モル)及び溶媒DMAc420gを、ODPA186g(0.600モル)及び溶媒NMP643gにそれぞれ変更し、且つNBDA108g(0.700モル)及び溶媒DMAc189gを、H-XDA59.7g(0.420モル)、HMDA20.8g(0.180モル)及び溶媒NMP162gに変更した以外は合成例2と同様にして、ポリアミド酸溶液(ワニス)を得た。
PMDA153g(0.700モル)及び溶媒DMAc420gを、6FDA267g(0.600モル)及び溶媒NMP643gにそれぞれ変更し、且つNBDA108g(0.700モル)及び溶媒DMAc189gを、H-XDA42.6g(0.300モル)、CHDA34.2g(0.300モル)及び溶媒NMP162gに変更した以外は合成例2と同様にして、ポリアミド酸溶液(ワニス)を得た。
PMDA153g(0.700モル)を、6FDA311g(0.700モル)に変更した以外は合成例2と同様にして、ポリアミド酸溶液(ワニス)を得た。
PMDA153g(0.700モル)及び溶媒DMAc420gを、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物(H-PMDA)112g(0.500モル)とDMAc590gとにそれぞれ変更し、且つNBDA108g(0.700モル)及び溶媒DMAc189gを、1,3-ビス(3-アミノフェノキシ)ベンゼン(APB)146g(0.500モル)と溶媒DMAc184gに変更した以外は合成例2と同様にして、ポリアミド酸溶液(ワニス)を得た。
NMP溶媒を用いて、ポリアミド酸の固形分濃度が0.5dL/gとなるように、ポリアミド酸溶液を調製した。次いで、該ポリアミド酸溶液の35℃における流速時間を、ウベローデ粘度計にて測定した(n=3)。別途、ブランク測定として、NMP溶媒のみの35℃における流速時間を、該ウベローデ粘度計にて測定した。そして、ポリアミド酸溶液とブランク(溶液のみ)の流速時間を、それぞれ下記式に当てはめて、固有対数粘度(ηinh)を求めた。尚、濃度cは、0.5g/dLとし、Tpは、n=3の平均値を採用した。
ηinh=ln(Tp/Tb)/c
(Tp:ポリアミド酸溶液の流下時間(sec)
Tb:ブランク(溶剤)の流下時間(sec)
c:ポリアミド酸溶液の濃度(g/dL))
(実施例1~11)
合成例1~12で得られたポリアミド酸溶液を、予め加圧ろ過(フィルター径:10μm)により異物除去及び脱泡操作を行った。
次いで、得られたポリアミド酸溶液を、ガラス基板(A3版サイズ)上に、ドクターブレードにて流延した。これを速やかにイナートオーブンに移して、窒素気流中(酸素濃度0.01%、実施例8は酸素濃度0.01%未満)、2時間かけて50℃から280℃まで昇温した後、さらに280℃で2時間保持して、自己支持性を有する厚み15~25μmの無色透明の硬化物を得た。
得られた硬化物の端部をスリットして、ガラス基板から当該硬化物を自発的に剥離させて、自己支持性を有する25cm四方以上のポリイミドフィルムを得た。
下記フィルム(又はシート)を準備した。
合成例8のフィルム
PP(ポリプロピレン):キングジム製PP(透明ポケット、No.103-100、A4-S、厚み35μm)
PS(ポリスチレン):サンプラテック製PSケース(8.5×5.5、厚み1.5mm)
PC(ポリカーボネート):タキロン製PCシート(銘柄:PC-1600、厚み2mm)
PET(ポリエチレンテレフタレート):東レ製(銘柄:ルミラーS10、厚み100μm)
PMMA(ポリメチルメタクリレート):日東樹脂工業製アクリルシート(銘柄:CLAREX H001、厚み2mm)
1)オートクレーブ滅菌処理
得られたフィルム(又はシート)をサーモフィッシャーサイエンティフィック社製簡易滅菌袋に入れた。その後、さらに専用カゴに入れて、平山製作所製 高圧蒸気滅菌機(HA-300MIV)にセットし、121℃で20分間滅菌処理を行った。滅菌処理終了後、装置から試験片を取り出して、室温で一晩静置してから、外観の変化・変形を目視確認した。そして、以下の基準に基づいて評価を行った。
○:滅菌処理前後で、サンプルの外観(変色・曇り等)変化なし・変形なしで、結果良好と判断
×:滅菌処理前後で、サンプルの外観(変色・曇り等)変化あり・変形ありで、結果不良と判断
得られたフィルム(又はシート)を、乾熱処理用オーブン(ヤマト科学製 Drying Oven DX602)のステンレス製トレイにセットし、180℃で3時間滅菌処理を行った。滅菌処理終了後、室温で一晩静置してから、外観の変化・変形を目視確認した。そして、前述と同様の基準に基づいて評価を行った。
まず、実施例1~11で得られたフィルムを3枚ずつ準備した。そのうち、1つは未処理とし、他の1つは前述のオートクレーブ滅菌処理を行い、残りの1つは前述の乾熱滅菌処理を行った。
各実施例のフィルムについて、以下の1)~7)の評価を行った。1)~6)の評価は、未処理、オートクレーブ滅菌処理後及び乾熱滅菌処理後のフィルムの全てについて行い;7)の評価は、未処理のフィルムについてのみ行った。尚、比較例1のフィルムは、上記滅菌処理前後の変化はなく良好であったが、色相が淡黄色であるため、1)~7)の評価は行わなかった。
上記フィルムの伸びを、島津製作所製TMA-50型を用いて、空気気流下、昇温速度5℃/分、単位断面積当たりの荷重14g/mm2の条件で測定した。Tgは、得られた温度-伸び曲線の変曲点として、接線の交点から算出した。CTEは、100~200℃の範囲における該温度-伸び曲線の傾きから算出した。
上記フィルムの全光線透過率及びヘイズを、日本電色工業製Haze Meter NDH2000型を用いて、JIS-K7136に準拠して測定した。
上記フィルムのL*a*b*表色系におけるb*値を、スガ試験機製Color Cute i型を用いて、透過モード、測光方式8°diにて白色標準板による校正を行った後、測定した。
MultiSpec-1500(島津製作所製)を用いて、上記フィルムの紫外・可視スペクトルを測定した。このときの、波長450nmにおける光線透過率を測定した。尚、10μmに厚み換算した光線透過率@450nmは、前述の波長450nmにおける光線透過率(実際の厚みでの光線透過率)から、Lambertの法則に従って求めた。
上記フィルムを、長さ約120mm×幅15mmの形状にカットし、試験片とした。この試験片を、安田精機製作所製 MIT型耐折試験機(307型)にセットして、曲率半径0.38mm、荷重0.5Kg、折り曲げ確度270度(左右135度)、折り曲げ速度175回/分の条件で破断するまでの回数を測定した。
耐折性は、MIT耐折性試験(安田精機製作所製、307型)を用い、上記試験片について、試験片の一端を固定したうえで、他端を把持して試験片を往復折り曲げし、試験片が破断するまでの折り曲げ回数を測定した。測定条件は以下の通りとした。
尚、試験時には、試験片の一方側への折り曲げを1回と数えた。試験は3回行い、3回の試験結果の算術平均値について有効数値2ケタで四捨五入した値を耐折性の測定結果とした。また、耐折性の測定結果の上限値は、100万回とした。
(測定条件)
曲げ半径:R=0.38mm
荷重:0.5kgf
折り曲げ角度:270°(左右135°)
折り曲げ速度:175回/分
試験回数:n=3
上記フィルムを、標線幅5mm、試験長30mmのダンベル型にカットし、ダンベル型試験片を得た。この試験片を、引張速度30mm/分の条件で破断に至るまでの応力と、その時の伸度を、島津製作所製EZ-S引張試験機を用いて測定し、応力―歪曲線を得た。得られた該曲線より、破断に至った点をそれぞれ引張強度及び引張伸度とし、5回の測定の平均値を採用した。
上記フィルムを、5cm角にカットし、試験片を得た。この試験片を、各種溶剤(アセトン、メタノール、エタノール、クレゾール、ジメチルスルホキシド(DMSO)、N-メチルピロリドン(NMP)、N,N-ジメチルアセトアミド(DMAc)、又はクロロホルムで満たしたシャーレ中に完全に浸るように静置し、室温(22℃)で24時間保存した。その後、試験片をシャーレから取り出して試験片の外観を目視観察し、以下の基準で評価した。
5:外観の変化なし
4:溶解しないが、カールやシワ又は表面の曇りが発生した
3:浸漬前の試験片の3質量%以下の範囲で溶解した
2:浸漬前の試験片の3質量%超5質量%以下の範囲で溶解したが、許容レベル
1:浸漬前の試験片の5質量%超の範囲で溶解し、許容できないレベル
2以上であれば許容レベルとして判断した。
(実施例12:積層フィルムで作製された袋状物(第一実施形態の実施例))
上記作製したポリイミドフィルム4(高Tg層、厚み21μm、Tg:270℃)上に、合成例6で調製したポリアミド酸溶液(ワニス)を塗布した後、イナートオーブンで窒素気流下、50℃から280℃まで昇温し、そのまま280℃で1時間保持して、ポリイミド層(低Tg層、厚み10μm、Tg:219℃)を形成し、積層フィルム(厚み31μm)を得た。
得られた積層体(厚み60μm)の180°ピール強度(剥離強度)を、上記引張試験と同じ装置を用い、治具を変えて10mm/分の速度で測定したところ、1.5kN/mであった。
画像伝送用に用いられる直径500μm、長さ3.5cmの石英系イメージファイバを、合成例4で得たワニス(ポリアミド酸溶液)に浸漬した後、3cm/minの速度で溶液から引き上げディップコートした。
次いで、ディップコートされたファイバを、窒素気流下のオーブンで、50℃から280℃に1.5時間かけて昇温した後、280℃のまま1時間保持して、脱溶剤及び熱イミド化を行い、厚み12μmのポリアミド酸溶液の硬化物からなる被覆層で被覆されたイメージファイバを得た。
11A 高Tg層
11B 低Tg層
Claims (16)
- 熱機械分析TMAで測定されるガラス転移温度が190℃以上である耐熱性樹脂を含む医療用フィルムであって、
前記医療用フィルムの、厚み10μmにおける全光線透過率が80%以上であり、且つL*a*b*表色系におけるb*値が10以下である、医療用フィルム。 - 前記医療用フィルムの、厚み10μmにおけるL*a*b*表色系におけるb*値が5以下である、請求項1に記載の医療用フィルム。
- 前記耐熱性樹脂は、ポリイミドである、請求項1に記載の医療用フィルム。
- 前記脂環族ジアミン由来の基が、1,4-ビス(アミノメチル)シクロヘキサン、トランス-1,4-シクロヘキシルジアミン、及びノルボルナンジアミンからなる群より選ばれる基であり、
前記芳香族テトラカルボン酸二無水物由来の基が、ピロメリット酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、及びビス(3,4-ジカルボキシフェニル)エーテル二無水物からなる群より選ばれる芳香族テトラカルボン酸二無水物由来の基である、請求項4に記載の医療用フィルム。 - 前記医療用フィルムの厚みは、1~100μmである、請求項1に記載の医療用フィルム。
- 前記医療用フィルムは、ガラス転移温度が相対的に高いポリイミドを含む層と、ガラス転移温度が相対的に低いポリイミドを含む層の積層フィルムである、請求項3に記載の医療用フィルム。
- 請求項1に記載の医療用フィルムを含む、医療用具。
- 請求項1に記載の医療用フィルムを折り曲げるか、又は少なくとも2つの前記医療用フィルムを積層して積層体を得る工程と、
前記積層体の少なくとも一部を熱圧着して、袋状物である医療用具を得る工程とを含む、医療用具の製造方法。 - ポリアミド酸を含む医療用コーティング組成物であって、
前記医療用コーティング組成物の硬化物からなる厚み10μmのフィルムの全光線透過率が80%以上であり、且つL*a*b*表色系におけるb*値が10以下である、医療用コーティング組成物。 - 前記脂環族ジアミン由来の基が、1,4-ビス(アミノメチル)シクロヘキサン、トランス-1,4-シクロヘキシルジアミン、及びノルボルナンジアミンからなる群より選ばれる基であり、
前記芳香族テトラカルボン酸二無水物由来の基が、ピロメリット酸二無水物、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物からなる群より選ばれる芳香族テトラカルボン酸二無水物由来の基である、請求項12に記載の医療用コーティング組成物。 - 溶媒をさらに含む、請求項11に記載の医療用コーティング組成物。
- 医療用部材と、請求項11に記載の医療用コーティング組成物の硬化物からなる被覆層とを含む、医療用具。
- 医療用部材の表面を、請求項11に記載の医療用コーティング組成物でコーティングする工程と、
前記医療用コーティング組成物の塗膜を不活性ガス雰囲気下で加熱して、前記医療用部材と、その表面を覆う前記医療用コーティング組成物の硬化物からなる被覆層とを有する医療用具を得る工程とを含む、医療用具の製造方法。
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US (1) | US11198280B2 (ja) |
EP (1) | EP3489285A4 (ja) |
JP (1) | JP6781756B2 (ja) |
KR (1) | KR102249571B1 (ja) |
CN (1) | CN109563282B (ja) |
TW (1) | TWI795363B (ja) |
WO (1) | WO2018016561A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2019244988A1 (ja) * | 2018-06-22 | 2019-12-26 | 三井化学株式会社 | ポリアミド酸およびこれを含むワニス、フィルム、タッチパネルディスプレイ、液晶ディスプレイ、ならびに有機elディスプレイ |
JP2020059785A (ja) * | 2018-10-09 | 2020-04-16 | 三井化学株式会社 | ポリアミド酸およびこれを含むワニス、ならびにポリイミドフィルムの製造方法 |
JP2021008610A (ja) * | 2019-06-28 | 2021-01-28 | エスケイシー・カンパニー・リミテッドSkc Co., Ltd. | 高分子フィルム |
Families Citing this family (1)
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CN114989432B (zh) * | 2022-07-08 | 2023-05-05 | 中国地质大学(北京) | 一种聚酰亚胺及其制备方法和应用、热塑性聚酰亚胺工程塑料及其制备方法和应用 |
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WO2019244988A1 (ja) * | 2018-06-22 | 2019-12-26 | 三井化学株式会社 | ポリアミド酸およびこれを含むワニス、フィルム、タッチパネルディスプレイ、液晶ディスプレイ、ならびに有機elディスプレイ |
JPWO2019244988A1 (ja) * | 2018-06-22 | 2021-03-11 | 三井化学株式会社 | ポリアミド酸およびこれを含むワニス、フィルム、タッチパネルディスプレイ、液晶ディスプレイ、ならびに有機elディスプレイ |
JP2020059785A (ja) * | 2018-10-09 | 2020-04-16 | 三井化学株式会社 | ポリアミド酸およびこれを含むワニス、ならびにポリイミドフィルムの製造方法 |
JP2021008610A (ja) * | 2019-06-28 | 2021-01-28 | エスケイシー・カンパニー・リミテッドSkc Co., Ltd. | 高分子フィルム |
JP7157778B2 (ja) | 2019-06-28 | 2022-10-20 | エスケイシー・カンパニー・リミテッド | 高分子フィルム |
Also Published As
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TW201809091A (zh) | 2018-03-16 |
US11198280B2 (en) | 2021-12-14 |
US20200129377A1 (en) | 2020-04-30 |
JP6781756B2 (ja) | 2020-11-04 |
KR102249571B1 (ko) | 2021-05-07 |
KR20190022674A (ko) | 2019-03-06 |
CN109563282A (zh) | 2019-04-02 |
EP3489285A1 (en) | 2019-05-29 |
TWI795363B (zh) | 2023-03-11 |
EP3489285A4 (en) | 2020-07-29 |
JPWO2018016561A1 (ja) | 2019-03-14 |
CN109563282B (zh) | 2022-04-15 |
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