Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/14—Polyamide-imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/02—Halogenated hydrocarbons
  • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/05—Alcohols; Metal alcoholates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a composition containing an aromatic polyamide and/or an aromatic polyamide-imide.
• a transparent resin varnish is used.
• a transparent resin film can be formed on the base material by applying the varnish onto the base material and then drying it.
• Patent Documents 1 to 3 disclose solutions containing aromatic polyamide and/or aromatic polyamideimide that can be formed into a film by coating and drying.
• Patent Document 4 discloses an aromatic polyamide film.
• the aromatic polyamide film disclosed in Patent Document 4 has both good colorless transparency and high Young's modulus, but when formed into a thick film or a complicated shape, the inorganic salt contained in the polymer solution tends to remain in the film, which may cause devitrification or warping of the film.
• An object of the present invention is to provide an aromatic polyamide and/or aromatic polyamide-imide composition that has excellent moldability, excellent quality such as transparency and color tone, and has a high Young's modulus.
• composition containing a compound having a structure represented by any of the following chemical formulas (I) to (III), and aromatic polyamide and/or aromatic polyamideimide is a composition containing a compound having a structure represented by any of the following chemical formulas (I) to (III), and aromatic polyamide and/or aromatic polyamideimide.
• R 1 is an arbitrary group consisting of a nonmetallic element, and Ar 1 and Ar 2 are groups having a structure represented by chemical formula (IV).
• R 2 and R 3 are arbitrary groups consisting of nonmetallic elements, and Ar 3 and Ar 4 are groups having a structure represented by chemical formula (IV).
• R 4 , R 5 , and R 6 are arbitrary groups consisting of nonmetallic elements, and Ar 5 and Ar 6 are groups having a structure represented by chemical formula (IV).
• R 7 , R 8 , R 9 , R 10 and R 11 are -H, -F, -Cl, -OMe, silyl group, aliphatic group having 1 to 3 carbon atoms, fluoroalkyl having 1 to 3 carbon atoms group, or a chloroalkyl group having 1 or more and 3 or less carbon atoms.
• an aromatic polyamide and/or aromatic polyamide-imide composition that has excellent moldability, excellent quality such as transparency and color tone, and has a high Young's modulus.
• the composition of the present invention can be particularly suitably used as a member or raw material for flexible display materials, transparent flexible printed circuit boards, diffractive optical elements, lenses for sensors, and the like.
• composition of the present invention contains 5 parts by weight or more of a compound having a structure represented by any of the following chemical formulas (I) to (III) based on 100 parts by weight of the aromatic polyamide and/or aromatic polyamide-imide resin component. Contains 180 parts by weight or less.
• R 1 is an arbitrary group consisting of a nonmetallic element, and Ar 1 and Ar 2 are groups having the structure shown in chemical formula (IV).
• R 2 and R 3 are arbitrary groups consisting of nonmetallic elements, and Ar 3 and Ar 4 are groups having the structure shown in chemical formula (IV).
• R 4 , R 5 , and R 6 are arbitrary groups consisting of nonmetallic elements, and Ar 5 and Ar 6 are groups having the structure shown in chemical formula (IV).
• R 7 , R 8 , R 9 , R 10 and R 11 are -H, -F, -Cl, -OMe, silyl group, aliphatic group having 1 to 3 carbon atoms, fluoroalkyl having 1 to 3 carbon atoms group, or a chloroalkyl group having 1 or more and 3 or less carbon atoms.
• the compound having the above structure coordinates to the molecular chain of aromatic polyamide and/or aromatic polyamideimide through the ⁇ - ⁇ interaction caused by the aromatic group, and eliminates the packing between the molecular chains due to the bent structure. Devitrification due to chain aggregation can be effectively suppressed. Thereby, transparency can be maintained even when formed into a molded article or film.
• a solution containing the compound and aromatic polyamide and/or aromatic polyamideimide can be easily detached from the molecular chain by heating because the ⁇ - ⁇ interaction is a weak intermolecular force, and after molding by solvent drying, The amount of residual volatile matter in the resulting molded product or film can be suppressed.
• R 12 is a group of -CH 2 -, -CH(OH)-, -O-, -NH-, and Ar 7 and Ar 8 are groups having the structure shown in chemical formula (XII).
• R 13 and R 14 are -CH 2 -, -CH(OH)-, -O-, -NH-, and Ar 9 and Ar 10 are groups having the structure shown in chemical formula (XII). .
• R 15 , R 16 , R 17 are any group of -CH 2 -, -CH(OH)-, -O-, -NH-, and Ar 11 and Ar 12 have the structure shown in chemical formula (XII) It is the basis.
• R 18 , R 19 , R 20 , R 21 and R 22 are -H, -F, -Cl, -OMe, silyl group, aliphatic group having 1 to 3 carbon atoms, fluoroalkyl having 1 to 3 carbon atoms group, or a chloroalkyl group having 1 or more and 3 or less carbon atoms.
• Examples of compounds having such a structure include diphenyl ether, diphenylmethane, diphenylamine, di(4-fluorophenyl)ether, 1,1'-(oxydimethanediyl)dibenzene, and benzhydrol.
• the content of the compound having such a structure is preferably 0.01 parts by weight or more and 180 parts by weight or less, and 0.01 parts by weight or more, based on 100 parts by weight of the aromatic polyamide and/or aromatic polyamide-imide resin component. It is more preferable that the amount is from 150 parts by weight to 150 parts by weight. If the content of the above compound is less than 0.01 part by weight, devitrification may occur.
• the aromatic polyamide and/or aromatic polyamideimide constituting the composition of the present invention preferably contains a structural unit represented by the following chemical formula (IX). Chemical formula (IX):
• Ar 13 and Ar 14 are arbitrary aromatic groups.
• the aromatic polyamide of the present invention include aramid and polyamic acid.
• aramid is an aromatic polyamide that does not have a carboxylic acid (-COOH) group at the ortho position of the carbonyl group that forms an amide group, and examples include the structure shown in the chemical formula (X) below.
• the acid is an aromatic polyamide having one or more carboxylic acid groups at the ortho position of the carbonyl group forming the amide group, and examples thereof include structures such as chemical formula (XI) and chemical formula (XII).
• the structures shown in chemical formulas (X) to (XII) are examples, and do not limit the structures of aramid and polyamic acids in the present invention.
• Ar 15 is any aromatic group
• R 23 is -H, an aliphatic group having 1 to 5 carbon atoms, -CF 3 , -CCl 3 , -OH, -F, -Cl, -Br, -OCH 3 , A silyl group or a group containing an aromatic ring.
• Ar 16 is any aromatic group
• R 24 is -H, an aliphatic group having 1 to 5 carbon atoms, -CF 3 , -CCl 3 , -OH, -F, -Cl, -Br, -OCH 3 , A silyl group or a group containing an aromatic ring.
• Ar 17 is any aromatic group
• R 25 is -H, an aliphatic group having 1 to 5 carbon atoms, -CF 3 , -CCl 3 , -OH, -F, -Cl, -Br, -OCH 3 , A silyl group or a group containing an aromatic ring.
• the aromatic polyamide-imide of the present invention may be a case in which both an amide group and an imide group are present in the structural unit as shown in chemical formula (XIII), or a diimide as shown in chemical formula (XIV) as described above.
• An example is a case where it is copolymerized with an aromatic polyamide structure, but in the present invention, either case is acceptable.
• Ar 18 is any aromatic group
• R 26 is -H, an aliphatic group having 1 to 5 carbon atoms, -CF 3 , -CCl 3 , -OH, -F, -Cl, -Br, -OCH 3 , A silyl group or a group containing an aromatic ring.
• Ar 19 is any aromatic group
• R 27 is -H, an aliphatic group having 1 to 5 carbon atoms, -CF 3 , -CCl 3 , -OH, -F, -Cl, -Br, -OCH 3 , A silyl group or a group containing an aromatic ring.
• aromatic polyamides and/or aromatic polyamideimides constituting the composition of the present invention aromatic polyamides are preferred among the above, since they can increase rigidity.
• the aromatic polyamide and/or aromatic polyamideimide constituting the composition of the present invention is represented by any of the following chemical formulas (XV) to (XVII) as Ar 19 and/or Ar 20 in the above chemical formula (IX). It is preferable that the structural unit contains the following structural units. Chemical formula (XV):
• R 28 is -H, an aliphatic group having 1 to 5 carbon atoms, -CF 3 , -CCl 3 , -OH, -F, -Cl, -Br, -OCH 3 , a silyl group, or a group containing an aromatic ring It is.
• R 29 and R 30 are -H, an aliphatic group having 1 to 5 carbon atoms, -CF 3 , -CCl 3 , -OH, -F, -Cl, -Br, -OCH 3 , a silyl group, or an aromatic ring It is a group containing Chemical formula (XVII):
• R31 is a group containing an Si atom, a group containing a P atom, a group containing an S atom, a halogenated hydrocarbon group, a group containing an aromatic ring, or a group containing an ether bond (however, these groups cannot be structural units having these may be mixed).
• R 32 is any aromatic group or any alicyclic group.
• R 33 is any aromatic group or any alicyclic group.
• the solution of the present invention contains the above compound, aromatic polyamide and/or aromatic polyamideimide, and an aprotic solvent.
• the aprotic solvent is a polar solvent that does not have proton (hydrogen ion) donating properties, such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylisobutyramide, 3-methoxy -N,N-dimethylpropanamide, tetrahydrofuran, ⁇ -butyrolactone, ethyl acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide and the like.
• the content of the above compound in the solution is preferably 5 parts by weight or more and 180 parts by weight or less based on 100 parts by weight of the aromatic polyamide and/or aromatic polyamide-imide resin component. If the content of the above compound is less than 5 parts by weight, the molded article or film obtained by solvent drying may suffer from devitrification. When the content of the above compound is greater than 180 parts by weight, the amount of volatile matter remaining in the film obtained after solvent drying may increase.
• the molded article of the present invention has aromatic polyamide and/or aromatic polyamideimide as a main component.
• the main component is the component that is the most abundant in the molded article.
• the content of the compound having a structure represented by any one of the above chemical formulas (I) to (III) in the molded article is 0.00 parts by weight based on 100 parts by weight of the aromatic polyamide and/or aromatic polyamide-imide resin component.
• the amount is preferably 01 parts by weight or more and 10 parts by weight or less. If the content of the compound is less than 0.01 part by weight, the molecular chains may aggregate, causing devitrification or a decrease in Young's modulus.
• the film of the present invention contains aromatic polyamide and/or aromatic polyamideimide as a main component, and the content of the compound having the structure represented by any of the above chemical formulas (I) to (III) is the same as that of aromatic polyamide and/or aromatic polyamideimide.
• the aromatic polyamide-imide is 100 parts by weight, it is 0.01 parts by weight or more and 10 parts by weight or less.
• the film of the present invention preferably has a thickness of 1 ⁇ m or more and 200 ⁇ m or less, more preferably 1 ⁇ m or more and 150 ⁇ m or less, and even more preferably 30 ⁇ m or more and 80 ⁇ m or less.
• the composition of the present invention may be a single polymer or a mixture of aromatic polyamides and/or aromatic polyimides having different chemical structures, as long as it contains aromatic polyamide and/or aromatic polyamideimide, and may contain different polymers. It doesn't matter if you stay there.
• the amount of polymer component (the sum of the weight of the aromatic polyamide and/or aromatic polyamideimide and the weight of the different polymer) is not particularly limited, but in a solution, it is 1 part by weight or more and 30 parts by weight or less based on 100 parts by weight of the entire solution. The amount is preferably 80 parts by weight or more, and more preferably 90 parts by weight or more in the molded article.
• the amount of the polymer component By setting the amount of the polymer component within the above range, the moldability of the solution and the high rigidity of the molded article can be better exhibited.
• different polymers that can be contained in the composition include, but are not limited to, polyimide, polyester, polyethylene, polypropylene, polysiloxane, and the like. When a different type of polymer is contained, it is preferable that the amount of the different type of polymer is 30 parts by weight or less per 100 parts by weight of the polymer component.
• the composition of the present invention when used, for example, in a display material, a circuit board, an optical element, etc., in order to make the member highly rigid, the composition of the present invention may mainly contain aromatic polyamide and/or aromatic polyamide-imide. It is preferable to use it as a component.
• the composition of the present invention contains organic-inorganic hybrid resins such as thermosetting resins, ultraviolet curable resins, hydrolysis/condensation resins, and alkoxysilane compounds for the purpose of increasing rigidity, thermal dimensional stability, etc. Good too. Further, particles may be included. Here, the particles may be either inorganic particles or organic particles, but for the purpose of improving hardness or thermal dimensional stability, it is preferable to contain inorganic particles. Inorganic particles are not particularly limited, but include metal and metalloid oxides, silicides, nitrides, borides, chlorides, carbonates, etc.
• silica SiO 2
• aluminum oxide Al 2 O 3
• zinc oxide ZnO
• zirconium oxide ZrO 2
• titanium oxide TiO 2
• antimony oxide Sb 2 O 3
• indium tin oxide ITO
• organic or inorganic pigments, dyes, or antioxidants may be contained.
• the molded article of the present invention preferably has a haze of 0.0% or more and 5.0% or less.
• the haze is more preferably 0.0% or more and 3.0% or less, and even more preferably 0.0% or more and 2.0% or less.
• one of the structures represented by the above chemical formulas (I) to (III) is added. It is effective to include a compound having
• the molded article of the present invention preferably has a yellowness index (YI) of 0.0 or more and 5.0 or less. If YI is greater than 5.0, the molded product may be significantly colored, resulting in poor color reproducibility and visibility when used as a display material, diffractive optical element, or other optical member.
• YI is more preferably 0.0 or more and 4.0 or less, and even more preferably 0.0 or more and 3.0 or less.
• one of the structures represented by the above chemical formulas (I) to (III) is added. It is effective to include a compound having
• the molded article of the present invention preferably has a Young's modulus in at least one direction of 6.0 GPa or more and 20.0 GPa or less. More preferably, it is 7.0 GPa or more and 20.0 GPa or less, and still more preferably 8.0 GPa or more and 20.0 GPa or less. If the Young's modulus is less than 6.0 GPa, handling properties and mechanical properties may deteriorate. In order to keep the Young's modulus within the above range, it is preferable to use aromatic polyamide and/or aromatic polyamideimide containing a structural unit represented by any one of the above chemical formulas (IX) to (XIII).
• the molded article of the present invention has an in-plane retardation (R 0 ) of 0 nm or more and 100 nm or less with respect to incident light with a wavelength of 548.3 nm.
• R 0 is more preferably 80 nm or less, and still more preferably 60 nm or less.
• R 0 is the refractive index in the direction in which the in-plane refractive index of the molded body is maximized (i.e., the slow axis direction) is n x , and the direction perpendicular thereto (i.e., the fast axis direction) It is defined as (n x - n y ) ⁇ d, where n y is the refractive index of the film and d (nm) is the thickness of the film.
• the in-plane retardation exceeds 100 nm, interference colors due to polarized light may occur, and visibility may deteriorate when used as a display member, a diffractive optical element, or the like.
• the above chemical formula (I) ⁇ It is effective to contain a compound having one of the structures shown in III) in the film to alleviate molecular chain packing.
• the optical element of the present invention is characterized by being provided with a structure formed of a resin containing the composition of the present invention.
• the structure can be formed on the element surface and/or on a portion adjacent to a different type of resin material, glass, or the like.
• the structure is preferably a structure formed of concave portions and/or convex portions, and examples thereof include a lens shape, a bell shape, and a comb shape.
• the size or repetition pitch of the structure it is preferably 300 nm or less when used as a diffractive optical element.
• it is effective to mold the solution of the present invention on a base material having a desired pattern shape by drying the solution with a solvent.
• a resin layer containing the composition of the present invention high total light transmittance can be obtained, and for example, when used as a diffractive optical element, the brightness and brightness of a diffraction image can be improved.
• the resin layer preferably contains particles with an average particle size of 400 nm or less, more preferably 200 nm or less.
• the average particle size here refers to the number average particle size, and can be measured by microscopically observing particles in an optical element. If the average particle size is larger than 200 nm, it may interfere with visible light to cause scattering or increase haze.
• the particles are preferably high refractive index fillers such as titanium oxide and zirconium oxide, which can obtain a high refractive index and improve the viewing angle when used in AR glasses, for example.
• the refractive index of the element is preferably 1.8 or more, more preferably 1.9 or more.
• the screen display device of the present invention is characterized by containing a laminate of the composition of the present invention, glass and/or a hard coat layer.
• a laminate of the composition of the present invention By including the laminate, visibility is improved due to transparency, and hardness is increased due to high Young's modulus derived from aromatic polyamide and/or aromatic polyamide-imide, thereby improving screen strength.
• the laminate contains the composition of the present invention, it is possible to reduce the in-plane retardation and prevent a decrease in screen visibility due to optical interference.
• the solution of the present invention may be cast directly onto the glass, or the hard coat layer may be applied to a film obtained by casting the solution of the present invention onto a substrate. Formation can be mentioned.
• the in-plane retardation is preferably 0 nm or more and 100 nm or less.
• the thickness of the resin layer made of the composition of the present invention is preferably 1 ⁇ m or more and 200 ⁇ m or less, more preferably 1 ⁇ m or more and 100 ⁇ m or less. By setting the thickness of the resin layer within the above range, handling properties, scratch resistance, and bending resistance of the laminate can be obtained.
• the material and manufacturing method of the glass are not particularly limited, and any commercially available glass, known glass, or newly manufactured glass may be used.
• aluminosilicate glass with a high surface smoothness for display materials lithium aluminosilicate glass, or alkali-free glass or quartz glass.
• the manufacturing method of the glass film for example, a method of directly manufacturing a glass film of a desired thickness using a down-draw method, a fusion method, an overflow method, etc., or a method that combines a float method and thinning by slimming, etc. can be used. Can be done.
• chemical strengthening treatment may be performed using a known method.
• a hard coat layer is a layer containing a curable resin
• a curable resin is a resin made of a crosslinked polymer compound that causes a polymerization reaction by absorbing energy such as heat or light.
• the curable resin is preferably a thermosetting resin or an ultraviolet curable resin
• the precursor of the curable resin is, for example, an organic silane type, a polyol type, a melamine type, an epoxy type, a polyfunctional acrylate type, Examples include polyfunctional thiol compounds, urethane compounds, isocyanate compounds, organic-inorganic hybrid compounds that are composite materials of organic and inorganic materials, and silsesquioxane compounds having a curable functional group.
• the hard coat layer may contain particles, which may be either inorganic particles or organic particles, but inorganic particles are suitable for improving surface hardness. Further, the hard coat layer may contain particles. Here, the particles may be either inorganic particles or organic particles, but it is preferable to include inorganic particles because high hardness is easily obtained. Inorganic particles are not particularly limited, but include metal and metalloid oxides, silicides, nitrides, borides, chlorides, carbonates, etc., such as silica (SiO2), aluminum oxide (Al2O3), zinc oxide, etc.
• the particles may be subjected to surface treatment.
• surface treatment refers to introducing a compound onto the particle surface through chemical bonding (eg, covalent bonding, hydrogen bonding, ionic bonding) or adsorption (eg, physical adsorption, chemical adsorption).
• various additives can be added to the hard coat layer within a range that does not impede the effects of the present invention.
• additives examples include polymerization initiators, fluorescent agents, pigments, organic lubricants, antistatic agents, and organic particles.
• a light absorber that selectively absorbs a specific wavelength of 380 nm to 420 nm, a fluorescent photosensitizer, or an organic/inorganic blue pigment.
• the hard coat layer may have two or more layers with different configurations on one side.
• the circuit board of the present invention is characterized in that wiring is formed on at least one surface of the composition of the present invention using a conductive material.
• the metal ions are alkali metal ions such as Li + , Na + , K + and/or alkaline earth metals such as Mg 2+ and Ca 2+ .
• the content of metal ions is preferably 3000 ppm or less, and to keep it within the above range, neutralizing agents, additives, etc. are added during polymerization of the aromatic polyamide and/or aromatic polyamide-imide constituting the composition of the present invention.
• neutralizing agents, additives, etc. are added during polymerization of the aromatic polyamide and/or aromatic polyamide-imide constituting the composition of the present invention.
• This is not adding materials containing metals.
• the magnetic recording medium of the present invention is characterized in that a magnetic material layer is provided on at least one surface of the composition of the present invention.
• the metal ions are alkali metal ions such as Li + , Na + , K + and/or alkaline earth metals such as Mg 2+ and Ca 2+ . It is preferable that the content of metal ions is 3000 ppm or less, and in order to keep it within the above range, it is necessary to use it as a neutralizing agent or additive during the polymerization of the aromatic polyamide and/or aromatic polyamideimide constituting the composition of the present invention.
• One example is not adding materials containing metals.
• the manufacturing method of the present invention is a method for manufacturing a molded article and/or a laminate mainly composed of aromatic polyamide and/or aromatic polyamide-imide, comprising the steps of: applying the solution of the present invention onto a base material; It is characterized by including a step of removing the solvent by drying.
• aromatic polyamide when aromatic polyamide is polymerized by solution polymerization, it can be synthesized by using acid dichloride and diamine as raw materials and reacting them in the aprotic solvent described above at low temperature.
• the moisture content of the solvent used for polymerization is preferably 500 ppm or less (based on mass, the same applies hereinafter), more preferably 200 ppm or less. If the molar ratio of acid dichloride and diamine is equal, an ultra-high molecular weight polymer tends to be produced, so the molar ratio of one to 96.0 to 99.8% of the other, more preferably 96.
• the polymerization reaction of aromatic polyamide is accompanied by heat generation, it is preferable to keep the temperature of the solution during polymerization at 40° C. or lower. If the temperature exceeds 40°C, side reactions may occur and the degree of polymerization may not be sufficiently increased or coloring may occur.
• the temperature of the solution during polymerization is more preferably 30°C or lower.
• Examples of methods for removing by-product hydrogen chloride include a method in which hydrogen chloride is neutralized and removed by adding a neutralizing agent during polymerization, and a method in which the polymer is precipitated and isolated.
• a method of neutralizing with an inorganic neutralizing agent such as lithium carbonate, calcium carbonate, or calcium hydroxide
• an inorganic neutralizing agent such as lithium carbonate, calcium carbonate, or calcium hydroxide
• the solution contains an inorganic salt (for example, lithium chloride, etc.) produced by the neutralization reaction.
• This inorganic salt acts as a solubility aid in the solvent by ionizing it in the solvent and coordinating with the amide group of the aromatic polyamide, so it is effective in improving the pot life of the solution and suppressing devitrification during film formation.
• a cleaning step is required to remove inorganic salts during the film forming process, and they may remain in the composition even after cleaning, so depending on the application in which the composition is incorporated, such as optical elements or image display devices, Manufacturing methods may not be available.
• a method in which the polymer is precipitated and separated from hydrogen chloride is preferred.
• a polymer When a polymer is precipitated and isolated, it can be precipitated by precipitation polymerization, or by mixing a polymer solution obtained by solution polymerization with a large amount of a poor solvent such as water to precipitate the polymer as a solid, and then remove it from the solution by filtration etc.
• a solution can be obtained by redissolving the isolated polymer in the above-mentioned aprotic solvent.
• an aromatic polyamide-imide precursor can be obtained by polymerizing in the same manner as described above, except that part of the acid dichloride is replaced with tetracarboxylic dianhydride. After this precursor is isolated in the same manner as above, the aromatic polyamideimide is obtained by heating at 200°C to 300°C in an inert gas atmosphere or under reduced pressure to advance the ring-closing reaction. It can be made into a solution by redissolving it in an aprotic solvent.
• the composition of the present invention is obtained by adding a compound having any of the structures represented by the aforementioned chemical formulas (I) to (III) to the aromatic polyamide and/or aromatic polyamideimide obtained by the above method or a solution thereof. You can get it by doing that.
• the composition of the present invention includes thermosetting resins, ultraviolet curable resins, hydrolyzed/condensed resins, organic-inorganic hybrid resins such as alkoxysilane compounds, inorganic or organic particles, organic or inorganic pigments and dyes, Antioxidants and the like may be included, and these may be added to the polymer solution and dispersed, or may be added to the solvent before polymerization to be included in the polymer.
• a molded article can be obtained by drying the solvent from the solution obtained as described above on a substrate or a mold.
• the solution of the present invention can be applied onto a base material such as a glass substrate to form a film.
• Film forming methods include, for example, a dry-wet method in which heat treatment is performed after a preliminary drying step and a washing step in a wet bath, a dry method in which solvent drying is performed without a washing step, or a wet bath method without a solvent drying step. Examples include a wet method in which heat treatment is applied after introduction.
• the coating method on the base material can be selected from known methods such as die coating, die coating, roller coating, wire bar coating, and gravure coating.
• methods for drying the solvent include hot air, infrared irradiation, microwave irradiation, etc., and are not particularly limited.
• the drying temperature is preferably 50 to 400°C. From the viewpoint of improving thermal dimensional stability, it is more preferable to include a step in the temperature range of 150 to 400° C. in the drying step. In order to prevent surface roughening due to rapid solvent evaporation, it is more preferable to carry out preliminary drying at 50 to 200°C and then perform solvent drying in stages at 200 to 400°C.
• the optical element of the present invention can be obtained by using a substrate having an inverted structure of a desired pattern structure on its surface as the substrate in the above molded body manufacturing method.
• the surface structure of the molded product obtained from the patterned substrate has a structure that is inverted with respect to the desired structure because, for example, the uneven structure of the patterned substrate is reversed and transferred to the surface of the molded product as unevenness. I need to be there.
• patterns include a lens shape, a bell shape, and a comb shape.
• the optical element of the present invention may be a resin molded body in which the resin layer is peeled off from a patterned substrate, or may be a laminate of a resin layer and a substrate without peeling, depending on the configuration of the final device such as AR glass.
• the average particle size of the particles contained in the optical element can be determined by measuring the particle size by microscopically observing the surface and/or cross section of the optical element, and calculating the average value. Specifically, particles contained in the optical element are observed using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) at a magnification of 50,000 to 200,000 times. If the particle is a true sphere, the diameter of the true sphere is measured and taken as the particle diameter of the particle.
• SEM scanning electron microscope
• TEM transmission electron microscope
• the longest diameter hereinafter referred to as major axis diameter
• minor axis diameter the longest diameter in the direction perpendicular to the major axis diameter
• the average diameter be the particle diameter of the particles. This measurement is performed on 20 or more randomly selected particles, and the arithmetic mean of the measurements is the number average particle diameter.
• the refractive index can be measured in the plane of the molded body and/or in the film thickness direction using an Abbe refractometer or spectroscopic ellipsometry.
• the image display device of the present invention includes a laminate of the above-mentioned composition, glass and/or a hard coat layer, a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescent display (ELD), a cathode tube display ( It can be obtained by incorporating it into a display such as a CRT.
• examples of the form of the composition to be incorporated include an electrode substrate film for a liquid crystal display, a polarizing film, a retardation film, a viewing angle expanding film, a diffusion sheet, a prism sheet, and a cover film, each of which can be obtained by the above method. It can be obtained by laminating or processing a film or optical element with other optical members via an adhesive.
• a laminate of the composition and glass is obtained by drying the solution on glass as described above.
• a laminate of the composition and the hard coat layer can be obtained by laminating the hard coat layer material onto the composition via an adhesive or by directly molding it onto the surface.
• the circuit board of the present invention can be obtained by forming wiring using a conductive material on the surface of the molded body obtained by the above method.
• the method of forming the metal film constituting the circuit pattern is not particularly limited.
• it can be formed by pasting a metal foil such as copper foil with an adhesive layer, or it can be formed by sputtering, plating, or a combination thereof. can be formed with.
• a photoresist is applied onto the surface on which the metal film has been formed using a spin coater, blade coater, roll coater, die coater, screen printer, etc., dried, exposed to light through a photomask with a predetermined pattern, and developed.
• a resist layer is formed in areas where a plating film is not required.
• the electrolytic plating solution a copper sulfate plating solution, a cyanide compound plating solution, a copper pyrophosphate plating solution, etc. are used. After forming a copper plating film with a thickness of 2 ⁇ m to 20 ⁇ m, the photoresist is peeled off, and then light etching is performed. Further, if necessary, plating with gold, nickel, tin, etc. is performed to obtain a circuit pattern.
• the magnetic recording medium of the present invention can be obtained by providing a magnetic material layer on at least one surface of the molded body obtained by the above method.
• Examples of means for forming the magnetic layer on the surface of the molded body include a wet method of applying a magnetic material to the surface of the molded body, a dry method such as a vapor deposition method, a sputtering method, and an ion plating method.
• the magnetic layer is a layer containing a ferromagnetic material, and examples of the ferromagnetic material include hexagonal ferrite powder and ferromagnetic metal powder.
• Examples of the hexagonal ferrite include barium ferrite, strontium ferrite, lead ferrite, calcium ferrite substituted products, and Co substituted products.
• the ferromagnetic metal powder used in the magnetic layer is not particularly limited, but it is preferable to use a ferromagnetic metal powder containing ⁇ -Fe as a main component.
• these ferromagnetic metal powders contain Al, Si, S, Sc, Ca, Ti, V, Cr, Cu, Y, Mo, Rh, Pd, Ag, Sn, Sb, Te, Ba, It may contain atoms such as Ta, W, Re, Au, Hg, Pb, Bi, La, Ce, Pr, Nd, P, Co, Mn, Zn, Ni, Sr, and B.
• a film to be used for measuring film physical properties was prepared from the solution of the present invention according to the following method.
• a sample solution was cast into a film onto a glass plate using an applicator.
• the temperatures of the sample solution, glass plate, and casting atmosphere were set to room temperature.
• the cast thickness was adjusted so that the film thickness after solvent drying was 25 ⁇ m.
• Metal ion content Sulfuric acid and perchloric acid were added to the sample film obtained by the above method for wet decomposition by heating, and the decomposition solution was diluted.
• the diluted solution was analyzed using an atomic absorption spectrophotometer (AA-6300 manufactured by Shimadzu Corporation) to measure the contents of Li, Na, K, Mg, and Ca, respectively, and the total was taken as the metal ion content.
• Polymer A was solidified into fibers by adding the obtained polymerization solution to a large amount of pure water with stirring, pulverizing it in a mixer for 5 minutes, heating it in a hot air oven at 80°C for 1 hour, and then heating it in a vacuum oven at 120°C for 1 hour. By drying for 12 hours, a powder of Polymer A was obtained.
• diphenyl ether (DPE) corresponding to 90 parts by weight based on 100 parts by weight of Polymer A is added to DMAc and dissolved by stirring at 60° C. for 2 hours to prepare a solution containing Polymer A. I got it.
• the obtained aromatic polyamide solution was cast into a film on a glass plate using an applicator at room temperature, dried at 115°C for 30 minutes and 265°C for 5 minutes in a hot air oven, and then removed from the glass substrate. By peeling, a film containing aromatic polyamide (polymer A) as a main component and having a thickness of 30 ⁇ m was obtained.
• the hot air oven used was Safety Oven SPH100 (manufactured by ESPEC Co., Ltd.), and was used one hour after the temperature display reached the set temperature with the opening/closing damper set at 50%.
• Table 1 shows the physical properties of the obtained film.
• Example 2 A film containing aromatic polyamide (polymer A) as a main component was obtained in the same manner as in Example 1 except that DPE corresponding to 150 parts by weight was added to the solution based on 100 parts by weight of polymer A. Table 1 shows the physical properties of the obtained film.
• Example 3 A film containing aromatic polyamide (polymer A) as a main component was obtained in the same manner as in Example 1 except that DPE corresponding to 180 parts by weight was added to the solution based on 100 parts by weight of polymer A. Table 1 shows the physical properties of the obtained film.
• Example 4 A film containing aromatic polyamide (polymer A) as a main component was obtained in the same manner as in Example 1 except that DPE corresponding to 5 parts by weight was added to the solution based on 100 parts by weight of polymer A. Table 1 shows the physical properties of the obtained film.
• Example 5 An aromatic polyamide (polymer A) was prepared as the main component in the same manner as in Example 1 except that dibenzyl ether (DBE) equivalent to 60 parts by weight per 100 parts by weight of polymer A was added to the solution instead of DPE. Got the film. Table 1 shows the physical properties of the obtained film.
• DBE dibenzyl ether
• Example 6 A film mainly composed of aromatic polyamide (polymer A) was prepared in the same manner as in Example 1 except that diphenylamine (DPA) corresponding to 60 parts by weight per 100 parts by weight of polymer A was added to the solution instead of DPE. Obtained. Table 1 shows the physical properties of the obtained film.
• DPA diphenylamine
• Example 7 An aromatic polyamide (polymer A) was prepared as the main component in the same manner as in Example 1 except that benzhydrol (BzH) corresponding to 60 parts by weight per 100 parts by weight of polymer A was added to the solution instead of DPE. Got the film. Table 1 shows the physical properties of the obtained film.
• Example 8 The raw material monomers are 2-chloro-1,4-phenylenediamine (CTPA) corresponding to 90 mol% of the total amount of diamine and 4,4'-diaminodiphenyl ether corresponding to 10 mol% of the total amount of diamine, and diamine as acid chloride.
• Powder of aromatic polyamide (Polymer B) was obtained in the same manner as in Example 1 except that CTPC was 99 mol% of the total amount. Together with the obtained powder of Polymer B, DPE equivalent to 120 parts by weight per 100 parts by weight of Polymer B was added to DMAc and dissolved by stirring at 60 ° C. for 2 hours to obtain a solution containing Polymer B. .
• a film containing aromatic polyamide (polymer B) as a main component was obtained in the same manner as in Example 1 using a solution containing polymer B. Table 1 shows the physical properties of the obtained film.
• Example 9 TFMB corresponding to 100 mol% of the total amount of diamine was dissolved in dehydrated DMAc at room temperature under a nitrogen stream. 4,4'-(hexafluoroisopropylidene) diphthalic anhydride corresponding to 25 mol % based on the total amount of diamine was added thereto over 15 minutes, and after the entire amount was added, the mixture was stirred for 30 minutes. Next, terephthaloyl chloride (TPC) corresponding to 74 mol % based on the total amount of diamine was added over 30 minutes. After the entire amount was added, the aromatic polyamic acid was polymerized by stirring for about 2 hours.
• TPC terephthaloyl chloride
• the obtained polymerization solution was added to a large amount of pure water with stirring to solidify the polymer into fibers, and the mixture was pulverized for 5 minutes with a mixer to obtain a powder of an aromatic polyamide-imide precursor. Together with the obtained precursor powder, DPE corresponding to 150 parts by weight per 100 parts by weight of the precursor was added and dissolved by stirring at 60°C for 2 hours to form a solution containing the aromatic polyamideimide precursor. Obtained. Using this solution, a film containing aromatic polyamideimide (polymer C) as a main component was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the obtained film.
• Example 10 A film mainly composed of aromatic polyamide (polymer A) was prepared in the same manner as in Example 1 except that diphenyl sulfide (DPS) corresponding to 90 parts by weight per 100 parts by weight of polymer A was added to the solution instead of DPE. I got it. Table 1 shows the physical properties of the obtained film.
• DPS diphenyl sulfide
• Example 11 A film containing aromatic polyamide (polymer A) as the main component was obtained in the same manner as in Example 1 except that the film was formed to have a film thickness of 50 ⁇ m. Table 1 shows the physical properties of the obtained film.
• Example 12 A film containing aromatic polyamide (polymer A) as a main component was obtained in the same manner as in Example 1 except that the film was formed to have a film thickness of 80 ⁇ m. Table 1 shows the physical properties of the obtained film.
• Example 13 A film containing aromatic polyamide (polymer A) as a main component was obtained in the same manner as in Example 1 except that the film was formed to have a film thickness of 200 ⁇ m. Table 1 shows the physical properties of the obtained film.
• Example 14 A film containing aromatic polyamide (polymer A) as the main component was obtained in the same manner as in Example 1 except that the film was formed to have a film thickness of 1 ⁇ m. Table 1 shows the physical properties of the obtained film.
• Example 15 A resin layer containing aromatic polyamide (polymer A) as the main component was prepared in the same manner as in Example 1, except that the substrate on which the aromatic polyamide solution was cast was a 20 ⁇ m glass film, and the resin layer was not peeled off from the glass after drying. A laminate consisting of glass and glass was obtained. Table 1 shows the physical properties of the obtained laminate. Note that the metal ion content was not measured.
• Example 16 As a curable resin precursor, pentaerythritol tri- and tetraacrylate (KAYARAD PET30 manufactured by Nippon Kayaku Co., Ltd.), which is a polyfunctional acrylate compound ( ⁇ ), and pentaerythritol tetrakis (3-mercapto), which is a polyfunctional thiol compound ( ⁇ ), are used.
• silica particles organosilica sol, MEK-AC-5140Z, manufactured by Nissan Chemical Industries, Ltd.
• bis(2-phenyl-2) as a photopolymerization initiator.
• -Oxoacetic acid) oxybisethylene compound (Omnirad 754 manufactured by IGM Resins) was used.
• the above hard coat paint was applied to one side of the film obtained by the method described in Example 1 using a gravure coater, and dried for 30 seconds in an oven at a drying temperature of 90° C. and a wind speed of 15 m/min.
• the coating film was cured by irradiating ultraviolet rays with an output of 120 W/cm and an integrated light amount of 400 mJ/cm 2 using a high-pressure mercury lamp to form a hard coat layer with a thickness of 20 ⁇ m on the surface.
• the ultraviolet irradiation step the coating film was cured while being heated in a nitrogen atmosphere with an oxygen concentration of less than 1% by volume so that the surface temperature of the coating film was 50°C. Thereby, a laminate consisting of a resin layer containing aromatic polyamide (polymer A) as a main component and a hard coat layer was obtained. Table 1 shows the physical properties of the obtained laminate. Note that the metal ion content was not measured.
• Example 1 A film containing aromatic polyamide (polymer A) as a main component was obtained in the same manner as in Example 1 except that DPE corresponding to 350 parts by weight based on 100 parts by weight of polymer A was added to the solution. Table 1 shows the physical properties of the obtained film. In-plane retardation could not be measured due to the opacity of the film.
• Example 2 A film containing aromatic polyamide (polymer A) as the main component was obtained in the same manner as in Example 1 except that only the polymer A powder was dissolved in DMAc. Table 1 shows the physical properties of the obtained film. In-plane retardation could not be measured due to the opacity of the film.
• Example 3 A film mainly composed of aromatic polyamide (polymer A) was produced in the same manner as in Example 1 except that 26 parts by weight of lithium chloride (LiCl) was added to the solution based on 100 parts by weight of polymer A in place of DPE. Although a film was tried, LiCl precipitated and no film could be obtained.
• LiCl lithium chloride
• the main component was aromatic polyamide (polymer A) in the same manner as in Example 1 except that 90 parts by weight of 1-phenoxy-2-propanol (PPH) was added to the solution based on 100 parts by weight of polymer A in place of DPE. A film was obtained. Table 1 shows the physical properties of the obtained film. In-plane retardation could not be measured due to the opacity of the film.
• PPH 1-phenoxy-2-propanol
• Example 7 A solution containing aromatic polyamide (polymer A) was obtained in the same manner as in Example 1 except that 26 parts by weight of lithium chloride (LiCl) was added to the solution based on 100 parts by weight of polymer A in place of DPE.
• This solution was cast into a film on a glass plate using an applicator at room temperature, and the resulting gel film was peeled off from the glass plate by drying at 115°C for 20 minutes and fixed by pasting it on a metal frame. .
• the gel film was washed with the metal frame under running water for 10 minutes. After the gel film was taken out of the water and drained, it was dried in a hot air oven at 265° C. for 5 minutes to obtain a 50 ⁇ m thick film mainly composed of aromatic polyamide (polymer A).
• Table 1 shows the physical properties of the obtained film.

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