Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a laminate containing a self-healing layer and a polyimide film. More specifically, the present invention relates to a laminate made of a polyimide film which exhibits excellent transparency, self-healing property, flexibility, and excellent adhesion to a self-healing layer.
• the front plate of an image display device such as a touch panel or a display
• the periphery of an electrode are hard coated on a transparent base film for the purpose of imparting scratch resistance so that the visibility is not deteriorated due to scratches during handling.
• a hard coat film provided with a layer is used (Patent Document 1).
• Patent Document 2 a touch panel or display having a foldable image display portion has been proposed, and the hard coat film has better flexibility than before. It came to be required.
• the hard coat layer provided on the hard coat film has a high surface hardness in order to impart scratch resistance, but the coat layer having a high surface hardness tends to be brittle, so it is difficult to achieve both excellent flexibility. there were. Therefore, as a means to replace the hard coat layer, a flexible and tough coat layer is formed, and a self-healing coat layer having a function of spontaneously eliminating deformations and scratches caused by stress during handling and processing, etc. (Patent Document 3) has been proposed.
• thermoplastic resin film made of polyethylene terephthalate (PET), acrylic, polycarbonate (PC), triacetyl cellulose (TAC), polyolefin or the like is generally used. It is used.
• PET polyethylene terephthalate
• PC polycarbonate
• TAC triacetyl cellulose
• polyolefin polyolefin
• the base film In order to directly form functional elements such as electrodes and display elements, the base film is required to have a high tensile elastic modulus, low CTE, heat resistance and chemical resistance.
• a polyimide film suitable for such a base film is to be used as a base film for a self-healing film having excellent flexibility and bending resistance exemplified in Patent Document 4, the surface of the polyimide film is flat and low. Due to its activity, the adhesion to the polyimide film is insufficient, and the coating layer tends to peel off or fall off during the processing process or bending.
• the self-healing layer has a function of absorbing external force during handling and processing to repair deformation and scratches, and since it is provided on the front surface of the image display device, it has low tackiness, antifouling property, and chemical resistance. It is necessary to combine the properties, and a component having a high degree of cross-linking and low activity in composition is used. Therefore, with respect to the self-repairing layer, the easy-adhesion layer exemplified in Patent Document 5 for the hard coat layer has insufficient adhesion, and the self-repairing layer is liable to peel off or fall off during the processing process or bending.
• both the polyimide film and the self-healing layer have low activity in this way, it is a problem to obtain adhesion between the self-healing layer and the polyimide film while exhibiting excellent transparency, self-healing property, and flexibility. there were.
• the present invention has the following configuration.
• Polyimide having a tensile elastic modulus of 3 GPa or more in both the MD direction and the TD direction, a CTE of -5 ppm / ° C. to + 55 ppm / ° C. in both the MD direction and the TD direction, and a solvent content of 0.5 to 5.0% by mass.
• a laminate comprising a film and a self-healing layer formed on at least one surface of the polyimide film.
• the laminate has a return rate of 80 after applying a minute load of 0.5 mN from a Vickers quadrangular pyramid diamond indenter to the surface with a micro hardness tester and holding it for 5 seconds, then unloading it to 0.005 mN and holding it for 60 seconds. % Or more is preferable.
• the adhesion rate of the self-repairing layer cut in a grid pattern to the polyimide film by the cross-cut method of JIS K 5600-5-6 (1999) is 80% or more.
• the laminated body has a yellow index of 10 or less, a light transmittance of 70% or more at a wavelength of 400 nm, and a total light transmittance of 85% or more.
• the self-repairing layer is preferably a polymer composition containing cross-linking points, and a part or all of the cross-linking points is a movable cross-linking point.
• the present invention even if a polyimide film having a low activity surface is used as a base film, it is possible to provide a laminate having excellent adhesion to a self-repairing layer while exhibiting excellent self-repairing properties. Further, since it has excellent transparency and flexibility, it is possible to provide a transparent laminate suitable for the front plate and the periphery of electrodes of an image display device such as a touch panel or a display in which an image display portion is foldable.
• the laminate of the present invention is a laminate containing a polyimide film and a self-healing layer formed on at least one surface of the polyimide film.
• the polyimide film constituting the laminate of the present invention is a polymer film having an imide bond in the main chain, preferably a polyimide film or a polyamide-imide film, and more preferably a polyimide film.
• the polyimide film of the present invention is preferably obtained by any of the following production methods.
• a polyamic acid (polyimide precursor) solution obtained by polymerizing diamines and tetracarboxylic acids in a solvent is applied to a support for producing a polyimide film, dried, and a green film (green film).
• precursor film "polyamic acid film” or “polyamic acid film”
• green film green film
• a polyimide solution obtained by a dehydration ring-closing polymerization reaction of diamines and tetracarboxylic acids in a solvent is applied to a support for producing a polyimide film, dried, and a solvent of 1 to 50% by mass is applied. It can also be obtained by treating a polyimide film containing 1 to 50% by mass of a solvent at a high temperature and drying it on a support for producing a polyimide film or in a state of being peeled off from the support.
• a polyamide-imide solution obtained by polymerizing diisocyanates and tricarboxylics in a solvent is applied to a support for producing a polyamide-imide film, dried, and a solvent of 1 to 50% by mass is used. It is obtained by treating a polyamide-imide film containing 1 to 50% by mass of a solvent at a high temperature and drying it on a support for producing a polyamide-imide or in a state of being peeled off from the support. ..
• Dicarboxylic acids can also be appropriately used in the above three production methods.
• tetracarboxylic acids examples include aromatic tetracarboxylic acids (including acid anhydrides thereof) and aliphatic tetracarboxylic acids (acid anhydrides thereof) usually used for polyimide synthesis or polyamideimide synthesis.
• aromatic tetracarboxylic acid anhydrides or alicyclic tetracarboxylic acid anhydrides are preferable, and aromatic tetracarboxylic acid anhydrides are more preferable from the viewpoint of heat resistance, and they are light-transmitting (transparent). From the viewpoint, alicyclic tetracarboxylic acids are more preferable.
• the tetracarboxylic acids are acid anhydrides, the number of anhydride structures in the molecule may be one or two, but those having two anhydride structures (dianhydride) are preferable. ) Is good.
• Tetracarboxylic acids, tricarboxylic acids, and dicarboxylic acids may be used alone or in combination of two or more.
• Examples include carboxylic acids and their acid anhydrides.
• dianhydride having two acid anhydride structures is preferable, and in particular, 4,4'-(2,2-hexafluoroisopropylidene) diphthalic acid dianhydride and 4,4'-oxydiphthal.
• Acid dianhydride is preferred.
• the aromatic tetracarboxylic acids may be used alone or in combination of two or more. When heat resistance is important, the aromatic tetracarboxylic acids are preferably, for example, 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 70% by mass or more of all tetracarboxylic acids. It is 80% by mass or more.
• Examples of alicyclic tetracarboxylic acids for obtaining a highly colorless and transparent polyimide include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, and 3- (carboxy).
• Tetracarboxylic acids and their acid anhydrides are preferable, and in particular, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride and 1,2,3,4-cyclohexanetetracarboxylic.
• Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride is preferred, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride is more preferred, and 1,2,3,4-cyclobutanetetracarboxylic hydride is even more preferred. These may be used alone or in combination of two or more.
• the alicyclic tetracarboxylic acids are preferably, for example, 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 70% by mass or more of all tetracarboxylic acids. Is 80% by mass or more.
• tricarboxylic acids examples include aromatic tricarboxylic acids such as trimeric acid, 1,2,5-naphthalene tricarboxylic acid, diphenyl ether-3,3', 4'-tricarboxylic acid, and diphenylsulfone-3,3', 4'-tricarboxylic acid.
• An acid or an alkylene such as a hydrogenated additive of the above aromatic tricarboxylic acid such as hexahydrotrimelic acid, ethylene glycol bistrimelite, propylene glycol bistrimerite, 1,4-butanediol bistrimelite, polyethylene glycol bistrimelite. Glycolbitrimeritate and these monoanhydrides and esterified products can be mentioned.
• a monoanhydride having one acid anhydride structure is preferable, and in particular, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride are preferable. These may be used alone or in combination of two or more.
• dicarboxylic acids examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, 4,4'-oxydibenzenedicarboxylic acid, and 1,4-.
• aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, 4,4'-oxydibenzenedicarboxylic acid, and 1,4-.
• Hydrogenated additives of the above aromatic dicarboxylic acids such as cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, heptanedioic acid, octanedioic acid. , Azelaic acid, sebacic acid, undecadioic acid, dodecanedioic acid, 2-methylsuccinic acid, and acidified or esterified products thereof.
• aromatic dicarboxylic acids and hydrogenated products thereof are preferable, and terephthalic acid, 1,4-cyclohexanedicarboxylic acid, and 4,4'-oxydibenzenedicarboxylic acid are particularly preferable.
• the dicarboxylic acids may be used alone or in combination of two or more.
• the diamines or isocyanates for obtaining a polyimide having high heat resistance and / or colorless transparency in the present invention are not particularly limited, and are aromatic diamines and aliphatic diamines usually used for polyimide synthesis or polyamide-imide synthesis. , Alicyclic diamines, aromatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates and the like can be used. From the viewpoint of heat resistance, aromatic diamines or aromatic diisocyanates are preferable, and from the viewpoint of transparency, alicyclic diamines or alicyclic diisocyanates are preferable.
• aromatic diamines or diisocyanates having a benzoxazole structure because it is possible to develop high elastic modulus, low coefficient of thermal expansion, and low linear expansion coefficient as well as high heat resistance.
• the diamines and isocyanates may be used alone or in combination of two or more.
• aromatic amines examples include 2,2'-dimethyl-4,4'-diaminobiphenyl, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, and 1,4-bis. (4-Amino-2-trifluoromethylphenoxy) benzene, 2,2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'- Bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone , 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,
• a part or all of the hydrogen atoms on the aromatic ring of the aromatic diamine may be substituted with a halogen atom, an alkyl group or an alkoxyl group having 1 to 3 carbon atoms, or a cyano group, and further, the carbon number of carbon atoms may be substituted.
• a part or all of the hydrogen atoms of the alkyl group or the alkoxyl group of 1 to 3 may be substituted with halogen atoms.
• the aromatic diamines may be used alone or in combination of two or more.
• the aromatic diamines having the benzoxazole structure are not particularly limited, and for example, 5-amino-2- (p-aminophenyl) benzoxazole and 6-amino-2- (p-aminophenyl) benzo.
• aromatic diamines having an oxazole structure may be used alone or in combination of two or more.
• alicyclic diamines examples include 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, and 1,4-diamino-2-n-propyl.
• Cyclohexane 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-Diamino-2-tert-butylcyclohexane, 4,4'-methylenebis (2,6-dimethylcyclohexylamine), cyclohexane-1,4-diyldimethaneamine, bicyclo [2,2,1] heptane- Examples thereof include 2,5-diamine.
• 1,4-diaminocyclohexane or 1,4-diamino-2-methylcyclohexane is particularly preferable, and 1,4-diaminocyclohexane is more preferable.
• the alicyclic diamines may be used alone or in combination of two or more.
• diisocyanates examples include diphenylmethane-2,4'-diisocyanate, 3,2'-or 3,3'-or 4,2'-or 4,3'-or 5,2'-or 5,3'. -Or 6,2'-or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'-or 3,3'-or 4,2'-or 4,3'-or 5,2 '-Or 5,3'-or 6,2'-or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'-or 3,3'-or 4,2'-or 4, 3'-or 5,2'-or 5,3'-or 6,2'-or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3, 3'-diisocyanate, diphen
• Didimethylbiphenyl-4,4'-diisocyanate, naphthalene-2,6-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, or 1,4-cyclohexanediisocyanate is preferred.
• the diisocyanates may be used alone or in combination of two or more.
• the solvent used in the polyamic acid solution, the polyimide solution, and the polyamide-imide solution of the present invention is not particularly specified as long as it dissolves a polyimide resin or a precursor thereof, but for example, N-methyl-2-pyrrolidone, N. , N-Dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, sulfolane, dimethyl sulfoxide, ⁇ -butyrolactone, cyclohexanone, cyclopentanone and the like. These may be used alone or in combination of two or more.
• N, N-dimethylacetamide as the main component of the organic solvent.
• a poor solvent such as toluene or xylene may be used to the extent that the polyimide resin or its precursor does not precipitate.
• the thickness of the polyimide film in the present invention is preferably 3 ⁇ m or more, more preferably 11 ⁇ m or more, and further preferably 24 ⁇ m or more.
• the upper limit of the thickness of the polyimide film is not particularly limited, but it is preferably 250 ⁇ m or less, more preferably 150 ⁇ m or less, and further preferably 100 ⁇ m or less for use as a flexible electronic device.
• the tensile elastic modulus of the polyimide film of the present invention needs to be 3 GPa or more in both the MD direction and the TD direction, preferably 4 GPa or more, and more preferably 5 GPa or more.
• the tensile elastic modulus in both the MD direction and the TD direction is preferably 20 GPa or less, more preferably 12 GPa or less, and further preferably 10 GPa or less.
• the polyimide film can be used as a flexible film.
• the tensile elastic modulus of the polyimide film refers to the average value of the tensile elastic modulus in the flow direction (MD direction) and the tensile elastic modulus in the width direction (TD direction) of the polyimide film.
• the method for measuring the tensile elastic modulus of the polyimide film is as described in Examples.
• the average CTE of the polyimide film in the present invention between 30 ° C. and 300 ° C. needs to be ⁇ 5 ppm / ° C. to + 55 ppm / ° C. It is preferably -4 ppm / ° C to + 45 ppm / ° C, more preferably -3 ppm / ° C to + 35 ppm / ° C, still more preferably -2 ppm / ° C to + 20 ppm / ° C, and even more preferably + 1 ppm / ° C to + 10 ppm. / ° C.
• CTE is a factor that represents reversible expansion and contraction with respect to temperature.
• the CTE of the polyimide film refers to the average value of the CTE in the flow direction (MD direction) and the CTE in the width direction (TD direction) of the polyimide film.
• the method for measuring CTE of the polyimide film is as described in Examples.
• the polyimide film showing the tensile elastic modulus and CTE of the present invention can be realized by stretching in the film forming process of the polyimide film.
• a polyimide solution is applied to a support for producing a polyimide film, dried to form a polyimide film containing a solvent of 1 to 50% by mass, and further peeled off on or from the support for producing a polyimide film.
• 1.5 to 4.0 times in the MD direction and 1.4 to 3.0 times in the TD direction It can be realized by stretching to.
• an unstretched thermoplastic polymer film is used as a support for producing a polyimide film, the thermoplastic polymer film and the polyimide film are stretched at the same time, and then the stretched polyimide film is peeled off from the thermoplastic polymer film.
• the preferred draw ratio in the MD direction is 1.7 to 3.5 times, more preferably 2.0 to 3.0 times.
• the preferred draw ratio in the TD direction is 1.7 times to 3.5 times, more preferably 2.0 times to 3.0 times.
• the ratio of the stretching ratio in the MD direction to the stretching ratio in the TD direction is preferably more than 1, more preferably 1.01 or more, still more preferably 1.05 or more, and even more. It is preferably 1.08 or more, and particularly preferably 1.1 or more. Further, it is preferably 2.0 or less, more preferably 1.8 or less, further preferably 1.5 or less, and particularly preferably 1.2 or less.
• the solvent content of the polyimide film of the present invention needs to be 0.5 to 5.0% by mass. It is preferably in the range of 0.7 to 4.0% by mass, more preferably in the range of 1.0 to 3.0% by mass.
• the solvent content to the above upper limit value or less, it becomes easy to keep the tensile elastic modulus and CTE within a preferable range, and it is possible to prevent the residual solvent from migrating to the self-repairing layer and causing whitening and devitrification. Therefore, deterioration of the light transmittance and the total light transmittance at a wavelength of 400 nm can be suppressed.
• the solvent contained in the polyimide film may be a residue (residual solvent) of the solvent in the process of producing the polyimide film (for example, the process of treating the polyimide film at a high temperature and drying it), or the solvent may be used after the polyimide film is produced. It may be added. It is preferably a residual solvent in the process of producing the polyimide film.
• the drying conditions for the polyimide film and / or the green film are not particularly limited, and may be dried in one step or in multiple steps. It is preferable to dry in multiple stages.
• the number of drying stages during multi-stage drying is not particularly limited, and is preferably two or more stages, and more preferably three or more stages. Further, it is preferably 10 steps or less, and more preferably 5 steps or less. It is preferable that the drying temperature in the multiple stages is higher as the latter stage is reached.
• the first step is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 200 ° C. or lower, and further preferably 150 ° C. or higher and 180 ° C. or lower.
• the second step is preferably more than 250 ° C. and 500 ° C. or lower, more preferably 280 ° C. or higher and 450 ° C. or lower, and further preferably 300 ° C. or higher and 400 ° C. or lower.
• the drying time can be set according to the above drying temperature and film thickness, the type of solvent, and the drying equipment used.
• the drying time of the first step is preferably 2 minutes or more and 15 minutes or less, more preferably 3 minutes or more and 12 minutes or less, and further preferably. It is 5 minutes or more and 8 minutes or less.
• the drying time of the second step is preferably more than 1 minute and 10 minutes or less, more preferably 2 minutes or more and 8 minutes or less, and further preferably 3 minutes or more and 5 minutes or less.
• the first step is preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 190 ° C. or lower, and further preferably 150 ° C. or higher and 180 ° C. or lower.
• the second step is preferably more than 200 ° C. and 300 ° C. or lower, more preferably 210 ° C. or higher and 280 ° C. or lower, and further preferably 220 ° C. or higher and 250 ° C. or lower.
• the third step is preferably more than 300 ° C. and 500 ° C. or lower, more preferably 320 ° C. or higher and 450 ° C. or lower, and further preferably 340 ° C.
• the drying time can be set by the drying temperature.
• the drying time of the first step is preferably 30 seconds or more and 10 minutes or less, more preferably 1 minute or more and 8 minutes or less, and further preferably 2 minutes or more and 5 minutes. Less than a minute.
• the drying time of the second step is preferably 30 seconds or more and 10 minutes or less, more preferably 1 minute or more and 8 minutes or less, and further preferably 2 minutes or more and 5 minutes or less.
• the drying time of the third step is preferably more than 1 minute and less than 10 minutes, more preferably 2 minutes or more and 9 minutes or less, and further preferably 3 minutes or more and 8 minutes or less.
• the laminate of the present invention is a laminate in which a self-repairing layer is laminated on at least one surface of a polyimide film exhibiting the above tensile elastic modulus and CTE, whereby the self-repairing property of the laminate is ensured.
• the self-healing property refers to the property of restoring deformation or scratches caused by strain due to stress concentration at the time of stress unloading, and specifically, by the "return rate" obtained by the measurement method described in the examples. Be evaluated.
• the return rate calculated by the measurement of the return rate is preferably 80% or more, more preferably 85% or more, further preferably 90% or more, and 95% or more. Even more preferably, 100% is particularly preferable.
• the self-healing layer constituting the laminate of the present invention is mainly provided on the front surface of the image display device, it has a cross-linking point from the viewpoint of requiring low tackiness, antifouling property, and chemical resistance, and further self-healing. From the viewpoint of achieving a return rate of 80% or more as a property, a polymer composition containing a cross-linking point in which a part or all of the cross-linking points is movable (hereinafter, also referred to as “self-repairing polymer composition”). Is preferable.
• the mobile cross-linking point in the present invention indicates a cross-linking point formed by a chemical bond other than a covalent bond as the first form, and examples of the chemical bond other than the covalent bond include an ionic bond and a hydrogen bond.
• the bond when the strain created by stress concentration propagates, the bond is broken and deformed or scratched, but after the stress is removed, the bond is regenerated by molecular motion, so the deformation or scratch disappears. Has self-healing properties.
• the mobile cross-linking point in the present invention indicates a cross-linking point consisting of a constraint due to a geometric shape that does not depend on a chemical bond as a second form, and the constraint due to the geometry is linear at the opening of a cyclic molecule.
• the polymer composition having a cross-linking point formed by a chemical bond other than the covalent bond, which is the first form as the cross-linking point having mobility in the present invention is a polymer composition utilizing an ionic bond, and is a metal ion.
• examples thereof include a metal ion-containing (meth) acrylic acid ethylene copolymer, a metal ion-containing sulfonic acid polyester polymer, and a metal ion-containing sulfonic acid polyester polyether copolymer, which utilize hydrogen bonding.
• a polyether urethane copolymer As the polymer composition, a polyether urethane copolymer, an aliphatic polyester urethane copolymer, a polyether polyester urethane copolymer, a polyurethane acrylate copolymer, a polyether polyamide copolymer, and an aliphatic polyester polyamide copolymer are included. Can be mentioned.
• Examples of the polymer composition having a cross-linking point consisting of constraints due to the geometric shape, which is the second form as the cross-linking point having mobility in the present invention include a cyclic polyether ring-penetrating polyether polymer and a cyclic polyether ring-penetrating fat.
• Examples thereof include group polyester copolymers, cyclic polyether ring-penetrating polyacrylic polymers, cyclodextrin ring-penetrating polyether polymers, and cyclodextrin ring-penetrating aliphatic polyester copolymers.
• the content of the self-repairing polymer composition contained in the self-repairing layer is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and particularly. It is preferably 99.9% by mass or more, and may be 100% by mass.
• the polymer composition containing a cross-linking point in which a part or all of the cross-linking points is movable may be used alone or in combination of a plurality of the cross-linking points, and if necessary, a solvent, a softening agent, and the like.
• the present invention includes plasticizers, antioxidants, antioxidants, ultraviolet absorbers, light stabilizers, surface lubricants, leveling agents, antifouling agents, mold release agents, heat stabilizers, lubricants, inorganic fine particles, surfactants, etc. Additives commonly used in the technical field to which the product belongs can be additionally included.
• the content thereof can be variously adjusted within a range that does not deteriorate the physical properties of the laminate of the present invention, and thus is not particularly limited.
• the thickness of the self-repairing layer constituting the laminate of the present invention is preferably 5 ⁇ m or more, more preferably 8 ⁇ m or more, and particularly preferably 10 ⁇ m or more, from the viewpoint of ensuring adhesion and sufficiently exhibiting the self-repairing function. preferable.
• the upper limit thickness is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
• the self-healing layer constituting the laminate of the present invention is formed by applying a self-healing polymer composition on a polyimide film, drying it if necessary, irradiating it with heat or active energy rays, and curing it. can do. That is, the self-repairing polymer composition for forming the self-repairing layer according to the present invention is preferably a thermosetting polymer composition or an active energy ray-curable polymer composition.
• the wet coating method is preferable as the coating method used for coating the self-healing polymer composition.
• Examples of such a wet coating method include a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, a roll coating method, and a lip coating method.
• the thickness of the laminate is preferably 8 ⁇ m or more, more preferably 15 ⁇ m, and even more preferably 20 ⁇ m or more. Further, it is preferably 300 ⁇ m or less, more preferably 200 ⁇ m or less, and further preferably 100 ⁇ m or less.
• the polyimide film and the self-repairing layer are laminated in this order, and the self-repairing layer has adhesion to the polyimide film, and the adhesion is specifically described in Examples. It is evaluated by the "adhesion rate" obtained by the measuring method.
• the adhesion of the self-repairing layer is preferably 80% or more, more preferably 85% or more, further preferably 90% or more, further preferably 95% or more, 100%. % Is particularly preferable.
• the adhesion rate can be a preferable value by setting the solvent content contained in the polyimide film to be equal to or higher than the above-mentioned lower limit value.
• the polyimide film may be subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment or the like as pretreatment on the surface as long as the transparency and adhesion to the self-repairing layer are not deteriorated. ..
• the yellowness index is preferably 10 or less, more preferably 7 or less, and further. It is preferably 5 or less, and even more preferably 3 or less.
• the lower limit of the yellowness of the polyimide film is not particularly limited, but it is preferably 0.1 or more, more preferably 0.2 or more, and further preferably 0.3 or more for use as a flexible electronic device. be.
• the light transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 72% or more. It is even more preferably 75% or more, and even more preferably 80% or more.
• the upper limit of the light transmittance of the polyimide film at a wavelength of 400 nm is not particularly limited, but is preferably 99% or less, more preferably 98% or less, still more preferably 97% or less for use as a flexible electronic device. Is.
• the total light transmittance is preferably 85% or more, more preferably 86% or more, and further preferably. Is 87% or more, and even more preferably 88% or more.
• the upper limit of the total light transmittance of the polyimide film is not particularly limited, but is preferably 99% or less, more preferably 98% or less, still more preferably 97% or less for use as a flexible electronic device. ..
• ⁇ Tension elastic modulus of polyimide film> A strip of 100 mm ⁇ 10 mm cut out in each of the flow direction (MD direction) and the width direction (TD direction) of the polyimide film was used as a test piece. The test piece was cut out from the central portion in the width direction. Using a tensile tester (manufactured by Shimadzu Corporation, Autograph (R), model name AG-5000A), 5 samples each in the MD direction and TD direction under the conditions of a temperature of 25 ° C., a tensile speed of 50 mm / min, and a distance between chucks of 40 mm. The tensile elastic modulus was measured, and the average value of all the measured values was obtained.
• a tensile tester manufactured by Shimadzu Corporation, Autograph (R), model name AG-5000A
• CTE Cost of linear expansion
• MD direction flow direction
• TD direction width direction
• the expansion / contraction rate / temperature was measured, and this measurement was performed up to 300 ° C., and the average value of all the measured values was calculated as CTE.
• ⁇ Solvent content in polyimide film The solvent content in the polyimide film was measured using a thermogravimetric analyzer (manufactured by TA Instruments, model name TGA2950). A sample of about 10 mg was set in an aluminum microcell and heated to 500 ° C. at a rate of 5 ° C./min. The measurement was carried out in a nitrogen atmosphere, and the weight reduced between 100 ° C. and 300 ° C. was defined as the solvent content.
• ⁇ Return rate of laminated body> Using a micro-hardness tester Fisherscope HM2000 (manufactured by Fisher) as a measuring device, the laminate is fixed to a slide glass with an instant adhesive Aron Alpha 221F (manufactured by Toagosei) and set in the above measuring device. A load is applied to the laminate fixed to the slide glass from the Vickers quadrangular pyramid diamond indenter to 0.5 mN over 15 seconds at a measurement temperature of 30 ° C. and held at 0.5 mN for 5 seconds. The maximum displacement at that time is (h1).
• ⁇ Adhesion rate of laminated body> By the cross-cut method of JIS K 5600-5-6 (1999), a grid peeling test jig is used on the self-repairing layer of the laminated sample under constant temperature and humidity conditions (23 ° C., 50% RH). Eleven linear cuts at 1 mm intervals were inserted in each of the vertical direction and the horizontal direction to prepare 100 cross cuts of 1 square mm.
• Adhesive tape No. 252 manufactured by Sekisui Chemical Co., Ltd. is attached onto the cross-cut squares, pressed evenly with a spatula, and then the adhesive tape is peeled off from the laminate in the 90-degree direction. ..
• the adhesion rate is determined as the number of self-repairing layer cross-cuts remaining on the polyimide film. In the evaluation, the remaining number out of 100 was determined by "%".
• ⁇ 400 nm light transmittance of laminated body> The light transmittance at a wavelength of 400 nm was measured using a spectrophotometer (“U-2001” manufactured by Hitachi, Ltd.), and the obtained value was converted to a thickness of 20 ⁇ m according to Lambert-Beer's law, and the obtained value was obtained.
• a spectrophotometer (“U-2001” manufactured by Hitachi, Ltd.)
• the obtained value was converted to a thickness of 20 ⁇ m according to Lambert-Beer's law, and the obtained value was obtained.
• the same measurement was performed three times, and the arithmetic mean value was adopted.
• Total light transmittance (TT) of the laminate The total light transmittance (TT) of the polyimide film was measured using HAZEMETER (NDH5000, manufactured by Nippon Denshoku Co., Ltd.). A D65 lamp was used as the light source. The same measurement was performed three times, and the arithmetic mean value was adopted.
• TFMB 4-amino-N- (4-aminophenyl) benzamide
• DABAN 4-amino-N- (4-aminophenyl) benzamide
• 2000 g of N, N-dimethylacetamide were charged and dissolved, and then at room temperature.
• the mixture was stirred for 24 hours to carry out a polymerization reaction.
• it was diluted with 1000 g of N, N-dimethylacetamide to obtain a polyamic acid solution A having a reducing viscosity of 4.50 dl / g.
• BPDA 4,4'-biphenyltetracarboxylic acid dianhydride
• ODPA 4,4 Dissolve ′ -oxydi
• the polyamic acid solution A was applied to a mirror-finished stainless steel endless continuous belt as a film-making support using a die coater (coating width 1240 mm), and dried at 90 to 115 ° C. for 10 minutes.
• a polyamic acid film (containing 9% by mass of residual solvent) that became self-supporting after drying was peeled off from the support and both ends were cut to obtain a green film.
• the obtained green film is conveyed by a pin tenter so that the final pin sheet spacing is 1140 mm, and heat-treated at 170 ° C. for the first stage for 2 minutes, 230 ° C. for the second stage for 2 minutes, and 350 ° C. for the third stage for 6 minutes.
• the film was cooled to room temperature in 2 minutes, and the portions having poor flatness at both ends of the film were cut off with a slitter and wound into a roll to obtain the polyimide film 1A shown in Table 1.
• the polyamic acid solution A was changed to the polyimide solution B or the polyamic acid solution G, and the coating thickness on the support was changed to obtain the polyimide film 1B or the polyimide film 1G shown in Table 1.
• the polyamic acid solution A which is a film-making support, has a region surface roughness (Sa) of 1 nm, a maximum protrusion height (Sp) of 7 nm, and a peak density (Spd) of 20 / square ⁇ m or less.
• a polyester film having no coat layer on its surface was coated with a comma coater (coating width 1240 mm) and dried at 90 to 115 ° C. for 10 minutes.
• a polyamic acid film (containing 10% by mass of residual solvent) that became self-supporting after drying was peeled off from the support and both ends were cut to obtain a green film.
• the obtained green film is conveyed by a pin tenter so that the final pin sheet spacing is 1140 mm, and heat-treated at 170 ° C. for the first stage for 2 minutes, 230 ° C. for the second stage for 2 minutes, and 350 ° C. for the third stage for 6 minutes. Was applied, and the residual solvent was removed so as to be within a predetermined value range. Then, the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain the polyimide film 2A shown in Table 1.
• the polyamic acid solution A was changed to the polyimide solution C or the polyamic acid solution G, and the coating thickness on the support was changed to obtain the polyimide film 2C or the polyimide film 2G shown in Table 1.
• Unstretched polyimide solution B which is a film-making support, has a region surface roughness (Sa) of 3 nm, a maximum protrusion height (Sp) of 12 nm, and a peak density (Spd) of 25 / square ⁇ m or less.
• a polypropylene film is coated with a comma coater (coating width 450 mm) and dried at 85 to 105 ° C. for 30 minutes to form a two-layer film of a support and a polyimide film (containing about 8% mass of residual solvent). Obtained.
• this bilayer film was stretched 2.8 times in the MD direction by utilizing the difference in peripheral speed of the rolls at the same time.
• the rolls were arranged so that the rolls did not come into contact with the polyimide film-side surface of the two-layer film between the rolls having a difference in peripheral speed.
• both ends of the double-layer film are grasped with a clip tenter, and heat treatment is performed at 150 ° C. for 6 minutes so that the final pin sheet spacing is 1140 mm, that is, the stretch is 2.5 times in the TD direction.
• the polyimide film was peeled off from the support of the double-layer film, and further heat-treated at 350 ° C. for 3 minutes to remove the residual solvent within a predetermined value range.
• the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain the polyimide film 3B shown in Table 1.
• the polyimide solution B was changed to the polyimide solution C, and the coating thickness on the support was changed to obtain the polyimide film 3C shown in Table 1.
• the polyamic acid solution A was applied to a mirror-finished stainless steel endless continuous belt as a film-making support using a die coater (coating width 1240 mm), and dried at 90 to 115 ° C. for 10 minutes.
• a polyamic acid film (containing 9% by mass of residual solvent) that became self-supporting after drying was peeled off from the support and both ends were cut to obtain a green film.
• the obtained green film is conveyed by a pin tenter so that the final pin sheet spacing is 1140 mm, and heat-treated at 170 ° C. for the first stage for 2 minutes, 230 ° C. for the second stage for 2 minutes, and 350 ° C. for the third stage for 10 minutes.
• the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain the polyimide film 4A shown in Table 1.
• the polyamic acid solution A which is a film-making support, has a region surface roughness (Sa) of 1 nm, a maximum protrusion height (Sp) of 7 nm, and a peak density (Spd) of 20 / square ⁇ m or less.
• a polyester film having no coat layer on its surface was coated with a comma coater (coating width 1240 mm) and dried at 90 to 115 ° C. for 10 minutes.
• a polyamic acid film (containing 10% by mass of residual solvent) that became self-supporting after drying was peeled off from the support and both ends were cut to obtain a green film.
• the obtained green film is conveyed by a pin tenter so that the final pin sheet spacing is 1140 mm, and heat-treated at 170 ° C. for the first stage for 2 minutes, 230 ° C. for the second stage for 2 minutes, and 350 ° C. for the third stage for 10 minutes. Was applied, and the residual solvent was removed so as to be within a predetermined value range. Then, the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain the polyimide film 5A shown in Table 1.
• the surface of the polyimide solution C which is a film-making support, has a region surface roughness (Sa) of 1 nm, a maximum protrusion height (Sp) of 7 nm, and a peak density (Spd) of 20 / square ⁇ m or less.
• the polyester film having no coat layer was coated with a comma coater (coating width 1240 mm) and dried at 90 to 115 ° C. for 10 minutes.
• a polyamic acid film (containing 10% by mass of residual solvent) that became self-supporting after drying was peeled off from the support and both ends were cut to obtain a green film.
• the obtained green film is conveyed by a pin tenter so that the final pin sheet spacing is 1140 mm, and heat-treated at 170 ° C. for the first stage for 2 minutes, 230 ° C. for the second stage for 2 minutes, and 350 ° C. for the third stage for 1 minute. Was applied, and the residual solvent was removed so as to be within a predetermined value range. Then, the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain the polyimide film 6C shown in Table 1.
• Unstretched polyimide solution B which is a film-making support, has a region surface roughness (Sa) of 3 nm, a maximum protrusion height (Sp) of 12 nm, and a peak density (Spd) of 25 / square ⁇ m or less.
• a polypropylene film is coated with a comma coater (coating width 450 mm) and dried at 85 to 105 ° C. for 30 minutes to form a two-layer film of a support and a polyimide film (containing about 8% mass of residual solvent). Obtained.
• this bilayer film was stretched 2.8 times in the MD direction by utilizing the difference in peripheral speed of the rolls at the same time.
• the rolls were arranged so that the rolls did not come into contact with the polyimide film-side surface of the two-layer film between the rolls having a difference in peripheral speed.
• both ends of the double-layer film are grasped with a clip tenter, and the film is conveyed while being heat-treated at 150 ° C. so that the final pin sheet spacing is 1140 mm, that is, the film is stretched 2.5 times in the TD direction.
• the polyimide film was peeled off from the support of the two-layer film, and further heat treatment was performed at 350 ° C. for 1 minute to remove the residual solvent within a predetermined value range.
• the film was cooled to room temperature in 2 minutes, and the portions of the film having poor flatness were cut off with a slitter and wound into a roll to obtain the polyimide film 7B shown in Table 1.
• composition D for forming a self-repairing layer A composition for forming a polyurethane acrylate copolymer as a polymer composition having a cross-linking point formed by a chemical bond other than a covalent bond was weighed as follows, and mixed and prepared at room temperature.
• AUP-787 (Urethane acrylate containing photoinitiator, manufactured by Tokushiki Co., Ltd.): 100 parts by mass Methyl ethyl ketone: 50 parts by mass Propylene glycol monomethyl ether: 30 parts by mass BYK-381 (surfactant, manufactured by Big Chemie Japan): 1 part by mass
• composition E for forming a self-repairing layer A composition for forming a cyclodextrin ring-penetrating polyether polymer as a polymer composition having a cross-linking point consisting of a constraint due to a geometric shape that does not depend on a chemical bond was weighed as follows, and mixed and prepared at room temperature.
• SM3405P modified polyrotaxane, manufactured by Advanced Soft Materials
• 50 parts by mass M-309 trimethylolpropane triacrylate, manufactured by Toa Synthetic
• 35 parts by mass M284 polyethylene glycol diacrylate, manufactured by Toyo Chemicals
• 15 parts by mass Methyl ethyl ketone 40 parts by mass propylene glycol monomethyl ether: 10 parts by mass Omnirad184 (photopolymerization initiator, manufactured by IGM Resins): 4 parts by mass
• composition F for forming a hard coat layer As the polymer composition for forming the hard coat layer, the composition for forming the (meth) acrylate copolymer was weighed as follows, and mixed and prepared at room temperature.
• OPSTAR Z7530 mixture of organically modified silica fine particles and polyfunctional acrylate, manufactured by Arakawa Chemical Industry Co., Ltd.
• Pentaerythritol triacrylate 34 parts by mass 1-hydroxycyclohexylphenyl ketone: 1.8 parts by mass
• BYK-300 Leveling agent, manufactured by Big Chemie Japan
• propylene glycol monomethyl ether 80 parts by mass
• Example 1 Manufacturing of laminated body>
• the self-healing layer forming composition D was applied to the entire surface of the polyimide film 1A obtained in Production Example 1 with a roll coater. Next, after drying at 80 ° C., while purging nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less, the illuminance of the irradiated portion is 100 mW / square cm using an ultraviolet lamp, and the irradiation amount is 0.3 J.
• the coating layer was cured at / square cm to prepare a laminate in which a self-repairing layer having a laminate thickness of 22.0 ⁇ m and a dry layer thickness of 9.5 ⁇ m was formed.
• Examples 2 to 13 Similarly, a laminate was prepared using the polyimide film shown in Table 1 and the self-repairing layer forming compositions D and E, and the characteristics of the laminate were evaluated. The results are shown in Table 2.
• Comparative Examples 1 to 8 Similarly, a laminate was prepared using the polyimide film shown in Table 1 and the self-repairing layer forming compositions D, E, and F, and the characteristics of the laminate were evaluated. The results are shown in Table 3.
• the laminate of the present invention exhibits excellent transparency, self-healing property, and flexibility, and has excellent adhesion to the self-healing layer. It is extremely useful around the front plate and electrodes of the image display device.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Materials Engineering (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Laminated Bodies (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=77891622

Family Applications (1)

Country Status (4)

Citations (8)

Family Cites Families (24)

• 2021
  • 2021-02-24 CN CN202180017406.9A patent/CN115175816B/zh active Active
  • 2021-02-24 KR KR1020227028038A patent/KR20220156808A/ko active Search and Examination
  • 2021-02-24 JP JP2021559197A patent/JPWO2021192789A1/ja active Pending
  • 2021-02-24 WO PCT/JP2021/006845 patent/WO2021192789A1/ja active Application Filing

Patent Citations (8)

Also Published As

Similar Documents

Legal Events