WO2022137951A1 - Ensemble de feuilles pour mesure de pression, feuille pour mesure de pression, microcapsules, dispersion, procédé de production d'ensemble de feuilles pour mesure de pression, procédé de production de feuille pour mesure de pression - Google Patents

Ensemble de feuilles pour mesure de pression, feuille pour mesure de pression, microcapsules, dispersion, procédé de production d'ensemble de feuilles pour mesure de pression, procédé de production de feuille pour mesure de pression Download PDF

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Publication number
WO2022137951A1
WO2022137951A1 PCT/JP2021/042916 JP2021042916W WO2022137951A1 WO 2022137951 A1 WO2022137951 A1 WO 2022137951A1 JP 2021042916 W JP2021042916 W JP 2021042916W WO 2022137951 A1 WO2022137951 A1 WO 2022137951A1
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Prior art keywords
sheet
microcapsules
layer
pressure measurement
substituent
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PCT/JP2021/042916
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English (en)
Japanese (ja)
Inventor
政宏 八田
宏和 鬼頭
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富士フイルム株式会社
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Priority to CN202180086265.6A priority Critical patent/CN116635502A/zh
Priority to JP2022571987A priority patent/JPWO2022137951A1/ja
Priority to KR1020237020619A priority patent/KR20230106691A/ko
Publication of WO2022137951A1 publication Critical patent/WO2022137951A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L1/00—Measuring force or stress, in general
    • G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/04—Isoindoline dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L5/00—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties

Definitions

  • the present invention relates to a method for manufacturing a pressure measurement sheet set, a pressure measurement sheet, a microcapsule, a dispersion liquid, a pressure measurement sheet set, and a method for manufacturing a pressure measurement sheet.
  • Patent Documents 1 to 3 disclose a pressure measurement sheet set or the like using microcapsules containing a color former.
  • the data measured by lowering the temperature may not reflect the pressure distribution in a high temperature environment, and a pressure measurement sheet set or the like that can accurately measure the pressure in a high temperature environment of 180 ° C or higher is required. It had been.
  • a pressure measurement sheet set or the like that can accurately measure the pressure in a high temperature environment of 180 ° C or higher is required. It had been.
  • the present inventors measured the pressure distribution in a high temperature environment of 180 ° C. or higher with a conventional pressure measurement sheet set or the like, color development occurred even in a region other than the pressurized region, and the pressure was applied. It has been found that the shape of the colored region cannot be easily recognized and the precise pressure distribution cannot be measured. It was also newly found that the color of the coloring region differs depending on the pressure time when the pressure is measured in a high temperature environment.
  • the ability to easily recognize the shape of a region that has been pressurized and developed a color and to suppress the color change of the color-developing region due to the pressurization time is also referred to as being excellent in high-temperature suitability.
  • the conventional pressure measurement sheet set or the like is used at a temperature of less than 150 ° C., not in a high temperature environment (particularly 180 ° C. or higher).
  • the present inventors also examined the pressure measurement sheet sets and the like described in Patent Documents 2 and 3, and found that they were inferior in high-temperature suitability when used in a high-temperature environment (particularly 180 ° C. or higher).
  • Another object of the present invention is to provide a pressure measuring sheet set having excellent high temperature aptitude and a pressure measuring sheet having excellent high temperature aptitude. Another object of the present invention is to provide a method for manufacturing a microcapsule, a dispersion liquid, a sheet set for pressure measurement, and a method for manufacturing a sheet for pressure measurement.
  • the color former contains a compound represented by the formula (1) described later, and contains the compound.
  • a pressure measuring sheet set having excellent high temperature aptitude and a pressure measuring sheet having excellent high temperature aptitude. Further, according to the present invention, it is possible to provide a method for manufacturing a microcapsule, a dispersion liquid, a sheet set for pressure measurement, and a method for manufacturing a sheet for pressure measurement.
  • the numerical range represented by using “-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. good.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
  • substituent T examples of the substituent include the groups exemplified by the following substituent T.
  • substituent T examples include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and a cyano group.
  • halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • acyloxy group carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino Group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl Group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphin
  • the feature of the pressure measuring sheet set and the pressure measuring sheet of the present invention is that the coloring agent contains a compound represented by the formula (1) (hereinafter, also referred to as "specific compound”), and the capsule wall is thermally decomposed.
  • the temperature is 250 ° C. or higher.
  • the present inventors have found that when the color former contains a specific compound and is a capsule wall having a predetermined thermal decomposition temperature, it is excellent in high temperature suitability for a pressure measurement sheet set or the like. Specifically, since it contains a specific compound having excellent thermal stability, it can suppress color change in the color-developing region even when heated for a long time, and by including a capsule wall that does not easily undergo thermal decomposition, it is used under high temperature (especially 180).
  • FIG. 1 is a cross-sectional view of an embodiment of a pressure measuring sheet set.
  • the pressure measurement sheet set 10 includes a first sheet 16 having a first layer 14 including microcapsules 13 arranged on the first support 12 and the first support 12, and a second support 18 and a second support. It comprises a second sheet 22 having a second layer 20 containing a developer disposed on the body 18.
  • the first layer 14 in the first sheet 16 and the second layer 20 in the second sheet 22 face each other.
  • the sheet 16 and the second sheet 22 are laminated and used.
  • the microcapsules 13 are formed in the pressurized region.
  • the color-developing agent contained in the microcapsules 13 is broken and comes out of the microcapsules 13, and the color-developing reaction proceeds with the color-developing agent in the second layer 20. As a result, color development progresses in the pressurized region.
  • the first sheet 16 may have the first layer 14 and may not have the first support 12.
  • the second sheet 22 may have the second layer 20 and may not have the second support 18.
  • the first support 12 and the first layer 14 are directly laminated, but the present invention is not limited to this embodiment, and as will be described later, the first support 12 and the first layer 14 are combined.
  • Another layer for example, an adhesion layer
  • the second support 18 and the second layer 20 are directly laminated, but the present invention is not limited to this embodiment, and as will be described later, the second support 18 and the second layer 20 are combined.
  • Another layer for example, an adhesion layer
  • the first sheet 16 shown in FIG. 1 has a first support 12 and a first layer 14 containing microcapsules 13 containing a color former.
  • the heat shrinkage rate Sa1 in the longitudinal direction of the first sheet and the heat shrinkage rate Sa2 in the width direction orthogonal to the longitudinal direction of the first sheet are both ⁇ 0. It is preferably 5 to 3.0%.
  • the method for measuring the heat shrinkage rate Sa1 and the heat shrinkage rate Sa2 of the first sheet is as shown in the Example column.
  • the method of setting the heat shrinkage rate of the first sheet within the above range is not particularly limited, but the heat shrinkage rate in the longitudinal direction and the width direction when the first support is heated at 220 ° C. for 10 minutes is ⁇ 0.5. It is preferable to apply a film having a temperature of about 3.0, and it is more preferable to apply a polyethylene naphthalate film or a polyimide film.
  • the longitudinal direction of the first sheet means the long direction of the first sheet, and specifically, when the first sheet 16 is rectangular, it means the direction along the long side.
  • the width direction of the first sheet means a direction orthogonal to the longitudinal direction of the first sheet (short direction), and for example, when the first sheet is rectangular, it means a direction along the short side. ..
  • the first sheet is a square, the direction along any one side constituting the square is the major axis direction, and the direction along the side orthogonal to the major axis direction is the width direction.
  • the first sheet may be a single leaf (single sheet) or a long sheet.
  • the first support is a member for supporting the first layer. If the first layer itself can be handled, the first sheet may not have the first support.
  • the first support may have either a sheet shape or a plate shape.
  • the first support include a resin film and synthetic paper.
  • the resin film include polyester films such as polyethylene naphthalate and polyethylene terephthalate films; cellulose derivative films such as cellulose triacetate; polyolefin films such as polypropylene and polyethylene; and polystyrene films.
  • the synthetic paper for example, a synthetic paper produced by biaxially stretching polypropylene or polyethylene terephthalate or the like to form a large number of microvoids (for example, YUPO), or synthetic fibers such as polyethylene, polypropylene, polyethylene terephthalate and polyamide.
  • Examples include paper and synthetic paper in which these are laminated on a part, one side or both sides of the paper.
  • a resin film or synthetic paper is preferable, a resin film is more preferable, a polyester film is further preferable, and a polyethylene naphthalate film is particularly preferable.
  • examples of commercially available polyethylene naphthalate films include Theonex (registered trademark) Q51, Q53, Q81 and Q83 (manufactured by Teijin Film Solutions Co., Ltd.).
  • the first support is preferably transparent because the color-developing property can be visually recognized even when the first support is visually recognized from the support side.
  • the thickness of the first support is preferably 10 to 200 ⁇ m.
  • the first layer contains microcapsules containing a specific compound and having a capsule wall having a predetermined thermal decomposition temperature.
  • microcapsules containing a specific compound and having a capsule wall having a predetermined thermal decomposition temperature.
  • the microcapsule has a core portion and a capsule wall for encapsulating a core material (encapsulated material (hereinafter, also referred to as “encapsulating component”) forming the core portion).
  • encapsulated material hereinafter, also referred to as “encapsulating component”
  • the microcapsule contains a color former containing a specific compound as a core material (encapsulating component).
  • the color former can be present in the microcapsules until it is pressurized and the microcapsules are destroyed.
  • the microcapsules have a capsule wall that encloses the core material.
  • the thermal decomposition temperature of the capsule wall of the microcapsule is 250 ° C. or higher, preferably more than 250 ° C., more preferably 255 ° C. or higher, still more preferably 260 ° C. or higher.
  • the upper limit is not particularly limited, but is often 500 ° C. or lower.
  • the method for measuring the thermal decomposition temperature of the capsule wall is as follows. 50 sheets of the first layer (microcapsule layer) having a length of 1 cm and a width of 1 cm are prepared, and all of them are immersed in 10 mL of water and allowed to stand for 24 hours to obtain an aqueous dispersion of microcapsules.
  • the first sheet includes the first support
  • 50 sheets of 1 cm in length ⁇ 1 cm in width may be prepared and immersed.
  • the obtained aqueous dispersion of microcapsules is centrifuged at 15,000 rpm for 30 minutes, and the microcapsules are separated. 1000 times or more of ethyl acetate is added to the separated microcapsules, and the mixture is further stirred at 25 ° C. for 24 hours.
  • the obtained solution is filtered and the obtained residue is vacuum dried at 60 ° C. for 48 hours to obtain microcapsules containing nothing inside (hereinafter, also simply referred to as “measurement material”). Be done. That is, a capsule wall material of microcapsules, which is an object for measuring the thermal decomposition temperature, can be obtained.
  • thermogravimetric differential thermal analyzer TG-DTA device name: DTG-60, manufactured by Shimadzu Corporation.
  • TGA thermogravimetric differential thermal analyzer
  • the thermal decomposition temperature is the temperature of the measurement material raised from room temperature at a constant temperature rise rate (10 ° C./min) with respect to the mass of the measurement material before heating.
  • the thermogravimetric temperature (° C.) is defined as the temperature at which the weight is reduced by 5% by mass.
  • the material (wall material) for the capsule wall of the microcapsules include known resins conventionally used as the wall material for microcapsules containing a color former in the applications of pressure-sensitive copying paper and thermal recording paper. .. It is preferred that the capsule wall of the microcapsules is substantially made of resin. Substantially composed of resin means that the content of the resin is 90% by mass or more with respect to the total mass of the capsule wall of the microcapsules, and 100% by mass is preferable. That is, the capsule wall of the microcapsule is preferably made of resin.
  • the resin examples include polyurethane, polyurea, polyurethane urea, melamine resin, acrylic resin and gelatin.
  • the capsule wall of the microcapsule preferably contains at least one selected from the group consisting of polyurethane, polyurea, polyurethane urea and melamine resin, and polyurethane urea and melamine resin are preferable. It is more preferable to contain at least one selected from the group consisting of, and it is further preferable to contain a polyurethane urea or a melamine resin having a polymethylene polyphenylene structure.
  • the polymethylene polyphenylene structure means a structure represented by the formula (Y). In the formula (Y), n represents an integer of 1 or more, n is preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.
  • the melamine resin is preferably a reaction product formed by polycondensation of melamine and formaldehyde.
  • Polyisocyanate is a compound having two or more isocyanate groups. Examples of the polyisocyanate include aromatic polyisocyanates and aliphatic polyisocyanates, and aromatic polyisocyanates are preferable because aromatic ring groups can be introduced into the capsule wall of microcapsules.
  • aromatic polyisocyanate examples include aromatic diisocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, naphthalene-1,4-diisocyanate, and the like.
  • aliphatic polyisocyanate examples include aliphatic diisocyanates, such as trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanis, butylene-1,2-diisocyanis, cyclohexylene-1,2-diisocyanis, and cyclohex.
  • aliphatic diisocyanates such as trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanis, butylene-1,2-diisocyanis, cyclohexylene-1,2-diisocyanis, and cyclohex.
  • examples thereof include diisocyanate, lysine diisocyanate and hydrided xylylene diisocyanate.
  • polyisocyanate examples include trifunctional or higher functional polyisocyanates (for example, trifunctional triisocyanate and tetrafunctional tetraisocyanate).
  • the polyisocyanate is an adduct (additional body) of a polyol such as a burette or isocyanurate, which is a trimer of the above bifunctional polyisocyanate, or a polyol such as trimethylolpropane, and a bifunctional polyisocyanate.
  • Formalin condensate of benzene isocyanate, polyisocyanate having a polymerizable group such as methacryloyloxyethyl isocyanate and lysine triisocyanate can also be mentioned.
  • polyisocyanates the "Polyurethane Resin Handbook” (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)) can be used.
  • a trifunctional or higher functional polyisocyanate is preferable.
  • the trifunctional or higher functional polyisocyanate include a trifunctional or higher functional aromatic polyisocyanate and a trifunctional or higher functional aliphatic polyisocyanate.
  • the trifunctional or higher functional polyisocyanate is an adduct of an aromatic or alicyclic diisocyanate and a compound having three or more active hydrogen groups in one molecule (for example, a trifunctional or higher functional polyol, polyamine, polythiol, etc.).
  • a trimeric (additive) trifunctional or higher polyisocyanate (adduct type trifunctional or higher polyisocyanate) and an aromatic or alicyclic diisocyanate trimerate (biuret type or isocyanurate type) are also preferable.
  • a trifunctional or higher polyisocyanate (additive) is more preferable.
  • a trifunctional or higher polyisocyanate which is the adduct body a trifunctional or higher functional polyisocyanate which is an adduct body of an aromatic or alicyclic diisocyanate and a polyol having three or more hydroxy groups in one molecule is preferable.
  • As the adduct body it is preferable to use an adduct body obtained by using an aromatic diisocyanate because the effect of the present invention is more excellent.
  • the above-mentioned polyol for example, a small molecule polyol having trifunctionality or higher, which will be described later, is preferable, and trimethylolpropane is more preferable.
  • Examples of the adduct-type trifunctional or higher-functional polyisocyanate include Takenate (registered trademark) D-102, D-103, D-103H, D-103M2, P49-75S, D-110N, D-120N, and D-.
  • adduct-type trifunctional or higher polyisocyanate Takenate (registered trademark) D-110N, D-120N, D-140N, D-160N (manufactured by Mitsui Chemicals, Inc.) or Barnock (registered trademark) manufactured by DIC Corporation. ) D-750 is preferable, and Barnock (registered trademark) D-750 manufactured by DIC is more preferable.
  • Examples of the isocyanurate-type trifunctional or higher-functional polyisocyanate include Takenate (registered trademark) D-127N, D-170N, D-170HN, D-172N, D-177N, and D-204 (manufactured by Mitsui Kagaku Co., Ltd.).
  • Biuret-type trifunctional or higher functional isocyanates include, for example, Takenate (registered trademark) D-165N, NP1100 (manufactured by Mitsui Chemicals, Inc.), Death Module (registered trademark) N3200 (Sumika Bayer Urethane) and Duranate (registered trademark). 24A-100 (manufactured by Asahi Kasei Corporation) can be mentioned.
  • polymethylene polyphenyl polyisocyanate polymethylene polyphenyl polyisocyanate is also preferable.
  • polymethylene polyphenyl polyisocyanate a compound represented by the formula (X) is preferable.
  • n represents an integer of 1 or more. As n, an integer of 1 to 10 is preferable, and an integer of 1 to 5 is more preferable, because the pressure distribution can be measured better at a high temperature.
  • Examples of the polyisocyanate containing polymethylene polyphenyl polyisocyanate include Millionate MR-100, Millionate MR-200, Millionate MR-400 (manufactured by Tosoh), WANNAME PM-200, and WANNAME PM-400 (manufactured by Manka Japan). ), Cosmonate M-50, Cosmonate M-100, Cosmonate M-200, Cosmonate M-300 (manufactured by Mitsui Chemicals, Inc.) and Boranate M-595 (manufactured by Dow Chemicals, Inc.).
  • a polyol is a compound having two or more hydroxy groups.
  • the polyol include low molecular weight polyols (for example, aliphatic polyols and aromatic polyols), polyvinyl alcohols, polyether polyols, polyester-based polyols, polylactone-based polyols, castor oil-based polyols, polyolefin-based polyols, and hydroxy group-containing amines. Examples include polyols.
  • the low molecular weight polyol means a polyol having a molecular weight of 400 or less, and for example, bifunctional low molecular weight polyols such as ethylene glycol, diethylene glycol and propylene glycol; glycerin, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol and the like. Examples thereof include low molecular weight polyols having trifunctionality or higher.
  • Examples of the hydroxy group-containing amine compound include oxyalkylated derivatives of amino compounds, and amino alcohols are preferable.
  • Examples of the amino alcohol include propylene oxide and ethylene oxide adducts of amino compounds such as ethylenediamine, and specific examples thereof include N, N, N', N'-tetrakis [2-hydroxypropyl] ethylenediamine and N, Examples thereof include N, N', N'-tetrakis [2-hydroxyethyl] ethylenediamine.
  • a polyamine is a compound having two or more amino groups (primary amino group or secondary amino group).
  • the polyamine include aliphatic polyvalent amines such as diethylenetriamine, triethylenetetramine, 1,3-propylenediamine and hexamethylenediamine; epoxy compound adducts of aliphatic polyvalent amines; alicyclic polyvalent amines such as piperazine. Examples thereof include heterocyclic diamines such as 3,9-bis-aminopropyl-2,4,8,10-tetraoxaspiro- (5,5) undecane.
  • a preferred embodiment of the resin contained in the capsule wall of the microcapsule is to have a structure A or a structure B.
  • the rigidity can be improved while maintaining a high crosslink density, so that the contained color former can be more suppressed from moving out of the capsule, and the effect of the present invention can be further improved.
  • the structure A includes an aromatic or alicyclic diisocyanate, a compound having three or more active hydrogen groups in one molecule, and a polymethylene polyphenyl polyisocyanate (preferably a compound represented by the formula (X)).
  • I a reaction structure.
  • Structure B is a structure formed by reacting melamine and formaldehyde.
  • the resin contained in the capsule wall of the microcapsule is a trifunctional adduct of an aromatic or alicyclic diisocyanate and a compound having three or more active hydrogen groups in one molecule.
  • Polyisocyanate A hereinafter, also simply referred to as "polyisocyanate A”
  • polyisocyanate B selected from the group consisting of aromatic diisocyanate and polymethylene polyphenyl polyisocyanate (hereinafter, simply “polyisocyanate B"). Also referred to as)). That is, it is preferable that the capsule wall of the microcapsules contains a resin formed by using the polyisocyanate A and the polyisocyanate B from the viewpoint of excellent effects of the present invention.
  • aromatic diisocyanate may be used alone, polymethylene polyphenyl polyisocyanate may be used alone, or both may be used in combination.
  • polyisocyanate B a mixture of aromatic diisocyanate and polymethylene polyphenyl polyisocyanate is preferable.
  • the mass ratio of the mass of polymethylene polyphenyl polyisocyanate to the mass of aromatic diisocyanate is preferably 0.1 to 10, and is 0. .5-2 is more preferable, and 0.75 to 1.5 is even more preferable.
  • the viscosity of the polyisocyanate B is preferably 100 to 1000 mPa ⁇ s.
  • the viscosity is the viscosity at 25 ° C.
  • the mass ratio of the mass of polyisocyanate A to the mass of polyisocyanate B (mass of polyisocyanate A / mass of polyisocyanate B) from the viewpoint of excellent effect of the present invention. Is preferably 20/80 to 98/2, more preferably 20/80 to 90/10, and even more preferably 20/80 to 70/30.
  • the volume-based median diameter (D50) of the microcapsules is preferably 1 to 80 ⁇ m, more preferably 5 to 70 ⁇ m, and even more preferably 10 to 50 ⁇ m.
  • the median diameter based on the volume of the microcapsules can be controlled by adjusting the manufacturing conditions of the microcapsules and the like.
  • the volume-based median diameter of microcapsules is the volume of particles on the large diameter side and the small diameter side when the entire microcapsule is divided into two with the particle diameter at which the cumulative volume is 50% as a threshold. The diameter at which the total of is equal. That is, the median diameter corresponds to the so-called D50.
  • the thickness of the capsule wall (number average wall thickness) of the microcapsules is often 0.01 to 2.0 ⁇ m, preferably 0.05 to 1.0 ⁇ m, more preferably 50 to 500 nm, and the effect of the present invention is more effective. From the viewpoint of superiority, 80 to 300 nm is more preferable, and from the viewpoint of more excellent gradation at high temperature, 80 to 250 nm is particularly preferable, and 100 to 200 nm is most preferable.
  • the thickness of the microcapsules refers to the thickness of the capsule wall forming the capsule particles of the microcapsules, and the number average wall thickness refers to the thickness of the individual capsule walls of the five microcapsules by a scanning electron microscope (SEM). The average value obtained and averaged.
  • a cross-sectional section of the first sheet having the first layer containing the microcapsules was prepared, and the cross section was observed at 200 times by SEM [(microcapsule volume-based median diameter (D50)). (Value of) ⁇ 0.9] to [(Value of median diameter (D50) based on the volume of microcapsules) ⁇ 1.1] Any five microcapsules having a major axis in the range were selected and selected. The cross section of each microcapsule is observed at 15,000 times, the thickness of the capsule wall of the microcapsule is obtained, and the average value is calculated. The major axis means the longest diameter when observing the microcapsules.
  • the ratio ( ⁇ / Dm) of the number average wall thickness ⁇ of the microcapsules to the median diameter (D50) Dm based on the volume of the microcapsules is not particularly limited, but is often 0.001 or more. Above all, it is preferable to satisfy the relationship of the formula (1) in that the effect of the present invention is more excellent. Equation (1) 0.100> ⁇ / Dm> 0.001 That is, the above ratio ( ⁇ / Dm) is preferably more than 0.001 and less than 0.100. If the relationship of the equation (1) is satisfied, the color density gradation can be easily recognized according to the pressure.
  • the microcapsules may be used alone or in combination of two or more.
  • the content of the microcapsules in the first layer is preferably 50 to 90% by mass, more preferably 55 to 80% by mass, based on the total mass of the first layer.
  • the microcapsules contain a color former containing the compound represented by the formula (1).
  • the color-developing agent is a compound that develops a color when it comes into contact with a color-developing agent described later from a colorless state.
  • an electron-donating dye precursor precursor of a dye that develops color
  • an electron-donating colorless dye is preferable.
  • R 1 represents an alkyl group which may have a substituent.
  • R 3 represents -NR A R B.
  • RA and RB each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • R 2 and R 4 each independently represent a halogen atom.
  • Q represents a benzene ring or a naphthalene ring.
  • X represents -O- or -NR 5- .
  • R 5 represents an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • p and q each independently represent an integer of 0 to 4.
  • r represents an integer of 1 to 3.
  • s represents an integer of 0 to 3.
  • p + q is an integer of 0 to 4
  • r + s is an integer of 1 to 4.
  • R 1 represents an alkyl group which may have a substituent.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • Examples of the substituent that the above-mentioned alkyl group may have include the group exemplified by the above-mentioned substituent T.
  • a plurality of R 1s may be the same or different.
  • R 3 represents -NR A R B.
  • RA and RB each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the aryl group may be either monocyclic or polycyclic. Examples of the substituent that the alkyl group and the aryl group may have include the groups exemplified by the above-mentioned substituent T.
  • at least one of RA and RB preferably represents an alkyl group which may have a substituent, and more preferably represents an unsubstituted alkyl group.
  • a plurality of R3s may be the same or different.
  • R 2 and R 4 each independently represent a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom or a bromine atom is preferable, and a bromine atom is more preferable.
  • X represents -O- or -NR 5- . Among them, —O— is preferable as X.
  • R 5 represents an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the alkyl group may be linear, branched or cyclic, and is preferably linear or branched.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the aryl group may be either monocyclic or polycyclic.
  • an alkyl group which may have a substituent or an aryl group which may have a substituent is preferable, and an aryl group which may have a substituent is more preferable.
  • the substituent which the above-mentioned alkyl group and the above-mentioned aryl group may have include the group exemplified by the above-mentioned substituent T, and are selected from the group consisting of a halogen atom, a cyano group, a nitro group and a carboxy group. At least one is preferable, and a nitro group is more preferable.
  • p and q each independently represent an integer of 0 to 4.
  • r represents an integer of 1 to 3.
  • s represents an integer of 0 to 3.
  • p + q is an integer of 0 to 4, and r + s is an integer of 1 to 4.
  • p an integer of 0 to 2 is preferable.
  • q an integer of 0 to 1 is preferable.
  • r an integer of 1 to 2 is preferable, and 1 is more preferable.
  • s an integer of 0 to 1 is preferable, and 0 is more preferable.
  • Q represents a naphthalene ring
  • 0 is preferable as p and q.
  • an integer of 0 to 3 is preferable, and an integer of 0 to 2 is more preferable.
  • r + s an integer of 1 to 3 is preferable, an integer of 1 to 2 is more preferable, and 1 is even more preferable.
  • R 6 represents an alkyl group which may have a substituent.
  • R 7 represents a halogen atom.
  • RA and RB each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • Q represents a benzene ring or a naphthalene ring.
  • t and u each independently represent an integer of 0 to 4. However, t + u is an integer of 0 to 4.
  • R 6 represents an alkyl group which may have a substituent.
  • the alkyl group has the same meaning as R 1 in the formula (1), and the preferable range is also the same.
  • R 7 represents a halogen atom.
  • R 7 has the same meaning as R 2 in the formula (1), and the preferable range is also the same.
  • RA and RB each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • Q represents a benzene ring or a naphthalene ring.
  • RA , RB, and Q in the formula (2) have the same meaning as RA , RB , and Q in the above - mentioned formula (1), respectively, and the preferable range is also the same.
  • t and u each independently represent an integer of 0 to 4.
  • t + u is an integer of 0 to 4.
  • t an integer of 0 to 2 is preferable.
  • u an integer of 0 to 1 is preferable.
  • Q represents a naphthalene ring
  • 0 is preferable as t and u.
  • t + u an integer of 0 to 3 is preferable, and an integer of 0 to 2 is more preferable.
  • Examples of the specific compound include the following compounds.
  • the microcapsules may contain other color-developing agents in addition to the specific compound.
  • the other color-developing agent is not particularly limited as long as it is a color-developing agent other than a specific compound, and examples thereof include color-developing agents known for use in pressure-sensitive copying paper or thermal recording paper.
  • the compound represented by the formula (D) is preferable from the viewpoint of excellent visibility.
  • R D1 and R D3 independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • the number of carbon atoms of the alkyl group represented by RD1 and RD3 is preferably 1 to 10, and more preferably 1 to 5.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • Examples of the substituent which the above-mentioned alkyl group and the above-mentioned aryl group may have include the groups exemplified by the above-mentioned substituent T, and RD1 and RD3 each independently have a substituent.
  • a optionally alkyl group or an aryl group which may have a substituent is preferable, an alkyl group which may have a substituent is more preferable, and an unsubstituted alkyl group is further preferable.
  • R D2 and R D4 each independently represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the number of carbon atoms of the alkyl group represented by RD2 and RD4 is preferably 1 to 10, and more preferably 1 to 5.
  • the aryl group represented by RD2 and RD4 may be either monocyclic or polycyclic.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • Examples of the substituent that the alkyl group and the aryl group may have include the groups exemplified by the above-mentioned substituent T. Among them, as RD2 and RD4 , an alkyl group which may independently have a substituent is preferable, and an unsubstituted alkyl group is more preferable.
  • RD1 to RD4 are preferably unsubstituted alkyl groups, and more preferably the same unsubstituted alkyl groups.
  • RD5 represents -O- or -NR D6- . Of these, -NR D6 -is preferable.
  • RD6 represents an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the number of carbon atoms of the alkyl group represented by RD6 is preferably 1 to 10, and more preferably 1 to 5.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the aryl group represented by RD6 may have a monocyclic structure or a compound ring structure. Examples of the substituent that the alkyl group and the aryl group may have include the groups exemplified by the above-mentioned substituent T.
  • an aryl group which may have a substituent is preferable, and an aryl group substituted with a group selected from the group consisting of a halogen atom, a cyano group, a nitro group and a carboxyl group is preferable. More preferably, an aryl group substituted with a nitro group is further preferable.
  • the molecular weight of the compound represented by the formula (D) is not particularly limited, but is preferably 300 or more, more preferably 500 or more.
  • the upper limit is not particularly limited, but is preferably 2000 or less, and more preferably 1000 or less.
  • color formers examples include triphenylmethanephthalide-based compounds, fluorene-based compounds, phenothiazine-based compounds, indolylphthalide-based compounds, azaindolylphthalide-based compounds, leukooramine-based compounds, and rhodamine lactam-based compounds. , Triphenylmethane-based compounds, diphenylmethane-based compounds, triazene-based compounds, spiropyran-based compounds and fluorene-based compounds.
  • color formers examples include 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide and 3- (4-diethylamino-).
  • the molecular weight of the color former is often 300 or more.
  • the upper limit is often 1000 or less, and 600 or less is preferable because the effect of the present invention is more excellent.
  • the color former may be used alone or in combination of two or more.
  • the content of the color former in the first layer is preferably 0.1 to 10 g / m 2 , more preferably 0.1 to 4 g / m 2 .
  • the content of the specific compound is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and excellent in light resistance after color development, with respect to the total mass of the color former. Mass% or more is particularly preferable.
  • the upper limit is preferably 100% by mass or less with respect to the total mass of the color former.
  • the microcapsules may contain other components in addition to the coloring agent described above.
  • examples of other components include a solvent and additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, a wax and an odor suppressant, and a solvent is preferable.
  • an ultraviolet absorber a compound having a benzotriazole structure is preferable.
  • the solvent preferably contains an aromatic solvent from the viewpoint of improving the solubility of the color former.
  • the solvent examples include an alkylnaphthalene compound such as diisopropylnaphthalene, a diallylalkane compound such as 1-phenyl-1-xsilylethane, an alkylbiphenyl compound such as isopropylbiphenyl, a triarylmethane compound, an alkylbenzene compound and a benzylnaphthalene.
  • Aromatic hydrocarbons such as system compounds, diarylalkylene compounds and arylindane compounds; aliphatic hydrocarbons such as dibutyl phthalate and isoparaffin; soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, palm oil, castor oil and fish oil, etc.
  • Natural animal and vegetable oils and natural products such as mineral oils and high boiling point distillates can be mentioned.
  • the solvent may be used alone or in combination of two or more.
  • the mass ratio of the mass of the color-developing agent to the mass of the solvent is preferably 98/2 to 30/70 from the viewpoint of color-developing property. , 97/3 to 40/60 are more preferable.
  • the method for producing microcapsules containing a color former is not particularly limited, and examples thereof include known methods such as an interfacial polymerization method, an internal polymerization method, a phase separation method, an external polymerization method, and a core selvation method. Is preferable.
  • an interfacial polymerization method a raw material containing a color former and a capsule wall material (for example, polyisocyanate and at least one selected from the group consisting of polyols and polyamines), and polyisocyanates and water are reacted to form polyamines.
  • an oil phase containing a polyol and a polyamine When produced in a system, an oil phase containing a polyol and a polyamine may not be used) is dispersed in an aqueous phase containing an emulsifier to prepare an emulsion (emulsification step), and a capsule wall material.
  • a surface polymerization method including a step of forming a capsule wall by polymerizing at the interface between the oil phase and the aqueous phase to form microcapsules containing a color former (encapsulation step) is preferable.
  • the mass ratio of the total amount of polyol and polyamine to the amount of polyisocyanate (total amount of polyol and polyamine / amount of polyisocyanate) in the above raw materials is not particularly limited, but is 0.1 / 99.9 to.
  • the polyisocyanate A and the polyisocyanate B may be used in combination as the polyisocyanate. When both are used in combination, the preferable range of the mixing ratio of both is as described above.
  • the type of emulsifier used in the emulsification step is not particularly limited, and examples thereof include a dispersant and a surfactant.
  • examples of the dispersant include polyvinyl alcohol.
  • the first layer may contain other components in addition to the above-mentioned microcapsules.
  • other components include polymer binders, inorganic fillers (for example, colloidal silica), fluorescent whitening agents, defoaming agents, penetrants, ultraviolet absorbers, surfactants and preservatives.
  • the polymer binder include styrene-butadiene copolymer, polyvinyl acetate, polyacrylic acid ester, polyvinyl alcohol, polyacrylic acid, maleic anhydride-styrene copolymer, starch, casein, gum arabic, gelatin, and carboxy. Examples thereof include methyl cellulose or a salt thereof, synthetic polymers such as methyl cellulose, and natural polymers.
  • the content of the polymer binder is not particularly limited, but is preferably 0 to 50% by mass with respect to the total mass of the first layer. In terms of being suitable for a low pressure region of 20 MPa or less, 0.1 to 20% by mass is preferable, and 0.2 to 10% by mass is more preferable.
  • the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants and the like, and anionic surfactants or nonions in terms of maintaining the dispersibility of microcapsules. Sexual surfactants are preferred.
  • the surfactant examples include a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, and the like, which are hydrocarbon-based surfactants in terms of maintaining coatability and dispersibility of microcapsules. Agents are preferred.
  • the content of the surfactant is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total mass of the first layer.
  • the inorganic filler it is preferable to introduce the inorganic filler after the first sheet and the second sheet are overlapped with each other and the heating pressure is measured, so that both of them can be easily peeled off.
  • Silica particles or alumina particles are preferable as the inorganic filler in that the first sheet and the second sheet can be easily peeled off.
  • the median diameter of the inorganic filler is preferably 0.001 to 1 ⁇ m, more preferably 0.005 to 0.1 ⁇ m, still more preferably 0.005 to 0.05 ⁇ m.
  • the content of the inorganic filler is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and more preferably 5 to 20% by mass with respect to the total mass of the first layer.
  • the thickness of the first layer is not particularly limited, but is preferably 0.01 to 5 ⁇ m, preferably 0.02 to 3 ⁇ m.
  • the thickness of the first layer means the thickness excluding the microcapsules exposed from the layer surface when the average particle size of the microcapsules is larger than the layer thickness.
  • the thickness of the first layer is preferably 50% or less, preferably 25% or less, based on the average particle size of the microcapsules.
  • the mass (g / m 2 ) per unit area of the first layer is not particularly limited, but is preferably 0.5 to 20 g / m 2 .
  • the method for forming the first layer is not particularly limited, and examples thereof include known methods. For example, a method of applying a composition for forming a first layer containing microcapsules onto a first support and, if necessary, performing a drying treatment can be mentioned.
  • the composition for forming the first layer may be a dispersion liquid in which microcapsules are dispersed in water or the like.
  • the dispersion liquid in which the microcapsules are dispersed can be prepared by mechanically dispersing the microcapsules in water or the like.
  • the composition for forming the first layer preferably contains at least microcapsules and a solvent.
  • the microcapsule dispersion obtained by the above-mentioned interfacial polymerization method may be used as the composition for forming the first layer.
  • the composition for forming the first layer may contain other components that may be contained in the first layer described above.
  • the method of applying the composition for forming the first layer is not particularly limited, and examples of the coating machine used at the time of application include an air knife coater, a rod coater, a bar coater, a curtain coater, a gravure coater, and an extrusion coater. , Die coater, slide bead coater and blade coater.
  • the coating film After applying the composition for forming the first layer on the first support, the coating film may be subjected to a drying treatment, if necessary.
  • a drying treatment include heat treatment.
  • the present invention is not limited to the above embodiment.
  • the temporary support may be peeled off to form the first sheet composed of the first layer.
  • the temporary support is not particularly limited as long as it is a peelable support.
  • the first sheet may have other members in addition to the above-mentioned members.
  • the first sheet may have, for example, an adhesion layer for enhancing the adhesion between the first support and the first layer.
  • the adhesion layer is not particularly limited, but is preferably a layer having a resin.
  • the thickness of the adhesion layer is preferably 0.005 to 5 ⁇ m, more preferably 0.01 to 1 ⁇ m.
  • the second sheet 22 described in FIG. 1 has a second support 18 and a second layer 20 containing a color developer arranged on the second support 18.
  • the preferred ranges of the heat shrinkage rate Sc1 and the heat shrinkage rate Sc2 in the second sheet are the same as the heat shrinkage rate Sa1 and the heat shrinkage rate Sa2 in the first sheet, respectively.
  • the method for measuring the heat shrinkage rate Sc1 and the heat shrinkage rate Sc2 of the second sheet is the same as the method for measuring the heat shrinkage rate Sa1 and the heat shrinkage rate Sa2 of the first sheet, except that the second sheet is used instead of the first sheet.
  • the definitions of the longitudinal direction and the width direction in the second sheet are the same as the definitions of the longitudinal direction and the width direction of the first sheet except that the first sheet is read as the second sheet.
  • the second sheet may be a single leaf (single sheet) or a long sheet. In the following, each member will be described in detail.
  • the second support is a member for supporting the second layer. Since the aspect of the second support is the same as the aspect of the first support described above, the description thereof will be omitted.
  • the second layer is a layer containing a color developer.
  • the color developer is a compound that does not have a color-developing function by itself, but has a property of developing a color-developing agent by contact with the color-developing agent.
  • an electron-accepting compound is preferable.
  • the color developer include inorganic compounds and organic compounds.
  • the inorganic compound include clay substances such as acid clay, activated clay, attapargite, zeolite, bentonite and kaolin.
  • the organic compound include a metal salt of an aromatic carboxylic acid, a phenol formaldehyde resin, and a metal salt of a carboxylated terpene phenol resin.
  • metal salt of the aromatic carboxylic acid examples include 3,5-di-t-butylsalicylic acid, 3,5-di-t-octylsalicylic acid, 3,5-di-t-nonylsalicylic acid, and 3,5-di-t.
  • a clay substance, a metal salt of an aromatic carboxylic acid or a metal salt of a carboxylated terpenephenol resin is preferable, and a clay substance or a metal salt of an aromatic carboxylic acid is more preferable, and the effect of the present invention is effective.
  • clay substances are more preferable, and acidic clay, active clay or kaolin is particularly preferable.
  • the content of the color developer in the second layer is preferably 20 to 95% by mass, more preferably 30 to 90% by mass, based on the total mass of the second layer, because the effect of the present invention is excellent.
  • the content of the color developer in the second layer is preferably 0.1 to 30 g / m 2 .
  • the content of the developer in the second layer is preferably 3 to 20 g / m 2 and more preferably 5 to 15 g / m 2 .
  • the content of the developer in the second layer is preferably 0.1 to 5 g / m 2 , more preferably 0.2 to 3 g / m 2 .
  • the second layer may contain other components other than the above-mentioned developer.
  • other components include polymer binders, pigments, optical brighteners, defoamers, penetrants, ultraviolet absorbers, surfactants and preservatives.
  • the polymer binder include styrene-butadiene copolymer, polyvinyl acetate, polyacrylic acid ester, polyvinyl alcohol, polyacrylic acid, maleic anhydride-styrene copolymer, starch, casein, gum arabic, gelatin, and carboxy.
  • examples thereof include synthetic polymers such as methyl cellulose and methyl cellulose, and natural polymers.
  • Pigments include, for example, heavy calcium carbonate, light calcium carbonate, talc and titanium dioxide.
  • the thickness of the second layer is preferably 1 to 50 ⁇ m, more preferably 2 to 30 ⁇ m, from the viewpoint of excellent effects of the present invention.
  • the mass (g / m 2 ) per unit area of the second layer is preferably 0.5 to 20 g / m 2 .
  • the method for forming the second layer is not particularly limited, and examples thereof include known methods. For example, a method of applying a composition for forming a second layer containing a color developer on a second support and, if necessary, performing a drying treatment can be mentioned.
  • the composition for forming the second layer may be a dispersion liquid in which a color developer is dispersed in water or the like.
  • the dispersion liquid in which the developer is dispersed can be prepared by mechanically dispersing the inorganic compound in water.
  • the color developer is an organic compound, it can be prepared by mechanically dispersing the organic compound in water or dissolving it in an organic solvent.
  • the composition for forming the second layer may contain other components that may be contained in the second layer described above.
  • the method for applying the composition for forming the second layer is not particularly limited, and examples thereof include a method using a coating machine used for applying the composition for forming the first layer described above.
  • the coating film may be subjected to a drying treatment, if necessary.
  • a drying treatment include heat treatment.
  • the present invention is not limited to the above embodiment.
  • the temporary support may be peeled off to form a second sheet composed of the second layer.
  • the temporary support is not particularly limited as long as it is a peelable support.
  • the first sheet and the second sheet are laminated by laminating the first sheet and the second sheet so that the first layer of the first sheet and the second layer of the second sheet face each other. It is used by obtaining a body and applying pressure to the laminate. That is, the first sheet corresponds to the sheet used for measuring the pressure together with the second sheet.
  • the chromaticity in the color system is not particularly limited, but the chromaticity a * from the viewpoint of easy visibility of color development. Is preferably more than 30 and 80 or less, and chromaticity b * is preferably more than -50 and 50 or less.
  • the first sheet and the second sheet of the laminated body after applying pressure are peeled off, and a second sheet is used with a densitometer RD-19 (manufactured by Gretag Macbeth). Measure the chromaticity of the color-developing part of the sheet. If the second sheet contains a transparent second support and the chromaticity of the color-developing portion can be measured from the second support side, the chromaticity of the color-developing portion can be measured from the second support side. good.
  • the second sheet may have other members in addition to the above-mentioned members.
  • the second sheet may have an adhesion layer between the second support and the second layer for enhancing the adhesion between the two.
  • the adhesion layer include the adhesion layer that the above-mentioned first sheet may have.
  • FIG. 3 is a cross-sectional view of an embodiment of a pressure measuring sheet.
  • the pressure measuring sheet 30 has a support 32, a second layer 20 containing a color developer, and a first layer 14 containing a predetermined microcapsule 13 in this order.
  • the pressure measuring sheet 30 by applying pressure from at least one side of the support 32 side and the first layer 14 side, the microcapsules 13 are broken in the pressurized region and are contained in the microcapsules 13.
  • the color-developing agent comes out of the microcapsules 13 and the color-developing reaction proceeds with the color-developing agent in the second layer 20. As a result, color develops in the pressurized area.
  • the pressure measuring sheet 30 may have the first layer 14 and the second layer 20, and may not have the support 32. Further, in FIG. 3, the support 32 and the second layer 20 are directly laminated, but the present invention is not limited to this aspect. As will be described later, another layer (for example, an adhesion layer) may be arranged between the support 32 and the second layer 20. Further, in FIG. 3, a pressure measuring sheet 30 having a support 32, a second layer 20, and a first layer 14 in this order is disclosed, but the present invention is not limited to this aspect. It may be a pressure measuring sheet having a support 32, a first layer 14, and a second layer 20 in this order.
  • the heat shrinkage rate Sb1 in the longitudinal direction of the pressure measuring sheet and the heat shrinkage rate Sb2 in the width direction orthogonal to the longitudinal direction of the pressure measuring sheet 22 will be either. Also preferably -0.5 to 3.0%.
  • the method for measuring the heat shrinkage rate Sb1 and the heat shrinkage rate Sb2 of the pressure measurement sheet is the method for measuring the heat shrinkage rate Sa1 and the heat shrinkage rate Sa2 of the first sheet described above, except that the measurement target is changed to the pressure measurement sheet. Is the same as.
  • first layer 14 and the second layer 20 in the pressure measurement sheet 30 are the same members as the first layer 14 and the second layer 20 described in the first embodiment described above, the description thereof will be omitted.
  • the support 32 will be mainly described in detail.
  • the support is a member for supporting the first layer and the second layer. If the laminated body of the first layer and the second layer itself can be handled, the pressure measuring sheet does not have to have a support. Since the preferred embodiment of the support is the same as the preferred embodiment of the first support described above, the description thereof will be omitted.
  • the method for producing the pressure measuring sheet is not particularly limited, and examples thereof include known methods.
  • a composition for forming a second layer containing a color developer is applied onto the support, and if necessary, a drying treatment is performed to form the second layer on the support, and then a predetermined microcapsule is further formed.
  • a method of applying a composition for forming a first layer containing the above to the second layer and, if necessary, performing a drying treatment to form the first layer can be mentioned.
  • the method for forming the microcapsules is as described above.
  • the method for forming the first layer using the composition for forming the first layer is as described in the first embodiment.
  • the method for forming the second layer using the composition for forming the second layer is also as described in the first embodiment.
  • the pressure measuring sheet may include other members in addition to the above-mentioned members.
  • the pressure measuring sheet may have an adhesion layer between the support and the second layer to enhance the adhesion between the two.
  • the adhesion layer include the adhesion layer that the above-mentioned first sheet may have.
  • the pressure measuring sheet set of the present invention can be used for various purposes, for example, for verification or control of various manufacturing processes including a high temperature press in a process. More specifically, pressure distribution confirmation in the laminating process in the battery (lithium ion battery, fuel cell) field, pressure distribution confirmation in the laminating process in the printed wiring board (FPC, BWB) field, ACF bonding and laminating of the wiring take-out part, etc.
  • the pressure distribution confirmation in the heat crimping process and the pressure distribution confirmation of the mold tightening portion can be mentioned.
  • a dispersion liquid containing microcapsules containing a color former which is used to form a layer used in combination with a layer containing a color developer (hereinafter, also simply referred to as “first dispersion liquid”). ) (Dispersion liquid for forming a pressure measurement layer).
  • the first dispersion liquid is a dispersion liquid of microcapsules containing microcapsules containing a coloring agent containing a specific compound and having a thermal decomposition temperature of the capsule wall of the microcapsules of 250 ° C. or higher.
  • Each component contained in the first dispersion has the same meaning as the component contained in the first layer described above, and the preferred range is also the same.
  • Examples of the first dispersion liquid include the above-mentioned composition for forming the first layer.
  • the first dispersion liquid preferably contains a solvent. Examples of the solvent contained in the first dispersion liquid include water and an organic solvent.
  • the first dispersion liquid is used to form a layer used for pressure measurement (corresponding to the first layer described above), similarly to the composition for forming the first layer.
  • the first dispersion may be used in combination with a dispersion used for forming a layer containing a developer (hereinafter, also simply referred to as "second dispersion"). That is, the first dispersion liquid and the second dispersion liquid may be used as a set (dispersion liquid set).
  • the second dispersion is a dispersion containing a color developer. Each component contained in the second dispersion has the same meaning as the component contained in the second layer described above, and the preferred range is also the same. Examples of the second dispersion liquid include the above-mentioned second layer forming composition.
  • the second dispersion liquid preferably contains a solvent. Examples of the solvent contained in the second dispersion liquid include water and an organic solvent.
  • the first dispersion liquid does not contain coarse particles from the viewpoint of not clogging when the first dispersion liquid is applied by spraying or the like and used.
  • the volume-based median diameter (D50) of the microcapsules is preferably 1 to 80 ⁇ m, more preferably 5 to 70 ⁇ m, and even more preferably 10 to 50 ⁇ m.
  • the second dispersion liquid does not contain coarse particles.
  • an organic compound is preferable as the color developer contained in the second dispersion liquid.
  • a metal salt of aromatic carboxylic acid is preferable, a metal salt of salicylic acid is more preferable, and a zinc salt of salicylic acid is further preferable.
  • the first dispersion liquid can be applied to an object whose pressure measurement is difficult with a pressure measurement sheet set or the like. More specifically, the first dispersion liquid is applied in a required amount to a region requiring pressure measurement of the pressure measurement object without being influenced by the surface shape of the pressure measurement object, and the above-mentioned region is covered with the first dispersion liquid.
  • pressure measurement is possible. In particular, it can be suitably applied when measuring pressure on a curved surface.
  • a dispersion liquid containing a microcapsule containing a color-developing agent and a color developer used for forming a layer for pressure measurement (hereinafter, also simply referred to as “third dispersion liquid”).
  • third dispersion liquid (Dispersion liquid for forming a pressure measurement layer).
  • Each component contained in the third dispersion has the same meaning as the component contained in the first layer or the second layer described above, and the preferred range is also the same.
  • the microcapsules contained in the third dispersion liquid include the microcapsules contained in the composition for forming the first layer.
  • Examples of the mode of the color developer contained in the third dispersion liquid include the mode of the color developer contained in the composition for forming the second layer.
  • the third dispersion liquid preferably contains a solvent.
  • the solvent contained in the third dispersion liquid include water and an organic solvent.
  • the third dispersion liquid include a mode in which a color developer is mixed with the above-mentioned first layer forming composition and a mode in which the above-mentioned second layer forming composition is mixed with the first layer forming composition.
  • the third dispersion liquid does not contain coarse particles from the viewpoint of not clogging when the first dispersion liquid is applied by spraying or the like and used.
  • the median diameter (D50) based on the volume of the microcapsules is preferably 1 to 50 ⁇ m.
  • the organic compound is preferable as the color developer contained in the third dispersion liquid.
  • a metal salt of aromatic carboxylic acid is preferable, a metal salt of salicylic acid is more preferable, and a zinc salt of salicylic acid is further preferable.
  • the third dispersion liquid contains microcapsules containing a color-developing agent and a color developer
  • pressure measurement can be performed only with the layer formed by applying the third dispersion liquid. That is, the third dispersion can be applied to an object such as the first dispersion and the second dispersion, for which pressure measurement is difficult with a sheet such as a pressure measurement sheet set and a pressure measurement sheet. More specifically, regardless of the surface shape of the object to be pressure-measured, a required amount of the third dispersion is applied to a region requiring pressure measurement of the object to be pressure-measured, and a layer is applied to the region. By forming the above, pressure measurement is possible.
  • the above-mentioned first dispersion liquid, second dispersion liquid, and third dispersion liquid are mainly used for high-temperature heat pressing, heat pressing, bonding, etc. for pressure measurement during automobile manufacturing, but also include other uses. It can be used for various purposes. For example, in the manufacture of vehicles such as automobiles or aircraft, confirmation of pressure distribution in molding of various components, bodies, etc. or assembly of components, confirmation of pressure distribution in assembly of building materials, curved surface processing of electronic products, etc.
  • Example 1 [Preparation of color-developing agent-encapsulating microcapsules] 1,1-Diphenylethane (manufactured by JXTG Energy Co., Ltd., SAS-296) (50 parts by mass), 3', 6'-bis (diethylamino) -2- (4-nitrophenyl) spiro [isoindole-] as a coloring agent 1,9'-Xantene] -3-one (Pink-DCF manufactured by Hodoya Chemical Industry Co., Ltd.) (3 parts by mass), 6'-(diethylamino) -1', 3'-dimethylfluorane (Hodoya Chemical Industry Co., Ltd.) Orange-DCF) (4 parts by mass) and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (Johoku Chemical Industry, JF-77-P) (3 parts by mass) as an ultraviolet absorber.
  • Pink-DCF manufactured by Hodoya Chemical Industry Co., Ltd
  • Millionate MR-200 is a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate. Then, the above solution C was added to a solution in which polyvinyl alcohol (JP-45, manufactured by Japan Vam & Poval Co., Ltd.) (4 parts by mass) was dissolved in water (140 parts by mass), and the solution was emulsified and dispersed. Water (200 parts by mass) was added to the emulsified liquid after emulsification and dispersion, the mixture was heated to 70 ° C. with stirring, stirred for 1 hour, and then cooled.
  • polyvinyl alcohol JP-45, manufactured by Japan Vam & Poval Co., Ltd.
  • the volume-based median diameter (D50) of the obtained color-developing agent-encapsulating microcapsules was 20 ⁇ m.
  • the volume-based median diameter (D50) was measured by the method described above with an optical microscope.
  • the adhesive layer forming composition having styrene butadiene latex was applied and dried on the first support, a polyethylene naphthalate sheet having a thickness of 75 ⁇ m (Teijin Film Solution Co., Ltd., Theonex (registered trademark) Q53), and the thickness was increased.
  • a 100 nm adhesion layer was formed on the first support to obtain a first support having an adhesion layer.
  • the first layer forming composition is applied on the adhesion layer of the first support having the obtained adhesion layer by a bar coater and dried to form a first layer having a diameter of about 500 nm to prepare a first sheet. did.
  • the composition for forming the second layer is coated on a polyethylene naphthalate sheet (Teijin Film Solution Co., Ltd., Theonex (registered trademark) Q53) having a thickness of 75 ⁇ m, which is a second support, with a solid content of 12.0 g / m 2 .
  • the second sheet was obtained by forming a second layer by applying the mixture so as to form a second layer.
  • Example 2 to 24, Comparative Examples 1 to 2, Reference Examples 1 to 2 As shown in Table 1, the first sheet of each Example, each Comparative Example, and each Reference Example was followed in the same procedure as in Example 1 except that various conditions such as each material and the content of each material were changed. And the second sheet was prepared. Comparative Example 1 referred to Comparative Example 1 described in Patent Document 2. Comparative Example 2 referred to Example 13 described in Patent Document 3.
  • the first sheet obtained by the above (preparation of the first sheet) and the second sheet obtained by cutting the second sheet obtained by the above (preparation of the second sheet) into a size of 5 cm ⁇ 5 cm are combined with the first sheet.
  • the surface of the color-developing layer and the surface of the color-developing layer of the second sheet were superposed so as to face each other to obtain a laminated body.
  • the obtained laminate was placed on a hot plate at 200 ° C., and a ring-shaped SUS mold having a width of 5 mm was further placed on the laminate, and the pressure was measured at 2.5 MPa with a pressure measurement time of 5 seconds. ..
  • the obtained laminate was taken down from the hot plate, the laminated first sheet and the second sheet were peeled off, the shape of the color-developing region of the second sheet was visually confirmed, and the evaluation was performed according to the following evaluation criteria. Further, the shape of the color-developing region of the second sheet was visually confirmed by the same procedure as above except that the pressure measurement time was changed to 2 minutes, and the evaluation was performed according to the following evaluation criteria.
  • evaluation criteria A: When the pressure measurement time is 5 seconds or 2 minutes, it can be well recognized that the shape of the color-developing region is a ring shape similar to that of the SUS mold, and the pressure measurement time is 5 seconds.
  • the link shape is similar to that of the SUS mold in most places, and the color of the coloring area when the pressure measurement time is 5 seconds and the color of the color development area when the pressure measurement time is 2 minutes. No change was seen in the color of the color development area.
  • D In both cases where the pressure measurement time is 5 seconds and 2 minutes, it cannot be recognized that the color development area has the same link shape as the SUS mold, and the color development area when the pressure measurement time is 5 seconds. Changes were observed in the color and the color of the color-developing region when the pressure measurement time was 2 minutes.
  • the first sheet obtained by the above (preparation of the first sheet) and the second sheet obtained by cutting the second sheet obtained by the above (preparation of the second sheet) into a size of 5 cm ⁇ 5 cm are combined with the first sheet.
  • the surface of the color-developing layer and the surface of the color-developing layer of the second sheet are overlapped so as to face each other, and a temperature of 200 ° C. and a pressure of 0.5 MPa, 1.5 MPa or 2.5 MPa are used using a hot press machine.
  • the sheet obtained in 1 was pressurized to develop a color.
  • the stacked first and second sheets were peeled off, and the density (DA) of the color-developed portion of the obtained second sheet was obtained at each pressure using a densitometer RD-19 (manufactured by Gretag Macbeth). Was measured.
  • the initial concentration (DB) was measured for the unused second sheet by the same method as described above. Then, the initial density (DB) was subtracted from the density (DA) of the color-developing portion at each pressure to obtain the color-developing density ⁇ D, which was evaluated according to the following evaluation criteria.
  • "B" is a practically acceptable range.
  • C At pressures of 0.5 MPa, 1.5 MPa and 2.5 MPa, ⁇ D is less than 0.1.
  • the first sheet obtained by the above (preparation of the first sheet) and the second sheet obtained by cutting the second sheet obtained by the above (preparation of the second sheet) into a size of 5 cm ⁇ 5 cm are combined with the first sheet.
  • the surface of the color-developing layer and the surface of the color-developing layer of the second sheet are overlapped so as to face each other, and the sheet obtained at a temperature of 200 ° C. and a pressure of 1.0 MPa is pressed and colored using a hot press machine. I let you.
  • the overlapped first sheet and the second sheet are taken down from the hot plate, the overlapped first sheet and the second sheet are peeled off, and the color-developed portion of the second sheet is the image analysis system FPD manufactured by FUJIFILM Corporation. Images were read using -8010J. Then, the obtained second sheet was stored at room temperature for one week. Then, the image of the color-developed portion of the second sheet after storage was read in the same manner, and the image data before and after one week had passed were compared and evaluated according to the following evaluation criteria. (Evaluation criteria) A: The color and density have not changed either. B: At least one of the color and the density was changed.
  • the first sheet produced in each Example, each Comparative Example, and each Reference Example has a length of 150 mm in the direction along the longitudinal direction of the first sheet and a length of 20 mm in the direction along the width direction.
  • Three samples cut in this way were prepared.
  • Position A which is about 25 mm ahead from the center point (starting point) of one short side of the sample toward the center point of the other short side along the direction parallel to the long side, and the center point of the other short side of the sample.
  • a marked line was attached to each of the position B, which was advanced by about 25 mm along the direction parallel to the long side from (starting point) toward the center point of one short side.
  • the distance between the position A and the position B was 100 mm ⁇ 2 mm. This was used as a sample for measuring the heat shrinkage rate Sa1 in the longitudinal direction of the first sheet. After heating the obtained measurement sample at 220 ° C. for 10 minutes, the measurement sample is returned to room temperature (23 ° C.), the distance between the marked lines of the measurement sample is measured, and the heat shrinkage rate Sa3 is according to the following formula. Was calculated.
  • Heat shrinkage rate Sa3 [%] 100 ⁇ ⁇ (distance between marked lines in the measurement sample before heating)-(distance between marked lines in the measurement sample after heating) ⁇ / (in the measurement sample before heating) Distance between marked lines)
  • the arithmetic mean value of the heat shrinkage rate Sa3 of the three measurement samples was obtained and used as the heat shrinkage rate Sa1.
  • the distance between the marked lines was measured up to a unit of 0.1 mm.
  • Heat shrinkage rate Sa4 [%] 100 ⁇ ⁇ (distance between marked lines in the measurement sample before heating)-(distance between marked lines in the measurement sample after heating) ⁇ / (in the measurement sample before heating) Distance between marked lines)
  • the arithmetic mean value of the heat shrinkage rate Sa4 of the three measurement samples was obtained and used as the heat shrinkage rate Sa2.
  • the distance between the marked lines was measured up to a unit of 0.1 mm.
  • the heat shrinkage rate Sa1 in the longitudinal direction of the first sheet and the heat shrinkage rate Sa2 in the width direction orthogonal to the longitudinal direction of the first sheet are obtained. , All were in the range of -0.5 to 3.0.
  • D-750 Corresponds to trimethylolpropane adduct of tolylene diisocyanate (manufactured by DIC, Burnock D-750, solid content concentration 75% by mass), polyisocyanate A. melamine
  • MR-200 Millionate MR-200 (manufactured by Tosoh Corporation), corresponds to polyisocyanate B.
  • Pink-DCF The following compounds (3', 6'-bis (diethylamino) -2- (4-nitrophenyl) spiro [isoindole-1,9'-xanthene] -3-one, manufactured by Hodogaya Chemical Co., Ltd. )
  • Color-developing agent A 3,3-Bis (2-methyl-1-octyl-3-indrill) Phthalide
  • Color-developing agent B The following compounds
  • the “mass ratio (A) / (B)” column shows the mass ratio of the mass of the wall material A to the mass of the wall material B (mass of the wall material A / mass of the wall material B).
  • the compound described in the “Specific compound (a)” column indicates a compound corresponding to the compound represented by the formula (1).
  • the compound described in the “Other color former (b)” column indicates a color former that does not correspond to the compound represented by the formula (1).
  • the mass ratio of the mass of the specific compound (a) to the mass of the other color former (b) (mass of the specific compound (a) / mass of the other color former (b)). ) Is shown.
  • Pressure measurement sheet set 12 1st support 14 1st layer 16 1st sheet 18 2nd support 20 2nd layer 22 2nd sheet 30 Pressure measurement sheet 32 Support 20 2nd layer 22 2nd sheet 30 Pressure Measuring sheet 32 Support

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Color Printing (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)
  • Force Measurement Appropriate To Specific Purposes (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

La présente invention concerne un ensemble de feuilles pour une mesure de pression ayant une excellente compatibilité à haute température, une feuille de mesure de pression, des microcapsules, une dispersion, un procédé de production d'un ensemble de feuilles pour une mesure de pression, et un procédé de production d'une feuille pour une mesure de pression. L'ensemble de feuilles pour mesure de pression selon la présente invention comprend une première feuille comportant une première couche qui renferme des microcapsules encapsulant un agent colorant, et une seconde feuille comprenant une seconde couche qui renferme un révélateur chromogène, l'agent de coloration comprenant un composé représenté par la formule (1) et la température de décomposition thermique des parois de capsule des microcapsules est égale ou supérieure à 250 °C.
PCT/JP2021/042916 2020-12-25 2021-11-24 Ensemble de feuilles pour mesure de pression, feuille pour mesure de pression, microcapsules, dispersion, procédé de production d'ensemble de feuilles pour mesure de pression, procédé de production de feuille pour mesure de pression WO2022137951A1 (fr)

Priority Applications (3)

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CN202180086265.6A CN116635502A (zh) 2020-12-25 2021-11-24 压力测定用片材组、压力测定用片材、微胶囊、分散液、压力测定用片材组的制造方法、压力测定用片材的制造方法
JP2022571987A JPWO2022137951A1 (fr) 2020-12-25 2021-11-24
KR1020237020619A KR20230106691A (ko) 2020-12-25 2021-11-24 압력 측정용 시트 세트, 압력 측정용 시트, 마이크로 캡슐, 분산액, 압력 측정용 시트 세트의 제조 방법, 압력 측정용 시트의 제조 방법

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61210691A (ja) * 1985-03-15 1986-09-18 新興化学工業株式会社 水平回路を有する配線板の製造方法
JPH08207435A (ja) * 1995-02-01 1996-08-13 Fuji Photo Film Co Ltd 改ざん防止機能を有する感圧記録用シート
JP2004216716A (ja) * 2003-01-15 2004-08-05 Fuji Photo Film Co Ltd 感熱マイクロカプセル、平版印刷原版および平版印刷版の製版方法
JP2015501404A (ja) * 2011-10-14 2015-01-15 ヴァルレック オイル アンド ガスフランス ねじ管状コンポーネント及び得られる接続部
US20170241849A1 (en) * 2016-02-23 2017-08-24 International Business Machines Corporation Pressure indicator films for high temperature applications

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2004024809A1 (ja) 2002-09-13 2006-01-05 旭化成ケミカルズ株式会社 微多孔膜及びその製造方法
KR102262970B1 (ko) 2016-09-29 2021-06-08 후지필름 가부시키가이샤 압력 측정용 재료 조성물, 압력 측정용 재료, 및 압력 측정용 재료 세트
WO2020149410A1 (fr) 2019-01-17 2020-07-23 富士フイルム株式会社 Matériau de mesure de pression et procédé de production de matériau de mesure de pression

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61210691A (ja) * 1985-03-15 1986-09-18 新興化学工業株式会社 水平回路を有する配線板の製造方法
JPH08207435A (ja) * 1995-02-01 1996-08-13 Fuji Photo Film Co Ltd 改ざん防止機能を有する感圧記録用シート
JP2004216716A (ja) * 2003-01-15 2004-08-05 Fuji Photo Film Co Ltd 感熱マイクロカプセル、平版印刷原版および平版印刷版の製版方法
JP2015501404A (ja) * 2011-10-14 2015-01-15 ヴァルレック オイル アンド ガスフランス ねじ管状コンポーネント及び得られる接続部
US20170241849A1 (en) * 2016-02-23 2017-08-24 International Business Machines Corporation Pressure indicator films for high temperature applications

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CN116635502A (zh) 2023-08-22

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