WO2022137893A1 - Ensemble de feuilles de mesure de la pression et procédé de mesure de la pression - Google Patents

Ensemble de feuilles de mesure de la pression et procédé de mesure de la pression Download PDF

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Publication number
WO2022137893A1
WO2022137893A1 PCT/JP2021/042071 JP2021042071W WO2022137893A1 WO 2022137893 A1 WO2022137893 A1 WO 2022137893A1 JP 2021042071 W JP2021042071 W JP 2021042071W WO 2022137893 A1 WO2022137893 A1 WO 2022137893A1
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Prior art keywords
sheet
pressure measurement
layer
pressure
support
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PCT/JP2021/042071
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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 JP2022571961A priority Critical patent/JPWO2022137893A1/ja
Priority to KR1020237020764A priority patent/KR20230106693A/ko
Priority to CN202180086925.0A priority patent/CN116670479A/zh
Publication of WO2022137893A1 publication Critical patent/WO2022137893A1/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
    • 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

Definitions

  • the present invention relates to a pressure measuring sheet set and a pressure measuring method.
  • the pressure measuring sheet (that is, the sheet used for pressure measurement) is used for applications such as a bonding process of liquid crystal glass, solder printing on a printed circuit board, and pressure adjustment between rollers.
  • Patent Document 1 discloses a pressure measuring sheet that utilizes a color-developing reaction between a color-developing agent and a color-developing agent, and describes that measurement can be performed in a pressure range of about 0.1 to 20 MPa.
  • Patent Document 2 discloses an invention relating to a method for producing a polyolefin film, and measures the area of a pressured region on a sheet using a pressure measuring sheet when the sheet is compressed by a pressure roll. What was done (page 65, line 16 to page 66, line 9) is described.
  • the present inventors may cause the above-mentioned problems by melting or deforming the support provided for supporting the layer containing microcapsules and / or the layer containing a color developer by heat. And tried to solve the above problem by providing a protective sheet. However, depending on the type of protective sheet and the type of pressure measurement sheet, the problem may not be solved. Further, when the protective sheet is provided, the resolvability of the pressure distribution may be lowered depending on the mode.
  • the present invention has deformation of the support, reduction of the resolution of the pressure distribution image (hereinafter, also simply referred to as resolution), and contamination of the object to be measured when the pressure measurement is performed under high temperature conditions. It is an object of the present invention to provide a sheet set for pressure measurement that can suppress the above. Another object of the present invention is to provide a pressure measuring method.
  • a pressure measuring sheet set comprising a second sheet having a second layer containing a developer and a protective sheet, wherein the protective sheet is a resin film or paper, and the resin film is provided.
  • the glass transition temperature is 100 ° C. or higher, or the glass transition temperature is not indicated, and the thickness T1 of the first support, the thickness T2 of the second support, and the thickness T3 of the protective sheet are A sheet set for pressure measurement that satisfies all of the formulas (a) to (d) described later.
  • a pressure measuring sheet set including a laminate having a first support, a second layer containing a color developer, and a first layer containing microcapsules containing a color former, and a protective sheet.
  • the protective sheet is a resin film or paper, and the resin film has a glass transition temperature of 100 ° C. or higher, or does not show a glass transition temperature, and has a thickness T1 of the first support and the above.
  • the pressure measurement sheet set according to [10] wherein the protective sheet is a polyethylene naphthalate film, a polyimide film, or paper.
  • [16] The pressure measurement sheet set according to any one of [10] to [15], wherein the arithmetic mean roughness Ra of the surface of the protective sheet is 0.1 ⁇ m or less.
  • It has a step A2 for manufacturing and a step B for pressurizing the pressure measuring sheet by two members arranged on both sides of the pressure measuring sheet, and in the step B, at least of the two members.
  • a pressure measurement sheet set capable of suppressing deformation of a support, deterioration of the resolution of a pressure distribution image, and contamination of a measurement object even when pressure measurement is performed under high temperature conditions. And a pressure measuring method can be provided.
  • the numerical range represented by using "-" in the present specification 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.
  • Each component described later may be used alone or in combination of two or more.
  • the polyisocyanate described later may be used alone or in combination of two or more.
  • the content of the component means the total content of two or more kinds of substances unless otherwise specified.
  • the pressure measuring sheet set according to the present invention is a sheet having a support, a first layer containing a microcapsule containing a coloring agent and / or a second layer containing a developing agent, and a sheet including a protective sheet.
  • the protective sheet is a resin film (hereinafter, also referred to as "specific resin film”) or paper having a glass transition temperature of 100 ° C. or higher or not showing a glass transition temperature, and is used for pressure measurement. It is characterized in that the thickness of the support and the thickness of the protective sheet of the sheet set satisfy a specific relational expression.
  • the present inventors use the above-mentioned protective sheet made of a specific resin film or paper, and use it as a pressure measurement sheet so as to satisfy all the specific relational expressions.
  • the present invention has been completed by finding that various pressure measurements can be performed.
  • the detailed mechanism that enables more accurate pressure measurement by the present invention is unknown, the provision of a specific protective sheet makes it difficult for heat to be transferred to the layer containing the microcapsules, resulting in leakage of the color former layer.
  • a protective sheet that is suppressed and has a specific hardness appropriate pressure is transmitted to the layer containing the microcapsules even through the protective sheet, enabling accurate pressure measurement.
  • the present inventors speculate.
  • FIG. 1 is a schematic diagram showing a configuration of an embodiment of a pressure measurement sheet set according to the present invention.
  • the sheet set 10 which is a pressure measurement sheet set according to the first embodiment, includes a first sheet 16, a second sheet 22, and a protective sheet 40.
  • the first sheet 16 has a first support 12 and a first layer 14 containing microcapsules 13 arranged on the first support 12.
  • the second sheet 22 has a second support 18 and a second layer 20 containing a color developer arranged on the second support 18.
  • the protective sheet 40 included in the sheet set 10 is a specific resin film or paper.
  • the thickness T1 of the first support, the thickness T2 of the second support, and the thickness T3 of the protective sheet all satisfy the following formulas (a) to (d).
  • the thickness T1 of the first support, the thickness T2 of the second support, and the thickness T3 of the protective sheet are not limited as long as all of the above formulas (a) to (d) are satisfied.
  • the thickness T1 preferably satisfies the following formula (a0), and more preferably satisfies the following formula (a1).
  • the thickness T2 preferably satisfies the following formula (b0), and more preferably satisfies the following formula (b1).
  • a combination in which the thickness T1 satisfies the above formula (a0) and the thickness T2 satisfies the above formula (b0) is preferable, and the deformation resistance and the resolution under high temperature conditions are improved.
  • a combination in which the thickness T1 satisfies the above formula (a1) and the thickness T2 satisfies the above formula (b1) is more preferable.
  • the thicknesses T1, T2 and T3 preferably satisfy the following formula (c1) and more preferably the following formula (c2) in that the deformation resistance under high temperature conditions is more excellent.
  • the upper limit of the value obtained by substituting the thicknesses T1, T2 and T3 into the formula of "T3- (T1 + T2) x 0.2" is not particularly limited, but the following formula ( It is preferable to satisfy c3).
  • the thicknesses T1, T2 and T3 preferably satisfy the following formula (d1) and more preferably the following formula (d2) in that they are more excellent in deformation resistance and resolution under high temperature conditions.
  • (D1) 100 ⁇ m ⁇ T1 + T2 + T3 ⁇ 275 ⁇ m
  • (D2) 135 ⁇ m ⁇ T1 + T2 + T3 ⁇ 275 ⁇ m
  • the first sheet 16, the second sheet 22 and the protective sheet 40 are used, and the first layer 14 and the second sheet of the first sheet 16 are used.
  • a pressure measurement sheet 100 is produced by laminating the 22 second layer 20 so as to face each other, and pressure measurement is performed by applying pressure to the obtained pressure measurement sheet 100.
  • a method of producing a pressure measuring sheet using the pressure measuring sheet set according to the present embodiment and measuring the pressure will be described later.
  • the pressure measurement sheet set according to the present embodiment is not limited to the mode shown in FIG.
  • the first support 12 and the first layer 14 are directly laminated, but another layer (for example, between the first support 12 and the first layer 14) is directly laminated.
  • Adhesion layer may be arranged.
  • the second support 18 and the second layer 20 are directly laminated, but another layer (for example, close contact) is between the second support 18 and the second layer 20. Layers) may be arranged.
  • the first sheet has a first support and a first layer, which is arranged on the first support and contains microcapsules containing a coloring agent.
  • 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.
  • the first support may have any of a sheet shape, a film shape, and a plate shape.
  • Examples of the first support include paper, resin film, and synthetic paper. Papers include high-quality paper, medium-quality paper, shaving paper, neutral paper, acidic paper, recycled paper, coated paper, machine-coated paper, art paper, cast-coated paper, finely coated paper, tracing paper, and recycled paper. Paper is mentioned.
  • Examples of the resin film include polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polyamide (PA) film, polyimide (PI) film, polysulfon (PSF), polyether sulfone (PES) film, cellulose derivative film, and the like. Examples thereof include polyolefin films such as polypropylene and polyethylene, and polystyrene films.
  • Synthetic paper includes polypropylene or polyethylene terephthalate stretched biaxially to form a large number of microvoids (Yupo, etc.), polyethylene, polypropylene, polyethylene terephthalate, synthetic fibers such as polyamide, and synthetic paper. Examples thereof include those obtained by laminating these on a part of paper, one side or both sides. Among them, a resin film or synthetic paper is preferable, and a resin film is more preferable, from the viewpoint of further increasing the color development density generated by pressurization.
  • the thickness T1 of the first support is as described above.
  • the first support preferably has a thermal resistance value of 0.0001 m 2 ⁇ K / W or more, preferably 0.0003 m 2 ⁇ K / W, in that it is more excellent in deformation resistance and antifouling property under high temperature conditions. It is more preferably W or more.
  • the upper limit is not particularly limited, but is preferably 0.1 m 2 ⁇ K / W or less.
  • Thermal conductivity (W / (m ⁇ K)) of the material constituting the first support is known, it is calculated from the thermal conductivity and the thickness T1 ( ⁇ m) of the first support based on the following formula. can.
  • Thermal resistance value (m 2 ⁇ K / W) thickness T1 ( ⁇ m) ⁇ 10-6 / thermal conductivity (W / (m ⁇ K))
  • the first layer contains microcapsules containing a color former.
  • the microcapsule usually has a core portion and a capsule wall for encapsulating a core material (encapsulated material (also referred to as an encapsulating component)) forming the core portion. Since the color-developing agent is encapsulated in microcapsules as a core material (encapsulating component), the color-developing agent can exist stably until the microcapsules are destroyed by pressure.
  • encapsulated material also referred to as an encapsulating component
  • Examples of the material (wall material) for the capsule wall include known resins used as wall materials for microcapsules for pressure-sensitive copying paper or heat-sensitive recording paper containing a coloring agent.
  • Examples of the resin include polyurethane, polyurea, polyurethane urea, melamine-formaldehyde resin, and gelatin.
  • the capsule wall 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, and 100% by mass is preferable. That is, the capsule wall of the microcapsule is preferably made of resin.
  • the polyurethane is a polymer having a plurality of urethane bonds, and is preferably a reaction product formed from a raw material containing a polyol and a polyisocyanate.
  • the polyurea is a polymer having a plurality of urea bonds, and is preferably a reaction product formed from a raw material containing a polyamine and a polyisocyanate.
  • the polyurethane urea is a polymer having a urethane bond and a urea bond, and is preferably a reaction product formed from a raw material containing a polyol, a polyamine, and a polyisocyanate.
  • a part of the polyisocyanate reacts with water to form a polyamine, and as a result, polyurethane urea may be obtained.
  • the melamine-formaldehyde resin is preferably a reaction product formed from polycondensation of melamine and formaldehyde.
  • the polyisocyanate is a compound having two or more isocyanate groups, and examples thereof include aromatic polyisocyanates and aliphatic polyisocyanates.
  • examples of the polyisocyanate include aromatic diisocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, naphthalene-1,4-diisocyanate, and diphenylmethane-.
  • 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 hydride xylylene diisocyanate.
  • trifunctional or higher functional polyisocyanates may also be used as polyisocyanates.
  • the polyisocyanate is an adduct (addition) 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.
  • 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 trifunctional or higher polyisocyanate (adduct type trifunctional or higher polyisocyanate) which is a body (additive) and a trimer of an aromatic or alicyclic diisocyanate (biuret type or isocyanurate type) are also preferable.
  • a trifunctional or higher polyisocyanate, which is the adduct body (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 hydroxyl groups in one molecule is preferable.
  • the adduct body it is preferable to use an adduct body obtained by using an aromatic diisocyanate because the pressure distribution can be measured better under high temperature conditions.
  • 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 DIC Corporation Barnock® D-750 is preferred.
  • isocyanurate-type trifunctional or higher functional isocyanate include Takenate (registered trademark) D-127N, D-170N, D-170HN, D-172N, D-177N, and D-204 (manufactured by Mitsui Chemicals, Inc.).
  • 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 (Sumitomo Bayer Urethane), and Duranate (registered trademark). ) 24A-100 (manufactured by Asahi Kasei Corporation).
  • polymethylene polyphenyl polyisocyanate is also preferable. That is, the resin is preferably polyurethane or polyurethane urea having a polymethylenepolyphenyl structure as a partial structure.
  • the polymethylene polyphenyl structure is a structure derived from polymethylene polyphenyl polyisocyanate.
  • Polymethylenepolyphenylpolyisocyanate is, for example, a compound represented by the formula (X).
  • n represents the number of repeating units.
  • the number of repeating units represents an integer of 1 or more, and n is preferably an integer of 1 to 10 and more preferably an integer of 1 to 5 in that the pressure distribution can be measured better under high temperature conditions.
  • Examples of the polyisocyanate containing polymethylene polyphenyl polyisocyanate include Millionate MR-100, Millionate MR-200, Millionate MR-400 (manufactured by Tosoh Co., Ltd.), WANNAME PM-200, and WANNAME PM-400 (Manhua Japan Co., Ltd.).
  • Cosmonate M-50, Cosmonate M-100, Cosmonate M-200, Cosmonate M-300 (manufactured by Mitsui Chemicals Co., Ltd.), and Boranate M-595 (manufactured by Dow Chemicals Co., Ltd.). Will be.
  • the polyol is a compound having two or more hydroxyl groups, and for example, a low molecular weight polyol (eg, an aliphatic polyol or an aromatic polyol.
  • the “low molecular weight polyol” is intended to be a polyol having a molecular weight of 400 or less.
  • the low molecular weight polyol means a polyol having a molecular weight of 400 or less, for example, bifunctional low molecular weight polyols such as ethylene glycol, diethylene glycol, and propylene glycol, as well as glycerin, trimethylolpropane, hexanetriol, and penta. Examples thereof include trifunctional or higher low molecular weight polyols such as erythritol and sorbitol.
  • Examples of the hydroxyl group-containing amine compound include amino alcohols as oxyalkylated derivatives of amino compounds.
  • the amino alcohol include N, N, N', N'-tetrakis [2-hydroxypropyl] ethylenediamine, which are propylene oxides or adducts of ethylene oxide of amino compounds such as ethylenediamine, and N, N, N'. , N'-Tetrakis [2-hydroxyethyl] ethylenediamine and the like.
  • a polyamine is a compound having two or more amino groups (primary amino group or secondary amino group), and is a fat such as diethylenetriamine, triethylenetetramine, 1,3-propylenediamine, and hexamethylenediamine.
  • Group polyvalent amines Epoxy compound adducts of aliphatic polyvalent amines; Alicyclic polyvalent amines such as piperazine; 3,9-bis-aminopropyl-2,4,8,10-tetraoxaspiro- (5, 5) Examples thereof include heterocyclic diamines such as 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 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 diisocyanates and polymethylene polyphenyl polyisocyanates (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 polymethylene polyphenyl polyisocyanate to aromatic diisocyanate is not particularly limited, but is preferably 0.1 to 10 and 0. .5-2 is more preferable, and 0.75 to 1.5 is even more preferable.
  • the mass ratio of polyisocyanate A to polyisocyanate B is not particularly limited, but is 98/2 to 20/80. Is preferable, 80/20 to 20/80 is more preferable, and 80/20 to 45/55 is even more preferable.
  • the mass ratio is within the above range, the pressure distribution can be better measured under high temperature conditions. In addition, the temperature dependence of color development is small.
  • the thermal decomposition temperature of the capsule wall of the microcapsules is preferably 250 ° C. or higher, more preferably 255 ° C. or higher, and even more preferably 260 ° C. or higher.
  • the upper limit 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. When 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. Ethyl acetate is added to the separated microcapsules, and the mixture is further stirred at 25 ° C. for 24 hours. Then, 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 average particle size of the microcapsules is not particularly limited, but is preferably 1 to 80 ⁇ m, more preferably 5 to 70 ⁇ m, still more preferably 10 to 50 ⁇ m.
  • the average particle size of the microcapsules can be controlled by adjusting the manufacturing conditions of the microcapsules and the like.
  • the average particle size of the above-mentioned microcapsules is a value obtained by the following method. Images taken from the surface of the first layer are analyzed with an optical microscope (OLYMPUS BX60, field size: 320 ⁇ m ⁇ 450 ⁇ m), and the major axis (particle size) of 30 microcapsules is measured in order from the largest microcapsule. Then, these are arithmetically averaged to obtain the average value. This operation is performed at any 5 locations (5 fields of view) of the first layer, the average of the average values obtained at each location is obtained, and the obtained value is used as the average particle size of the microcapsules.
  • the major axis means the longest diameter when observing the microcapsules.
  • the number average wall thickness of the capsule walls of the microcapsules is not particularly limited, but is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.0 ⁇ m in terms of excellent pressure responsiveness.
  • the wall thickness of the microcapsules refers to the thickness ( ⁇ m) of the capsule wall forming the capsule particles of the microcapsules, and the number average wall thickness is the thickness ( ⁇ m) of the individual capsule walls of the 20 microcapsules. Is obtained by a scanning electron microscope (SEM) and averaged. More specifically, a cross-sectional section of the first sheet having the first layer containing microcapsules was prepared, and the cross-section was observed by SEM at 15,000 times (value of average particle size of microcapsules) ⁇ 0. Select any 20 microcapsules having a diameter in the range of 9 to (average diameter of microcapsules) ⁇ 1.1, and observe the cross section of each selected microcapsule to observe the cross section of the capsule wall. Obtain the thickness and calculate the average value.
  • the ratio ( ⁇ / Dm) of the number average wall thickness ⁇ of the microcapsules to the average particle size of the microcapsules is not particularly limited, and is often 0.001 or more. Above all, it is preferable to satisfy the relationship of the formula (1) in that it is excellent in setting the color development density according to the pressure. Equation (1) ⁇ / Dm> 0.001 That is, the ratio ( ⁇ / Dm) is preferably larger than 0.001. Further, the above ratio ( ⁇ / Dm) is more preferably 0.002 or more. The upper limit is not particularly limited, but 0.2 or less is preferable. When the microcapsules satisfy the relationship of the above formula (1), the size of the capsule and the thickness of the capsule wall are well-balanced, and there is less concern that the inclusions of the microcapsules may leak under high temperature conditions.
  • the microcapsules contain a coloring agent.
  • the "color former” is a compound that develops a color when it comes into contact with a color developer described later from a colorless state.
  • the color-developing agent an electron-donating dye precursor (precursor of a dye that develops color) is preferable. That is, as the color former, an electron-donating colorless dye is preferable.
  • the color-developing agent those known in the application of pressure-sensitive copying paper or thermal recording paper can be used.
  • Examples of the color former include triphenylmethanephthalide-based compounds, fluorene-based compounds, phenothiazine-based compounds, indolylphthalide-based compounds, azaindrillphthalide-based compounds, leukooramine-based compounds, rhodamine lactam-based compounds, and triazene.
  • Examples thereof include phenylmethane-based compounds, diphenylmethane-based compounds, triazene-based compounds, spiropyran-based compounds, and fluorene-based compounds.
  • Japanese Patent Application Laid-Open No. 5-257272 and the description of International Publication No. 2009/0087248 [0029] to [0034].
  • the molecular weight of the color former is not particularly limited and is often 300 or more.
  • the upper limit is not particularly limited, but in many cases it is 1000 or less, and 600 or less is preferable in that the effect of the present invention is more excellent.
  • Preferred examples of the color former include 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide and 3- (4-diethylamino-2).
  • microcapsules may contain components other than the above-mentioned color former.
  • microcapsules preferably contain a solvent.
  • the solvent is not particularly limited, and for example, an alkylnaphthalene-based compound such as diisopropylnaphthalene, a diarylalkane-based compound such as 1-phenyl-1-xylylethane, an alkylbiphenyl-based compound such as isopropylbiphenyl, a triarylmethane-based compound, and an alkylbenzene-based compound.
  • Aromatic hydrocarbons such as benzylnaphthalene compounds, diarylalkylene compounds, and arylindan compounds; aliphatic hydrocarbons such as dibutyl phthalate and isoparaffin, soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, etc. Examples thereof include natural animal and vegetable oils such as coconut oil, castor oil and fish oil, and high boiling point distillates of natural products such as mineral oil.
  • the solvent preferably has an aromatic solvent from the viewpoint of improving the solubility of the color former.
  • the solvent may be used alone or in combination of two or more.
  • the mass ratio of the solvent to the color-developing agent is preferably in the range of 98/2 to 30/70 in terms of color-developing property.
  • the range of 97/3 to 40/60 is more preferable.
  • the microcapsules may contain one or more additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, a wax, and an odor suppressant, if necessary.
  • an ultraviolet absorber a compound having a benzotriazole structure is preferable.
  • the method for producing microcapsules 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. Of these, the interfacial polymerization method is preferable.
  • the interfacial polymerization method is a raw material containing a color former and a capsule wall material (for example, a polyisocyanate and at least one selected from the group consisting of a polyol and a polyamine. A polyisocyanate is reacted with water to form a polyamine.
  • 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 is used.
  • An interface 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 the polyol and the polyamine to the amount of the polyisocyanate (total amount of the polyol and the polyamine / the amount of the polyisocyanate) in the above raw materials is not particularly limited, but is 0.1 / 99.9 to. 30/70 is preferable, and 1/99 to 25/75 is more preferable.
  • 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 contains the microcapsules described above.
  • the content of the microcapsules in the first layer is not particularly limited, but 50 to 90% by mass is preferable with respect to the total mass of the first layer in that the pressure distribution can be measured better under high temperature conditions. , 55 to 85% by mass, more preferably 55 to 80% by mass.
  • the content of the color former in the first layer is not particularly limited, but 0.1 to 10 g / m 2 is preferable, and 0.1 is preferable because the pressure distribution can be measured better under high temperature conditions. ⁇ 4 g / m 2 is more preferable.
  • the first layer may contain components other than the above-mentioned microcapsules.
  • Other components include, for example, polymer binders, inorganic fillers (eg colloidal silica), optical brighteners, defoamers, penetrants, UV absorbers, surfactants, and preservatives.
  • the mass (solid content coating amount) (g / m 2 ) per unit area of the first layer is not particularly limited, but is, for example, 0.5 to 20.0 g / m 2 and 0.5 to 10.0 g / m 2. m 2 is preferred.
  • polymer binder examples 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 or salts thereof, methyl cellulose, polyolefins, and modified acrylic acid ester copolymers, or natural polymers.
  • the viscosity of the composition for forming the first layer can also be adjusted by adding a polymer binder.
  • the polymer binder may be used alone or in combination of two or more.
  • 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, etc., but in terms of maintaining the dispersibility of the microcapsules, anionic surfactants or Nonionic surfactants are preferred.
  • the surfactant examples include a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, and the like, but the hydrocarbon-based interface is used in terms of maintaining coatability and dispersibility of microcapsules. Activators 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. 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, still more preferably 5 to 20% by mass, based on 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, more 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, more preferably 25% or less, based on the average particle size of the microcapsules. The thinner the thickness of the first layer is with respect to the microcapsules, the more easily the microcapsules are broken, so that the thickness can be adjusted according to the pressure band to be measured.
  • the arithmetic mean roughness Ra of the surface of the first layer opposite to the first support is preferably 2 ⁇ m or more, more preferably 4.1 ⁇ m or more, in that it is suitable for pressure measurement under a low pressure region.
  • the upper limit is not particularly limited, but is preferably 10 ⁇ m or less.
  • the arithmetic mean roughness Ra of the first layer in the present embodiment is the arithmetic mean roughness Ra of the surface of the surface of the first layer facing the second sheet (contacting side) when the pressure measuring sheet set is used. Is.
  • the arithmetic mean roughness Ra of the first layer in the present specification means the arithmetic mean roughness Ra defined in JIS B 0681-6: 2014.
  • a scanning white interferometer using an optical interferometry (specifically, NewView5020 manufactured by Zygo: Stich mode; objective lens ⁇ 50 times; intermediate lens ⁇ 0.5 times). Is used.
  • the arithmetic mean roughness Ra of the first layer is at least the above lower limit value, a sufficient amount of the color-developing agent is often sufficient, so that a higher color-developing density is likely to occur.
  • the second layer of the second sheet when the arithmetic mean roughness Ra of the first layer is not more than the above upper limit value, the second layer of the second sheet appropriately absorbs the solvent flowing out together with the color former due to the disintegration of the microcapsules in the pressurized region. Since it can be done, good image quality with less bleeding can be obtained.
  • the arithmetic mean roughness Ra of the first layer can be controlled by adjusting the amount of solid content applied to the composition for forming the first layer and adjusting the amount of microcapsules in the first layer.
  • the method for forming the first layer is not particularly limited, and known methods can be mentioned. For example, a method of applying a composition for forming a first layer containing microcapsules on a first support and, if necessary, drying a coating film can be mentioned.
  • 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.
  • the coating machine used for applying the composition for forming the first layer include an air knife coater, a rod coater, a bar coater, a curtain coater, a gravure coater, an extrusion coater, a die coater, a slide bead coater, and a blade coater. Can be mentioned.
  • 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 first sheet may have members other than the first support and the first layer described above.
  • the first sheet may have an adhesion layer between the first support and the first layer for enhancing the adhesion between the two.
  • the first support may be subjected to surface treatment such as corona discharge treatment.
  • the adhesion layer preferably contains a resin from the viewpoint of adhesion.
  • the resin may be, for example, a layer containing a resin formed from a urethane polymer or a blocked isocyanate.
  • the layer may contain at least one selected from the group consisting of gelatin, styrene / butadiene rubber, cellulose analogs, and polystyrene.
  • the adhesion layer preferably has a polymer having an aromatic group.
  • the thickness of the adhesion layer is not particularly limited, and is preferably 0.005 to 5 ⁇ m, more preferably 0.01 to 1 ⁇ m.
  • the second sheet has a second support and a second layer containing a color developer placed on the second support.
  • the second sheet may be a single leaf (single sheet) or a long sheet.
  • the second support is a member for supporting the second layer. Since the shape of the second support and the materials constituting the second support are the same as those of the first support described above, the description thereof will be omitted. Further, the thickness T2 of the second support is as described above.
  • the second support preferably has a thermal resistance value of 0.0001 m 2 ⁇ K / W or more, and is 0.0003 m 2 ⁇ K / W or more in that it has better deformation resistance under high temperature conditions. Is more preferable.
  • the upper limit is not particularly limited, but is preferably 0.1 m 2 ⁇ K / W or less.
  • 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 by contacting with the color-developing agent.
  • an electron-accepting compound is preferable.
  • Examples of the color developer include inorganic compounds and organic compounds.
  • the inorganic compound examples include clay substances such as acid clay, activated clay, attapargite, zeolite, bentonite, and kaolin.
  • a dispersant for dispersing the inorganic compound in combination.
  • the dispersant is appropriately selected depending on the surface physical characteristics of the inorganic compound. For example, anionic hexametaphosphate or a salt thereof is used for acid-treated active clay.
  • the organic compound include a metal salt of an aromatic carboxylic acid, a phenol formaldehyde resin, a metal salt of a carboxylated terpene phenol resin, and the like.
  • 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-dodecylsalicylic acid.
  • the metal salt of the aromatic carboxylic acid the zinc salt, nickel salt, aluminum salt, or calcium salt of the above aromatic carboxylic acid is preferable.
  • the color developer the inorganic compounds and organic compounds described in International Publication No. 2009/008248 [0055] to [0056] can also be used, and this description is incorporated in the present specification.
  • 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 clay.
  • the substance is more preferable, and acidic clay, active clay, or kaolin is particularly preferable.
  • the clay substance is less likely to discolor when measuring pressure under high temperature conditions, so that the display quality of the pressure distribution in the pressure measurement sheet set is excellent.
  • the content of the color developer in the second layer is not particularly limited, but 20 to 95% by mass with respect to the total mass of the second layer is that the pressure distribution can be measured better under high temperature conditions. It is preferably 30 to 90% by mass, more preferably 30 to 90% by mass.
  • the color developer may be used alone or in combination of two or more.
  • the content of the color developer in the second layer is preferably 0.1 to 30 g / m 2 .
  • the content of the developer is preferably 3 to 20 g / m 2 and more preferably 5 to 15 g / m 2 .
  • the content of the developer is preferably 0.1 to 5 g / m 2 , more preferably 0.2 to 3 g / m 2 .
  • the second layer may contain components other than the above-mentioned developer.
  • other components include polymer binders, pigments, fluorescent whitening agents, antifoaming 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, polyolefins, modified acrylic acid ester copolymers or salts thereof, and synthetic polymers such as methyl cellulose and natural polymers.
  • the polymer binder may be used alone or in combination of two or more.
  • the content of the polymer binder is not particularly limited, but is preferably 0.1 to 80% by mass, more preferably 1 to 50% by mass, based on the total mass of the second layer.
  • the pigment include heavy calcium carbonate, light calcium carbonate, talc, and titanium dioxide.
  • the surfactant include the same embodiments as those of the surfactant contained in the first layer described above, and the preferred embodiments are also the same.
  • the thickness of the second layer is not particularly limited, but is preferably 1 to 50 ⁇ m, more preferably 2 to 30 ⁇ m, in that the pressure distribution can be measured better under high temperature conditions.
  • the mass (solid content coating amount) (g / m 2 ) per unit area of the second layer is not particularly limited, but may be, for example, 0.5 to 30.0 g / m 2 and 3.5 to 3 30.0 g / m 2 is preferable.
  • the method for forming the second layer is not particularly limited, and known methods can be mentioned. 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. Examples of the drying treatment include heat treatment.
  • the second sheet may have a member other than the above-mentioned second support and the second layer.
  • the second sheet may have an adhesion layer between the second support and the second layer for enhancing the adhesion between the two. Since the aspect of the adhesion layer is the same as the aspect of the adhesion layer that the first sheet may have, the description thereof will be omitted.
  • the pressure measurement sheet set according to the present embodiment is made of a specific resin film or paper having a glass transition temperature of 100 ° C. or higher or does not show a glass transition temperature, and is made of the above formulas (c) and (d). ) Is provided with a protective sheet having a thickness T3 (hereinafter, also referred to as “protective sheet P” in the present specification).
  • the protective sheet P may be a single sheet (single sheet) or a long sheet. Further, the protective sheet P may have any of a sheet shape, a film shape, and a plate shape.
  • paper examples include high-quality paper, medium-quality paper, shaving paper, neutral paper, acidic paper, recycled paper, coated paper, machine-coated paper, art paper, cast-coated paper, finely coated paper, tracing paper, and the like.
  • Recycled paper can be mentioned.
  • the resin constituting the specific resin film is not particularly limited as long as the film satisfies the above conditions.
  • the resin constituting the specific resin film include polyethylene naphthalate, polyethylene terephthalate, and a copolymer of polyethylene naphthalate, polyamide, polyimide, polyamideimide, polysulfone, polyethersulfone, polycarbonate, polyphenylsulfone, and polyetherimide. , And the polyether ether ketone and the like.
  • a polyethylene naphthalate film or a polyimide film is preferable because it is more excellent in antifouling property under high temperature conditions.
  • the polyethylene naphthalate film represents a film containing polyethylene naphthalate at a ratio of 70% by mass or more with respect to the total mass of the film
  • the polyimide film refers to a polyimide film containing 70% by mass with respect to the total mass of the film. Represents a film containing the above ratio.
  • Examples of commercially available polyethylene naphthalate films include Theonex (registered trademark) Q51, Q53, Q81 and Q83 (manufactured by Teijin Film Solutions Co., Ltd.).
  • polyimide films examples include Kapton (registered trademark) H, V, and EN (manufactured by Toray Industries, Inc.), and Apical AH, NPI, and AF (manufactured by Kaneka Corporation).
  • Kapton registered trademark
  • H, V, and EN manufactured by Toray Industries, Inc.
  • Apical AH, NPI, and AF manufactured by Kaneka Corporation.
  • a polyethylene naphthalate film, a polyimide film or paper is preferable, and a polyimide film or paper is more preferable in that the effect of the present invention can be further improved.
  • the glass transition temperature of the resin film can be measured using a differential scanning calorimeter (DSC, device name: DSC-60aPlus, manufactured by Shimadzu Corporation). Specifically, a sample obtained by cutting a resin film is placed in a closed pan of a differential scanning calorimeter and measured at a heating rate of 5 ° C./min in the range of 25 ° C. to 250 ° C. As the glass transition temperature of the resin film, the value at the time of raising the temperature in the second cycle is used. As used herein, the fact that the resin film does not exhibit a glass transition temperature means that the resin constituting the resin film does not exhibit a glass transition temperature in the temperature range of 25 ° C to 250 ° C. When a commercially available resin film is used, the catalog value of the glass transition temperature may be adopted.
  • DSC differential scanning calorimeter
  • the specific resin film is preferably a resin film having a glass transition temperature of 110 ° C. or higher or showing no glass transition temperature, and a glass transition temperature of 150 ° C. or higher, because it is more excellent in antifouling property under high temperature conditions. Or, a resin film that does not show a glass transition temperature is more preferable.
  • the thickness T3 of the protective sheet P is as described above.
  • the protective sheet P may be composed of a single layer made of a specific resin film or paper, or may be made of a layer made of a plurality of specific resin films or paper.
  • the arithmetic mean roughness Ra of the surface of the protective sheet P is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less.
  • the lower limit is not particularly limited, but 0.001 ⁇ m or more is preferable.
  • the arithmetic mean roughness Ra on the surface of the protective sheet P can be measured according to the above-mentioned method for measuring the arithmetic mean roughness Ra of the first layer.
  • the protective sheet P preferably has a thermal resistance value of 0.0001 m 2 ⁇ K / W or more, and is 0.0003 m 2 ⁇ K / W or more in that it has better deformation resistance under high temperature conditions. Is more preferable.
  • the upper limit is not particularly limited, but is preferably 0.1 m 2 ⁇ K / W or less.
  • the thermal resistance value of the protective sheet P can be measured by a thermal resistance measuring instrument. If the thermal conductivity (W / (m ⁇ K)) of the material constituting the protective sheet P is known, it may be calculated from the thermal conductivity and the thickness T3 ( ⁇ m) of the protective sheet P.
  • the protective sheet P may have a gap.
  • Examples of the protective sheet P having voids include a porous film Siporus SEF (manufactured by Chukoh Chemical Industries, Ltd.).
  • the first sheet, the second sheet, and the protective sheet P included in the pressure measuring sheet set are combined with the first layer in the first sheet and the second layer in the second sheet. It has a step A1 for producing a pressure measuring sheet by laminating so as to face each other, and a step B for pressurizing the pressure measuring sheet by two members arranged on both sides of the pressure measuring sheet. Further, at least one of the two members used in step B is heated by a heat source, and the protective sheet P is arranged at least on the surface side of the pressure measuring sheet in contact with the heated member.
  • FIG. 2 is a diagram for explaining a usage mode of the pressure measurement sheet set according to the present embodiment, and shows an example of the configuration of a pressure measurement sheet manufactured by using the sheet set 10 shown in FIG.
  • step A1 the first sheet 16, the second sheet 22, and the protective sheet 40, which is the protective sheet P, included in the sheet set 10 are laminated.
  • the stacking order is not particularly limited. For example, after laminating the first sheet 16 and the second sheet 22 so that the first layer 14 and the second layer 20 face each other to prepare a laminated body, two protective sheets are protected on both sides of the obtained laminated body. By laminating the sheets 40, the pressure measuring sheet 100 shown in FIG. 2 can be obtained.
  • the pressure measuring sheet produced by using the pressure measuring sheet set according to the present embodiment is not limited to the one having the configuration shown in FIG.
  • two protective sheets 40 are arranged on the outermost layer so as to sandwich the first sheet 16 and the second sheet 22, but the measurement for measuring the pressure in the step B is performed.
  • the protective sheet P may be provided only on the surface in contact with the heated member.
  • the other surface may be provided with a protective sheet other than the protective sheet P, or may not be provided with the protective sheet.
  • a pressure measuring sheet in which the two protective sheets P are arranged on the outermost layer may be used.
  • step B the pressure measuring sheet is pressurized by two members (not shown) which are measurement objects arranged on both sides of the pressure measuring sheet 100 produced in step A1.
  • step B when the pressure measuring sheet 100 is pressurized by the two members, the microcapsules 13 are broken in the pressurized region of the first layer 14 facing the second layer 20, and the microcapsules 13 are broken.
  • the color-developing agent contained in the microcapsules comes out of the microcapsules 13, and the color-developing reaction proceeds with the color-developing agent in the second layer 20.
  • an image pressure image
  • the pressure measuring sheet pressurized in step B is separated from the first sheet and the second sheet after peeling the protective sheet from the pressure measuring sheet as necessary, and appears in the second layer of the second sheet.
  • the pressure image color development according to the pressure
  • the magnitude and pressure distribution of the pressure applied to the pressure measuring sheet in step B can be analyzed.
  • the above pressure image may be confirmed visually or by using a pressure image analysis system (FPD-8010, manufactured by FUJIFILM Corporation).
  • FPD-8010 manufactured by FUJIFILM Corporation
  • the protective sheet P is arranged on the surface side of the pressure measuring sheet in contact with the heated member to measure the pressure under high temperature conditions. It is possible to suppress deformation of the support, decrease in resolution, and contamination of the object to be measured, and perform more accurate pressure measurement. That is, even under high temperature conditions, the pressure distribution can be measured with little difference from the measurement result at room temperature (23 ° C.) in terms of the resolution of the pressure distribution.
  • the temperature condition in step B is, for example, 180 to 220 ° C.
  • the pressure measurement sheet set according to the present invention can also be preferably used for pressure measurement under temperature conditions other than high temperature conditions (for example, room temperature).
  • the above temperature condition is the temperature of the surface of the member heated by the heat source in contact with the pressure measuring sheet.
  • the pressure measurement sheet set according to the present invention can be used for pressure measurement in a wide pressure range.
  • the range of 0.05 to 20 MPa is preferable, and the range of 0.5 to 10 MPa is more preferable.
  • Examples of the member heated by the heat source which is the target of the pressure measuring method according to the present embodiment, include a high temperature press machine used for a crimping operation under various high temperature conditions such as a thermocompression bonding step at the time of manufacturing a printed circuit board. ..
  • FIG. 3 is a schematic view showing the configuration of the pressure measurement sheet set according to the second embodiment of the present invention.
  • the sheet set 30, which is a pressure measuring sheet set according to the present embodiment, includes a laminated body 34 and a protective sheet 40.
  • the laminate 34 has a first support 32, a second layer 20 containing a color developer, and a first layer 14 containing microcapsules 13 in this order.
  • the protective sheet 40 included in the sheet set 30 is made of a specific resin film or paper.
  • the thickness T1 of the first support and the thickness T4 of the protective sheet satisfy all of the following formulas (a), (e) and (f).
  • the thickness T1 of the first support and the thickness T4 of the protective sheet are not limited as long as the above formulas (a), (e) and (f) are all satisfied.
  • the thickness T1 preferably satisfies the following formula (a0), and more preferably satisfies the following formula (a1).
  • the thicknesses T1 and T4 preferably satisfy the following formula (e1) in that the deformation resistance under high temperature conditions is more excellent.
  • the upper limit of the value obtained by substituting the thicknesses T1 and T4 into the equation of "T4-T1 ⁇ 0.4" is not particularly limited, but the following equation (e2) is satisfied in that the resolution under high temperature conditions is better. Is preferable.
  • the thicknesses T1 and T4 are more preferably satisfied with the following formula (f1) and more preferably with the following formula (f2) in that they are more excellent in deformation resistance and resolution under high temperature conditions.
  • (F1) 100 ⁇ m ⁇ T1 + T4 ⁇ 250 ⁇ m
  • (F2) 100 ⁇ m ⁇ T1 + T4 ⁇ 225 ⁇ m
  • pressure measurement is performed by laminating the laminated body 34 and the protective sheet 40 to prepare a pressure measurement sheet and applying pressure to the obtained pressure measurement sheet. To carry out.
  • the pressure measurement sheet set according to the present embodiment is not limited to the mode shown in FIG.
  • the first support 32 and the second layer 20 are directly laminated, but another layer (for example, close contact) is formed between the first support and the second layer. Layers) may be arranged.
  • the laminated body 34 shown in FIG. 3 has only the first support 32 as a support, but the laminated body has two supports sandwiching the first layer and the second layer. It may have a laminated structure including a support / two layers / a first layer / a support.
  • the laminate has a first support, a second layer containing a color developer, and a first layer containing microcapsules containing a color former in this order.
  • the laminated body may be a single leaf (single sheet) or may be long.
  • the first support body of the laminated body according to the present embodiment is a member for supporting the second layer and the first layer. Since the shape of the first support and the material constituting the first support in the present embodiment are the same as those in the first support described above, the description thereof will be omitted. Further, the thickness T1 of the first support is as described above.
  • the first layer and the second layer of the laminate according to the present embodiment are the same as the first layer and the second layer described in the first embodiment described above, including the preferred embodiments thereof. Is omitted.
  • the laminated body may have members other than the first support, the first layer, and the second layer.
  • other members include the above-mentioned adhesion layer and a second support arranged so as to sandwich the first layer and the second layer so as to face the first support. Since the adhesion layer that the laminated body may have in this embodiment is the same as the adhesion layer described in the first embodiment described above, the description thereof will be omitted. Further, the second support that the laminated body may have in the present embodiment is the same as the first support described above, including its preferred embodiment, and thus the description thereof will be omitted.
  • the method for producing the laminate is not particularly limited, and examples thereof include known methods.
  • a method for producing the laminate for example, a composition for forming a second layer containing a color developer is applied onto the first support, and if necessary, the coating film is subjected to a drying treatment, and the first After forming the second layer on the support, a composition for forming the first layer containing microcapsules is further applied onto the second layer, and if necessary, the coating film is dried.
  • a method of producing a laminate having the first support, the second layer, and the first layer in this order by forming the first layer on the second layer can be mentioned.
  • the composition for forming the second layer, the method for forming the second layer, the composition for forming the first layer, and the method for forming the first layer are all as described in the first embodiment.
  • the pressure measurement sheet set according to the present embodiment is made of a specific resin film or paper having a glass transition temperature of 100 ° C. or higher or does not show a glass transition temperature, and is made of the above formulas (e) and (f). ) Is provided with a protective sheet having a thickness T4 (hereinafter, also referred to as “protective sheet Q” in the present specification). Since the protective sheet Q is the same as the protective sheet P described in the first embodiment except for the thickness T4, the description thereof will be omitted. Further, the thickness T4 of the protective sheet Q is as described above.
  • a step A2 for laminating a laminated body and a protective sheet Q to produce a pressure measurement sheet and two members arranged on both sides of the pressure measurement sheet are used for pressure. It has a step B of pressurizing a measuring sheet. Further, at least one of the two members used in step B is heated by a heat source, and the protective sheet Q is arranged on at least the surface side of the pressure measuring sheet in contact with the heated member.
  • a pressure measurement sheet is produced using the pressure measurement sheet set according to the present embodiment. More specifically, the protective sheet Q is laminated on at least one of the two surfaces of the laminated body in contact with the member heated in the step B to prepare a pressure measurement sheet.
  • the protective sheet Q is laminated on both sides of the laminated body.
  • the protective sheet Q is laminated on the surface side of the laminated body in contact with the heated member.
  • the protective sheet Q may be laminated on the surface in contact with the member not heated by the heat source, the protective sheet other than the protective sheet Q may be laminated, or the protective sheet may not be laminated.
  • step B the pressure measuring sheet is pressurized by two members which are measurement objects arranged on both sides of the pressure measuring sheet produced in step A2. Since the process B is the same as the process B described in the first embodiment, the description thereof will be omitted.
  • step B For the pressure measuring sheet pressurized in step B, after peeling the protective sheet from the pressure measuring sheet as necessary, the pressure image (color development according to the pressure) appearing on the second layer is confirmed.
  • step B the magnitude and pressure distribution of the pressure applied to the pressure measuring sheet can be analyzed. The method for confirming the above pressure image is as described above.
  • 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.
  • the obtained composition for forming the first layer was applied to a polyethylene terephthalate (PET) sheet (manufactured by Toyobo Co., Ltd., Cosmoshine A4300) having a thickness T1 of 75 ⁇ m and having both sides easily bonded, and having a mass of 6 after drying.
  • PET polyethylene terephthalate
  • the first sheet was prepared by applying and drying with a bar coater so as to be 0.0 g / m 2 .
  • the arithmetic mean roughness Ra of the surface of the prepared first layer opposite to the PET sheet side was 5.0 ⁇ m.
  • NIPPOL LX814 manufactured by Nippon Kogyo Co., Ltd., solid content concentration 46% by mass
  • 35 parts 35 parts
  • a composition for forming a second layer containing a coloring agent was prepared.
  • the composition for forming the second layer containing the color developer was applied onto a PET sheet having a thickness T2 of 75 ⁇ m and a solid content coating amount of 7.0 g / m 2 . Then, the obtained coating film was dried to form a second layer, and a second sheet was obtained.
  • Example 1 As a protective sheet, a polyethylene naphthalate sheet having a thickness T3 of 75 ⁇ m (Teijin Film Solution Co., Ltd., Theonex (registered trademark) Q51) was used, and the first sheet produced in Production Example 1 and the production example 2 were produced. A pressure measurement sheet set according to the first embodiment was prepared, which comprises the second sheet and the protective sheet.
  • Examples 2 to 14 and Reference Examples 1 to 8 A pressure measurement sheet set was prepared in the same manner as in Example 1 except that the configuration of each layer shown in Table 1 was changed.
  • Example 15 A polyethylene terephthalate (PET) sheet (Cosmo Shine A4360, manufactured by Toyobo Co., Ltd.) with a thickness T1 of 75 ⁇ m and easy-adhesion treatment on both sides has a discharge power of 0.7 kW and a discharge electrode length of 0.66 m on one side. , Corona discharge treatment was performed under the condition of a transport speed of 12 m / min to obtain PET film A. The first support used in Production Example 1 was changed from a polyethylene terephthalate (PET) sheet (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) to the PET film A obtained above, and the surface of the PET film A treated with corona discharge.
  • PET polyethylene terephthalate
  • the first sheet 15 was prepared in the same manner as in Preparation Example 1 except that the first layer forming composition was applied to the mixture.
  • the arithmetic mean roughness Ra of the surface of the prepared first sheet 15 on the side opposite to the PET sheet side of the first layer was 5.0 ⁇ m.
  • a polyethylene naphthalate sheet having a thickness T3 of 75 ⁇ m Teijin Film Solution Co., Ltd., Theonex (registered trademark) Q51
  • the pressure measurement sheet set according to the first embodiment was prepared.
  • the first sheet, the second sheet and the protective sheet included in the pressure measurement sheet set prepared in each example and each reference example were cut into a size of 5 cm in length ⁇ 5 cm in length, respectively.
  • the protective sheet, the first sheet, the second sheet, and the protective sheet are laminated in this order so that the surface of the first layer of the first sheet and the surface of the second layer of the second sheet are in contact with each other for pressure measurement.
  • a sample for evaluation test of the sheet was prepared.
  • a hot press with two heatable stages was prepared and heated until the surface temperature of each stage reached 220 ° C.
  • the sample was sandwiched between the two stages and the sample was pressurized at a pressure of 5.0 MPa over 2 minutes.
  • the surface of each stage in contact with the sample was sufficiently wide and flat with respect to the sample.
  • the sample is taken out from the hot press machine, the first sheet and the second sheet are peeled off, each sheet is placed on a flat table, the shape is observed, and the deformation resistance is according to the following criteria. Was evaluated.
  • a sample for evaluation test of the pressure measurement sheet was prepared using the pressure measurement sheet set prepared in each Example and each reference example. Then, in the same manner as in the above-mentioned deformation resistance evaluation test, the stage was heated to 220 ° C. using a hot press machine. The sample was sandwiched between the two stages and the sample was pressurized at a pressure of 5.0 MPa over 2 minutes. After the pressurization was completed, the sample was removed from the stage, and the surface of the stage was observed to confirm the presence or absence of deposits derived from the sample and the state of adhesion. Based on the observation results, the antifouling property of the pressure measurement sheet was evaluated when the pressure was measured under high temperature conditions according to the following criteria.
  • a sample for evaluation test of the pressure measurement sheet was prepared using the pressure measurement sheet set prepared in each Example and each reference example.
  • the sample and the 1-cent coin were sandwiched between two stages heated so that the surface temperature of each stage was 220 ° C. using a hot press machine for 2 minutes.
  • the sample was pressurized over a pressure of 5.0 MPa. After the pressurization was completed, the sample was removed from the stage and the color development state of the sample was observed.
  • the antifouling property of the pressure measurement sheet was evaluated when the pressure was measured under high temperature conditions according to the following criteria.
  • the resolution of the pressure distribution displayed on the pressure measurement sheet when the pressure was measured under high temperature conditions was evaluated according to the following criteria.
  • Table 1 shows the configurations of the pressure measurement sheet sets of Examples 1 to 15 and Reference Examples 1 to 8 and the evaluation results.
  • the "material” column indicates the materials constituting the first support, the second support, or the protective sheet, respectively.
  • “PEN” is polyethylene terephthalate
  • PET is polyethylene terephthalate
  • PET / PEN is polyethylene terephthalate / polyethylene naphthalate copolymer
  • PI is polyimide
  • Al Means aluminum respectively.
  • the “T1 (a)” column indicates the thickness T1 (unit: ⁇ m) of the first support.
  • the “T2 (b)” column indicates the thickness T2 (unit: ⁇ m) of the second support.
  • the “T3” column indicates the thickness T3 (unit: ⁇ m) of the protective sheet.
  • the “Tg” column indicates the glass transition temperature Tg (unit: ° C.) of the material constituting the protective sheet.
  • “* 1" in the "Tg” column means that the glass transition temperature Tg of the material constituting the protective sheet was not shown in the measurement range of 250 ° C. or lower.
  • the "thermal resistance value” column shows the thermal resistance value (unit: m2 ⁇ K / W) material of the first support, the second support or the protective sheet calculated by the above method, respectively.
  • the thickness T1 of the first support, the thickness T2 of the second support, and the thickness T3 of the protective sheet are expressed by the formula (c) ("T3- (T1 + T2) x 0.2"). The value obtained by substituting into is shown.
  • the “(d)” column shows the total of the thickness T1 of the first support, the thickness T2 of the second support, and the thickness T3 of the protective sheet.
  • the arithmetic mean roughness Ra of the surface of the protective sheet used in Examples 1 to 15 was 0.02 to 0.03 ⁇ m.
  • Example 15 is different from Example 1 in that the first sheet 15 produced by using PET film A whose surface facing the first layer is subjected to corona discharge treatment is used as the first support. Is different. Further, as a result of performing pressure measurement under the above high temperature conditions using the pressure measurement sheet set prepared in Reference Example 8, the pressure sheet set melted and adhered to the stage, so that the evaluation of the resolution of the pressure distribution was performed. Can not be implemented.
  • the composition for forming the first layer prepared in Preparation Example 1 was applied onto the second layer so that the mass after drying was 6.0 g / m 2 , and the obtained coating film was dried.
  • the first layer a laminated body having the first support, the second layer, and the first layer in this order was produced.
  • Example 101 As the protective sheet, a polyethylene naphthalate sheet having a thickness T4 of 75 ⁇ m (Teijin Film Solution Co., Ltd., Theonex (registered trademark) Q51) is used, and the laminate is composed of the laminate produced in Production Example 101 and the protective sheet. , A sheet set for pressure measurement according to the first embodiment was prepared.
  • Example 102 to 117 and Reference Examples 101 to 107 A pressure measurement sheet set was prepared in the same manner as in Example 101 except that the configuration of each layer shown in Table 2 was changed.
  • Example 117 a paper sheet (manufactured by KOKUYO Co., Ltd., printer paper super fine grade, thick type) was used as the protective sheet.
  • Table 2 shows the configurations of the pressure measurement sheet sets of Examples 101 to 117 and Reference Examples 101 to 107, and the evaluation results.
  • the "material” column, "T1 (a)” column, “Tg” column, and “thermal resistance value” column in Table 2 are the same as those in Table 1.
  • the "T4" column indicates the thickness T4 (unit: ⁇ m) of the protective sheet.
  • the “(e)” column shows a value obtained by substituting the thickness T1 of the first support and the thickness T4 of the protective sheet into the equation (e) (“T4-T1 ⁇ 0.4”).
  • the “(f)” column shows the total of the thickness T1 of the first support and the thickness T4 of the protective sheet.
  • the arithmetic mean roughness Ra of the surface of the protective sheet used in Examples 101 to 117 was 0.02 to 0.03 ⁇ m.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Force Measurement Appropriate To Specific Purposes (AREA)
  • Laminated Bodies (AREA)
  • Measuring Temperature Or Quantity Of Heat (AREA)

Abstract

La présente invention aborde le problème de la mise en œuvre d'un ensemble de feuilles de mesure de la pression qui, lors de la réalisation d'une mesure de la pression dans des conditions de température élevée, est en mesure de supprimer la déformation d'un corps de support, la réduction de la résolution d'une image de répartition de pression et la contamination d'un objet à mesurer. La présente invention aborde également le problème de la mise en œuvre d'un procédé de mesure de la pression.　Cet ensemble de feuilles de mesure de la pression comprend : une première feuille comprenant un premier corps de support, et une première couche qui est disposée sur le premier corps de support et qui comprend des microcapsules qui contiennent une substance chromogène; une deuxième feuille comprenant un deuxième corps de support, et une deuxième couche qui est disposée sur le deuxième corps de support et qui comprend un révélateur; et une feuille de protection. La feuille de protection est un film ou papier de résine. Le film de résine a une température de transition vitreuse de 100 °C ou plus, ou ne présente pas de température de transition vitreuse; l'épaisseur T1 du premier corps de support, l'épaisseur T2 du deuxième corps de support, et l'épaisseur T3 de la feuille de protection satisfont à toutes les formules prédéterminées (a) à (d).
PCT/JP2021/042071 2020-12-24 2021-11-16 Ensemble de feuilles de mesure de la pression et procédé de mesure de la pression WO2022137893A1 (fr)

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CN202180086925.0A CN116670479A (zh) 2020-12-24 2021-11-16 压力测定用片材组、压力测定方法

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05140351A (ja) * 1991-11-18 1993-06-08 Toray Ind Inc 感圧フイルム
US20170241849A1 (en) * 2016-02-23 2017-08-24 International Business Machines Corporation Pressure indicator films for high temperature applications
JP2017181155A (ja) * 2016-03-29 2017-10-05 富士フイルム株式会社 応力表示部材および応力測定方法
JP2019532289A (ja) * 2016-09-23 2019-11-07 クロマティック テクノロジーズ インコーポレイテッドＣｈｒｏｍａｔｉｃ Ｔｅｃｈｎｏｌｏｇｉｅｓ， Ｉｎｃ． 高圧加工圧力センサー
JP2020148687A (ja) * 2019-03-14 2020-09-17 Ｎｉｓｓｈａ株式会社 静電容量検出装置および静電容量検出装置群

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003261597A1 (en) 2002-09-13 2004-04-30 Asahi Kasei Kabushiki Kaisha Microporous film and method for production thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05140351A (ja) * 1991-11-18 1993-06-08 Toray Ind Inc 感圧フイルム
US20170241849A1 (en) * 2016-02-23 2017-08-24 International Business Machines Corporation Pressure indicator films for high temperature applications
JP2017181155A (ja) * 2016-03-29 2017-10-05 富士フイルム株式会社 応力表示部材および応力測定方法
JP2019532289A (ja) * 2016-09-23 2019-11-07 クロマティック テクノロジーズ インコーポレイテッドＣｈｒｏｍａｔｉｃ Ｔｅｃｈｎｏｌｏｇｉｅｓ， Ｉｎｃ． 高圧加工圧力センサー
JP2020148687A (ja) * 2019-03-14 2020-09-17 Ｎｉｓｓｈａ株式会社 静電容量検出装置および静電容量検出装置群

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