CN114902026A - Pressure measurement sheet set and method for producing same, pressure measurement sheet and method for producing same, dispersion liquid, and microcapsule - Google Patents
Pressure measurement sheet set and method for producing same, pressure measurement sheet and method for producing same, dispersion liquid, and microcapsule Download PDFInfo
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- CN114902026A CN114902026A CN202080085210.9A CN202080085210A CN114902026A CN 114902026 A CN114902026 A CN 114902026A CN 202080085210 A CN202080085210 A CN 202080085210A CN 114902026 A CN114902026 A CN 114902026A
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- pressure measurement
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- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 238000010030 laminating Methods 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
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- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical group COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- CZXGXYBOQYQXQD-UHFFFAOYSA-N methyl benzenesulfonate Chemical group COS(=O)(=O)C1=CC=CC=C1 CZXGXYBOQYQXQD-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
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- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
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- 239000004408 titanium dioxide Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 150000004654 triazenes Chemical class 0.000 description 1
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- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
-
- 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
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Color Printing (AREA)
Abstract
The invention provides a pressure measurement sheet set with excellent storage stability at low temperature and a manufacturing method thereof, and a pressure measurement sheet with excellent storage stability at low temperature and a manufacturing method thereof. Another object of the present invention is to provide a dispersion and a microcapsule. The pressure measurement sheet set of the present invention includes: a 1 st sheet having a 1 st layer containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former; and a 2 nd sheet having a 2 nd layer containing a developer, wherein the solvent having a boiling point of 100 ℃ or higher contains 2 or more kinds of solvents containing an aromatic group, and the color former contains 2 or more kinds of color formers containing an aromatic group.
Description
Technical Field
The present invention relates to a sheet set for pressure measurement and a method for manufacturing the same, a sheet for pressure measurement and a method for manufacturing the same, a dispersion liquid, and a microcapsule.
Background
In recent years, the necessity of measuring the pressure distribution has been increasing due to the higher functionality and higher definition of products.
For example, patent document 1 proposes a pressure measurement sheet using microcapsules containing a color former and a solvent for dissolving the color former.
Prior art documents
Patent document
Patent document 1: japanese laid-open patent publication No. Sho 55-137992
Disclosure of Invention
Technical problem to be solved by the invention
The present inventors have made studies to produce the pressure-measuring sheet described in patent document 1, and have found that there is room for improvement in storage stability at low temperatures. Specifically, it was found that when the pressure-measuring sheet was used after being stored at a low temperature for a long period of time, the color development density of the color development part due to the reaction between the color former and the color developer in the pressurized region may be significantly deteriorated relative to the initial density (in other words, when the pressure-measuring sheet immediately after production was used, the color development density of the color development part due to the reaction between the color former and the color developer in the pressurized region).
The invention provides a pressure measurement sheet set with excellent storage stability at low temperature and a manufacturing method thereof, and a pressure measurement sheet with excellent storage stability at low temperature and a manufacturing method thereof.
Another object of the present invention is to provide a dispersion and a microcapsule.
Means for solving the technical problem
As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a specific composition of a color former encapsulated in microcapsules and a solvent for dissolving the color former.
That is, the following configuration was found to solve the above problems.
[ 1] A sheet set for pressure measurement, comprising:
a 1 st sheet having a 1 st layer containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former; and
a 2 nd sheet having a 2 nd layer containing a color developer,
the solvent having a boiling point of 100 ℃ or higher contains 2 or more aromatic group-containing solvents, and,
the color former contains 2 or more kinds of color formers containing aromatic groups.
[ 2] the set of pressure-measuring sheets according to [ 1], wherein the aromatic group-containing solvent comprises a solvent containing 2 aromatic groups in the molecule.
[ 3] the pressure-measuring sheet set according to [ 2], wherein a content of the solvent containing 2 aromatic groups in a molecule is 50% by mass or more based on a total mass of the solvents containing aromatic groups.
[ 4] the pressure measurement sheet set according to any one of [ 1] to [ 3], wherein the solvent having a boiling point of 100 ℃ or higher comprises 4 or more of the aromatic group-containing solvents.
[ 5] the pressure-measuring sheet set according to any one of [ 1] to [ 4], wherein,
the solvent having a boiling point of 100 ℃ or higher further contains a solvent containing an aliphatic structure,
the content of the aromatic group-containing solvent is 50 to 90% by mass based on the total mass of the aromatic group-containing solvent and the aliphatic structure-containing solvent.
[ 6] the set of pressure-measuring sheets according to any one of [ 1] to [ 5], wherein the aromatic group-containing solvent has an oil absorption of 2.0 to 20.0g/m with respect to the 2 nd sheet 2 。
[ 7] the set of pressure-measuring sheets according to any one of [ 1] to [ 6], wherein the arithmetic average roughness Ra of the 1 st sheet is 3.0 to 7.0. mu.m.
[ 8 ] the pressure-measuring sheet set according to any one of [ 1] to [ 7], wherein the arithmetic average roughness Ra of the 2 nd sheet is 1.2 μm or less.
[ 9] the pressure-measuring sheet set according to any one of [ 1] to [ 8 ], wherein,
the 1 st sheet and the 2 nd sheet further have a support,
the support is a resin film.
[ 10 ] A pressure-measuring sheet comprising:
a first layer 1 containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former; and
a 2 nd layer disposed on the 1 st layer and containing a color developer,
the solvent having a boiling point of 100 ℃ or higher contains 2 or more aromatic group-containing solvents, and
the color former contains 2 or more kinds of color formers containing aromatic groups.
The pressure-measuring sheet according to [ 10 ], wherein the aromatic group-containing solvent contains a solvent containing 2 aromatic groups in the molecule.
[12 ] the pressure-measuring sheet according to [ 11 ], wherein the content of the solvent having 2 aromatic groups in the molecule is 50% by mass or more based on the total mass of the solvents having aromatic groups.
The pressure-measuring sheet according to any one of [ 10 ] to [12 ], wherein the solvent having a boiling point of 100 ℃ or higher comprises 4 or more of the aromatic group-containing solvents.
[ 14 ] the pressure-measuring sheet according to any one of [ 10 ] to [ 13 ], wherein,
the solvent having a boiling point of 100 ℃ or higher further contains a solvent containing an aliphatic structure,
the content of the aromatic group-containing solvent is 50 to 90% by mass based on the total mass of the aromatic group-containing solvent and the aliphatic structure-containing solvent.
The pressure-measuring sheet according to any one of [ 10 ] to [ 14 ], wherein the aromatic group-containing solvent has an oil absorption of 2.0 to 20.0g/m with respect to the 2 nd layer 2 。
[ 16 ] the pressure-measuring sheet according to any one of [ 10 ] to [ 15 ], which further comprises a support,
the support is a resin film.
[ 17 ] A method for manufacturing a pressure-measuring sheet set according to any one of [ 1] to [ 9], comprising the steps of:
a layer 1 forming composition containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former is applied, and the obtained coating film is dried to form a layer 1.
[ 18 ] A method for producing a sheet for pressure measurement according to any one of [ 10 ] to [ 16 ], comprising the steps of:
a layer 1 forming composition containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former is applied, and the obtained coating film is dried to form a layer 1.
[ 19 ] A dispersion which is used for measuring pressure and for forming a layer to be used in combination with a layer containing a color developer, and which contains microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former,
the solvent having a boiling point of 100 ℃ or higher contains 2 or more aromatic group-containing solvents, and,
the color former contains 2 or more kinds of color formers containing aromatic groups.
[ 20 ] the dispersion according to [ 19 ], wherein the solvent having a boiling point of 100 ℃ or higher comprises 4 or more of the aromatic group-containing solvents.
[ 21 ] A microcapsule which comprises a solvent having a boiling point of 100 ℃ or higher and a color former,
the solvent having a boiling point of 100 ℃ or higher contains 2 or more aromatic group-containing solvents, and
the color former contains 2 or more types of color formers containing aromatic groups.
Effects of the invention
According to the present invention, a pressure measurement sheet set having excellent storage stability at low temperatures and a method for manufacturing the same, and a pressure measurement sheet having excellent storage stability at low temperatures and a method for manufacturing the same can be provided. Further, the present invention can provide a dispersion and a microcapsule.
Drawings
Fig. 1 is a sectional view of an embodiment of a pressure measurement sheet set.
Fig. 2 is a diagram for explaining a usage form of the pressure measurement sheet set.
Fig. 3 is a cross-sectional view of an embodiment of a pressure-measuring sheet.
Detailed Description
[ pressure measurement sheet set and method for producing same, pressure measurement sheet and method for producing same, dispersion liquid, and microcapsules ]
The present invention will be described in detail below.
In the present specification, the numerical range expressed by the term "to" means a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.
In the numerical ranges recited in the present invention, an upper limit or a lower limit recited in a certain numerical range may be replaced with an upper limit or a lower limit recited in another numerical range recited in a stepwise manner. In the numerical ranges described in the present specification, the upper limit or the lower limit described in a certain numerical range may be replaced with the values shown in the examples.
The pressure measurement sheet set and the pressure measurement sheet of the present invention are characterized by using microcapsules (hereinafter, also referred to as "specific microcapsules") that contain a solvent and a color former having a boiling point of 100 ℃ or higher and satisfy the following conditions X and Y.
Condition X: the solvent having a boiling point of 100 ℃ or higher contains 2 or more aromatic group-containing solvents.
Condition Y: the color former contains 2 or more types of color formers containing aromatic groups.
The pressure measurement sheet set and the pressure measurement sheet of the present invention having the above-described structures have excellent storage stability at low temperatures. That is, even when the pressure-measuring sheet set and the pressure-measuring sheet according to the present invention are used after being stored at low temperature for a long period of time, the color development part produced by the reaction between the color former and the developer in the pressurized region exhibits a color development density comparable to the initial density (the color development density of the color development part produced by the reaction between the color former and the developer in the pressurized region in the case of using the pressure-measuring sheet immediately after production).
The mechanism of action of the above-described structure and effect is not clear, but the present inventors presume as follows. The present inventors have found that the deposition of a color former encapsulated in microcapsules during long-term storage at low temperature is one of the causes of deterioration in the color development intensity of a color-developing part during use after long-term storage at low temperature.
On the other hand, in the specific microcapsule, the composition of the color former encapsulated in the microcapsule and the solvent in which the color former is dissolved satisfies the above-described conditions X and Y, and thus the solubility of the color former in the solvent at a low temperature is improved. As a result, even when the pressure measurement sheet set and the pressure measurement sheet are stored at a low temperature for a long period of time and then used, the color former moves to the 2 nd layer containing the color developer in a state of being dissolved in the solvent (a state in which precipitation can be suppressed) in the pressurized region, and easily penetrates into the inside of the 2 nd layer, and the color development reaction between the color former and the color developer is easily performed. That is, it is presumed that the deterioration of the color development intensity in the color development part is suppressed by the above mechanism.
Further, when the boiling point of the solvent contained in the specific microcapsule is 100 ℃ or higher, the solvent is easily maintained in the specific microcapsule by suppressing the volatilization of the solvent at the time of production and/or storage of the specific microcapsule and/or at the time of production and/or storage of the pressure measurement sheet set and the pressure measurement sheet. This is presumably because the color-developing reaction between the color-developing agent and the color-developing agent in the pressurized region is more likely to proceed when the pressure-measuring sheet set and the pressure-measuring sheet are used.
The structure of the pressure measurement sheet set and the pressure measurement sheet according to the present invention will be described in detail below. These manufacturing methods will also be described in detail.
[1 st embodiment ]
Fig. 1 is a sectional view of an embodiment of a pressure measurement sheet set.
The pressure measurement sheet set 10 includes a 1 st sheet 16 and a 2 nd sheet 22, the 1 st sheet 16 having a 1 st support body 12 and a 1 st layer 14 disposed on the 1 st support body 12 and containing a specific microcapsule 13, and the 2 nd sheet 22 having a 2 nd support body 18 and a 2 nd layer 20 disposed on the 2 nd support body 18 and containing a color developer.
As shown in fig. 2, when the pressure measurement sheet set 10 is used, the 1 st sheet 16 and the 2 nd sheet 22 are stacked and used such that the 1 st layer 14 of the 1 st sheet 16 and the 2 nd layer 20 of the 2 nd sheet 22 face each other. By applying pressure from at least one of the 1 st support body 12 side of the 1 st sheet 16 and the 2 nd support body 18 side of the 2 nd sheet 22 in the obtained laminate, the specific microcapsules 13 are ruptured in the pressurized region and the color former contained in the specific microcapsules 13 comes out of the specific microcapsules 13, thereby performing a color developing reaction with the color developer in the 2 nd layer 20. As a result, color development proceeds in the pressurized region.
As described later, the 1 st sheet 16 may have the 1 st layer 14, or may not have the 1 st support 12. The 2 nd sheet 22 may have the 2 nd layer 20, or may not have the 2 nd support 18.
In fig. 1, the 1 st support 12 and the 1 st layer 14 are directly laminated, but the present invention is not limited to this embodiment, and another layer (for example, an easy adhesion layer) may be disposed between the 1 st support 12 and the 1 st layer 14, as described later. In fig. 1, the 2 nd support 18 and the 2 nd layer 20 are directly laminated, but the present invention is not limited to this embodiment, and another layer (for example, an easy adhesion layer) may be disposed between the 2 nd support 18 and the 2 nd layer 20 as described later.
The structure of the 1 st sheet 16 and the 2 nd sheet 22 constituting the pressure measurement sheet set 10 will be described in detail below.
< 1 st sheet >
The 1 st sheet 16 shown in fig. 1 has a 1 st support 12 and a 1 st layer 14 containing a specific microcapsule 13.
Hereinafter, each member will be described in detail.
< No. 1 support >
The 1 st support is a member for supporting the 1 st layer. In addition, in the case of being able to be handled by the 1 st layer itself, the 1 st sheet may not have the 1 st support.
The 1 st support may have any one of a sheet shape, a film shape, and a plate shape.
Examples of the 1 st support include a resin film and a synthetic paper.
Examples of the resin film include polyester films such as polyethylene terephthalate films, cellulose derivative films such as cellulose triacetate films, polyolefin films such as polypropylene and polyethylene films, and polystyrene films.
Examples of the synthetic paper include synthetic paper having a plurality of micropores formed by biaxial stretching of polypropylene, polyethylene terephthalate, or the like (Yupo or the like), synthetic paper made of synthetic fibers of polyethylene, polypropylene, polyethylene terephthalate, polyamide, or the like, and synthetic paper having these layers laminated on a part, one surface, or both surfaces of the paper.
Among them, from the viewpoint of further increasing the color development intensity by pressurization and from the viewpoint of excellent image quality after color development, a resin film or a synthetic paper is preferable, and a resin film is more preferable.
The thickness of the No. 1 support is not particularly limited, but is preferably 10 to 200. mu.m.
< layer 1 >)
(specific microcapsules)
Layer 1 contains specific microcapsules.
Hereinafter, the material constituting the specific microcapsule will be described in detail.
The specific microcapsule generally has a core and a capsule wall for enclosing a core material (an enclosed component (also referred to as an enclosed component)) constituting the core.
The specific microcapsule contains a solvent having a boiling point of 100 ℃ or higher and a color former as a core material (an inclusion component). Since the microcapsules contain the color former therein, the color former can be stably present until the microcapsules are broken by pressurization.
Certain microcapsules have a capsule wall enclosing a core material.
As the material (wall material) of the capsule wall of the specific microcapsule, known resins conventionally used as the wall material of the microcapsule containing a color former in the application to pressure-sensitive copying paper or thermal recording paper can be cited. Specific examples of the resin include polyurethane, polyurea, polyurethaneurea, melamine-formaldehyde resin, and gelatin.
The capsule wall of the specific microcapsule is preferably substantially composed of a resin. The substantial resin composition means that the content of the resin is 90% by mass or more, preferably 100% by mass, based on the total mass of the capsule wall. That is, the capsule wall of the specific microcapsule is preferably made of a resin.
The polyurethane is a polymer having a plurality of urethane bonds, and is preferably a reaction product formed from raw materials including a polyol and a polyisocyanate.
The polyurea is a polymer having a plurality of urea bonds, and is preferably a reaction product formed from raw materials including polyamine and polyisocyanate. Further, a polyamine is formed by reacting a part of polyisocyanate with water, and polyurea can be synthesized using polyisocyanate without using polyamine.
The polyurethaneurea is a polymer having a urethane bond and a urea bond, and is preferably a reaction product formed from raw materials including a polyol, a polyamine, and a polyisocyanate. When the polyol is reacted with the polyisocyanate, a part of the polyisocyanate reacts with water to form a polyamine, and as a result, a polyurethaneurea can be obtained.
Also, the melamine-formaldehyde resin is preferably a reaction product formed by polycondensation of melamine and formaldehyde.
The polyisocyanate is a compound having 2 or more isocyanate groups, and examples thereof include aromatic polyisocyanates and aliphatic polyisocyanates. The polyisocyanate may be, for example, an adduct (adduct) of a polyol such as trimethylolpropane and a 2-functional polyisocyanate.
The polyol is a compound having 2 or more hydroxyl groups, and examples thereof include low-molecular polyols (e.g., aliphatic polyols and aromatic polyols), "low-molecular polyols" are polyols having a molecular weight of 400 or less), polyvinyl alcohols, polyether polyols, polyester polyols, polylactone polyols, castor oil polyols, polyolefin polyols, and hydroxyl group-containing amine compounds (e.g., aminoalcohols).
The polyamine is a compound having 2 or more amino groups (primary amino groups or secondary amino groups), and examples thereof include aliphatic polyamines such as diethylenetriamine, triethylenetetramine, 1, 3-propanediamine, and hexamethylenediamine; epoxy compound adducts of aliphatic polyamines; alicyclic polyamines such as piperazine; heterocyclic diamines such as 3, 9-bis-aminopropyl-2, 4,8, 10-tetraoxaspiro- (5,5) undecane.
The average particle diameter of the specific microcapsule is not particularly limited, but is preferably 1 to 100. mu.m, more preferably 3 to 50 μm, and still more preferably 5 to 30 μm.
The average particle diameter of the specific microcapsule can be controlled by adjusting the production conditions of the specific microcapsule, and the like.
The average particle diameter of the specific microcapsule is a value determined by the following method.
The image taken from the surface of the layer 1 was analyzed by an optical microscope (OLYMPUS BX60, size of field: 320. mu. m.times.450. mu.m), and the major axes (particle diameters) of 30 microcapsules were measured sequentially from the largest microcapsule, and the average value was obtained by arithmetically averaging these. This operation was performed at arbitrary 5 sites (5 fields) of the layer 1, and the average of the average values obtained at each site was obtained, and the obtained value was defined as the average particle diameter of the microcapsules. The major axis means the longest diameter when the microcapsules are observed.
The average particle diameter of the microcapsules contained in the dispersion can be measured by a laser diffraction/scattering particle diameter distribution measuring apparatus (LA-960/HORIBA).
The number average wall thickness of the capsule wall of the specific microcapsule is not particularly limited, but is preferably 0.01 to 2.0 μm, and more preferably 0.02 to 1.0 μm, from the viewpoint of excellent pressure responsiveness.
The thickness of the specific microcapsule is the thickness (μm) of the capsule wall of the capsule particle forming the specific microcapsule, and the number average thickness is an average value obtained by obtaining the thickness (μm) of each of the capsule walls of 20 specific microcapsules by a Scanning Electron Microscope (SEM). More specifically, a cross-sectional slice of the 1 st sheet having the 1 st layer containing the specific microcapsules was prepared, the cross-section was observed at 15000 times by SEM, and arbitrary 20 specific microcapsules having a particle diameter in the range of (the value of the average particle diameter of the specific microcapsules) × 0.9 to (the value of the average particle diameter of the specific microcapsules) × 1.1 were selected, and then the cross-section of each of the selected specific microcapsules was observed to determine the thickness of the capsule wall and calculate the average value.
The ratio (δ/Dm) of the number average wall thickness δ of the specific microcapsule to the average particle diameter of the specific microcapsule is not particularly limited, and is usually 0.001 or more. Among them, from the viewpoint of excellent color development intensity by pressure, it is preferable that the relationship of the formula (1) is satisfied.
Formula (1) delta/Dm > 0.001
That is, the ratio (δ/Dm) is preferably greater than 0.001. The ratio (δ/Dm) is preferably 0.002 or more. The upper limit is not particularly limited, but is preferably 0.2 or less.
Color former
A color former is encapsulated in the specific microcapsule.
The "color former" is a compound that develops color from a colorless state by contacting with a developer described later. The color former is preferably an electron-donating pigment precursor (a precursor of a color-forming pigment). That is, as the color former, an electron-donating leuco dye is preferable.
Among the color-developing agents contained in the specific microcapsule, 2 or more types are color-developing agents containing an aromatic group (hereinafter, also referred to as "specific color-developing agents"). In other words, the specific microcapsule contains 2 or more kinds of the color former containing an aromatic group as the color former.
The term "comprising an aromatic group" as used herein means that a monocyclic aromatic ring group and/or a condensed polycyclic aromatic ring group are contained in the molecule.
Examples of the aromatic ring include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
The aromatic hydrocarbon ring may be either a monocyclic ring or a condensed polycyclic ring, as described above. The aromatic hydrocarbon ring may have a substituent. When the aromatic hydrocarbon ring has a plurality of substituents, the substituents may be bonded to each other to form an alicyclic ring. In other words, the aromatic hydrocarbon ring may be an aromatic hydrocarbon ring containing an alicyclic structure (e.g., a benzolactone ring).
The number of carbon atoms of the aromatic hydrocarbon ring is not particularly limited, but is preferably 6 to 30, more preferably 6 to 18, and further preferably 6 to 10.
Examples of the monocyclic aromatic hydrocarbon ring include a benzene ring.
Examples of the condensed polycyclic aromatic hydrocarbon ring include a naphthalene ring.
The aromatic heterocyclic ring may be any of monocyclic ring and condensed polycyclic ring as described above. The aromatic heterocycle may have a substituent. When the aromatic heterocycle has a plurality of substituents, the substituents may be bonded to each other to form an alicyclic ring. In other words, the aromatic heterocycle may be an aromatic heterocycle having an alicyclic structure.
Examples of the hetero atom contained in the aromatic heterocyclic ring include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of ring members of the aromatic heterocycle is not particularly limited, but is preferably 5 to 18.
Examples of the aromatic heterocyclic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiophene ring, a thiazole ring, an imidazole ring, a xanthene ring, and a benzoxanthene ring.
The number of aromatic groups in the specific color former is not particularly limited, and may be 1 or 2 or more. In addition, when the specific color former contains 2 or more aromatic groups, the 2 aromatic groups may form a polycyclic structure (not including a condensed polycyclic structure) by bonding the substituents that can be present on the respective aromatic groups to each other.
As the specific color former, a color former known for use in pressure-sensitive copying paper or thermal recording paper can be used as long as it contains an aromatic group.
Examples of the specific color former include triphenylmethanephthalide compounds, fluoran precursor compounds, phenothiazine compounds, indolylphthalolide compounds, azaindolylphthalolide compounds, white gold amine compounds, rhodamine lactam compounds, triphenylmethane compounds, diphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds.
For details of the above-mentioned compounds, reference can be made to the descriptions of Japanese patent application laid-open No. 5-257272 and WO2009/8248[0029] to [0034 ].
The specific color former is preferably a color former having a xanthene ring in the molecule, from the viewpoint of more excellent storage stability at low temperatures and from the viewpoint of more excellent color development density.
The molecular weight of the specific color former is not particularly limited, but is preferably 300 or more. The upper limit is not particularly limited, but is preferably 1000 or less.
Specific examples of the coloring agent include 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-n-octyl-2-methylindol-3-yl) phthalide, 3- [2, 2-bis (1-ethyl-2-methylindol-3-yl) vinyl ] -3- (4-diethylaminophenyl) -phthalide, 2-anilino-6-dibutylamino-3-methylfluoran precursor, 6-diethylamino-3-methyl-2- (2, 6-stubborn amino) -fluoran precursor, 2- (2-chloroanilino) -6-dibutylaminofluoran precursor, 3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide, 2-anilino-6-diethylamino-3-methylfluoran precursor, 9- [ ethyl (3-methylbutyl) amino ] spiro [ 12H-benzo [ a ] xanthene-12, 1 '(3' H) isobenzofuran ] -3 '-one, and 2' -methyl-6 '- (N-p-tolyl-N-ethylamino) spiro [ isobenzofuran-1 (3H), 9' - [9H ] xanthene ] -3-one, 3 ', 6' -bis (diethylamino) -2- (4-nitrophenyl) spiro [ isoindoline- 1,9 '-xanthene ] -3-one, 6' - (diethylamino) -1 ', 3' -dimethylfluoran precursor, and the like. Furthermore, as the specific color former, Pink-DCF and Orange-DCF (both manufactured by Hodogaya Chemical Co., Ltd.) can also be used.
The content of the specific color former is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and still more preferably 90 to 100% by mass, based on the total amount of the color formers.
Solvents having a boiling point of 100 ℃ or higher
The specific microcapsule contains a solvent having a boiling point of 100 ℃ or higher. The "boiling point" refers to the boiling point at normal atmospheric pressure.
The boiling point of the solvent contained in the specific microcapsule is preferably 120 ℃ or higher, more preferably 150 ℃ or higher, and still more preferably 200 ℃ or higher. The upper limit of the boiling point is not particularly limited, and is, for example, 400 ℃.
The solvent having a boiling point of 100 ℃ or higher, which is included in the specific microcapsule, contains 2 or more kinds of solvents containing an aromatic group. In other words, the specific microcapsule has a boiling point of 100 ℃ or higher and contains 2 or more kinds of aromatic group-containing solvents (hereinafter also referred to as "specific solvents").
The term "comprising an aromatic group" as used herein means that a monocyclic aromatic ring group and/or a condensed polycyclic aromatic ring group are contained in the molecule.
Examples of the aromatic ring included in the aromatic ring group include an aromatic hydrocarbon ring and an aromatic heterocyclic ring.
The aromatic hydrocarbon ring may be either a monocyclic ring or a condensed polycyclic ring, as described above. The aromatic hydrocarbon ring may have a substituent. When the aromatic hydrocarbon ring has a plurality of substituents, the substituents may be bonded to each other to form an alicyclic ring. In other words, the aromatic hydrocarbon ring may be an aromatic hydrocarbon ring having an alicyclic structure.
The number of carbon atoms of the aromatic hydrocarbon ring is not particularly limited, but is preferably 6 to 30, more preferably 6 to 18, and further preferably 6 to 10.
Examples of the monocyclic aromatic hydrocarbon ring include a benzene ring.
Examples of the condensed polycyclic aromatic hydrocarbon ring include a naphthalene ring.
The aromatic heterocyclic ring may be any of monocyclic ring and condensed polycyclic ring as described above. The aromatic heterocycle may have a substituent. When the aromatic heterocycle has a plurality of substituents, the substituents may be bonded to each other to form an alicyclic ring. In other words, the aromatic heterocycle may be an aromatic heterocycle having an alicyclic structure.
Examples of the hetero atom contained in the aromatic heterocyclic ring include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of ring members of the aromatic heterocycle is not particularly limited, but is preferably 5 to 18.
Examples of the aromatic heterocyclic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiophene ring, a thiazole ring, an imidazole ring, and a xanthene ring.
The number of aromatic groups in the specific solvent is not particularly limited, and may be 1 or 2 or more. In addition, when the specific solvent contains 2 or more aromatic groups, the 2 aromatic groups may form a polycyclic structure (not including a condensed polycyclic structure) by bonding the substituents that can be present on each aromatic group to each other.
Among the specific solvents, a solvent containing 2 aromatic groups is preferable from the viewpoint of more excellent storage stability at low temperature and more excellent color development intensity.
The lower limit of the content of the specific solvent containing 2 aromatic groups in the molecule is, for example, 5 mass% or more based on the total mass of the specific solvent, and is preferably 50 mass% or more, and more preferably 70 mass% or more, from the viewpoint of further excellent storage stability at low temperatures and further excellent color development intensity. The upper limit of the content of the specific solvent containing 2 aromatic groups in the molecule is, for example, 100 mass% or less.
The molecular weight of the specific solvent is not particularly limited, but is at most 100 or more. Among them, 150 or more is preferable. The upper limit is not particularly limited, but is preferably 1000 or less, more preferably 500 or less, and still more preferably 300 or less.
The specific solvent includes, for example, a compound represented by the following general formula (1), preferably compounds represented by the following general formulae (1A) to (1C), and more preferably a compound represented by the following general formula (1A) from the viewpoint of more excellent storage stability at low temperature and more excellent color development intensity.
[ chemical formula 1]
In the general formula (1), m 1 Represents 0 or 1. As m 1 From the viewpoint of further excellent storage stability at low temperatures and further excellent color development density, 1 is preferred.
·m 1 Case representing 0:
m 1 when 0 is represented, Ar 1 Is represented by the formula-L A -R A Aryl of the substituent (hereinafter, also referred to as "substituent W")An aromatic ring.
As by Ar 1 The aromatic ring includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic hydrocarbon ring and the aromatic heterocyclic ring are as described above.
In the substituent W, L A Represents a single bond, an oxysulfonyl group (.) 1 -SO 2 -O-* 2 ) Or sulfonyloxy (.) 1 -O-SO 2 -* 2 ). In addition, a 1 Is represented by the formula Ar 1 Bonding site of 2 Is represented by the formula A The bonding position of (2).
In the substituent W, R A Represents a 1-valent aliphatic hydrocarbon group.
As a group consisting of R A The 1-valent aliphatic hydrocarbon group may be any of a 1-valent saturated aliphatic hydrocarbon group and a 1-valent unsaturated aliphatic hydrocarbon group. The polymer may be linear, branched, or cyclic. The number of carbon atoms of the 1-valent aliphatic hydrocarbon group is not particularly limited, and is, for example, 1 to 15, preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 4. The aliphatic hydrocarbon group having a valence of 1 includes an alkyl group, an alkenyl group and an alkynyl group, and is preferably an alkyl group.
The aliphatic hydrocarbon group having a valence of 1 may further have a substituent.
From Ar 1 The aromatic ring represented may have 1 ring represented by-L A -R A The number of the substituents may be 2 or more.
·m 1 Case of expression 1:
m 1 in the case of 1, Ar 1 And Ar 2 Each independently represents an aromatic group having a valence of 1 which may have a substituent.
As by Ar 1 And Ar 2 The 1-valent aromatic group includes a 1-valent aromatic hydrocarbon group and a 1-valent aromatic heterocyclic group. The aromatic hydrocarbon ring contained in the 1-valent aromatic hydrocarbon group and the aromatic heterocyclic ring contained in the 1-valent aromatic heterocyclic group are as described above. In addition, the 1-valent aromatic hydrocarbon group and the 1-valent aromatic heterocyclic group can be obtained by removing 1 from the aromatic hydrocarbon ring and the aromatic heterocyclic groupHydrogen atoms.
As by Ar 1 And Ar 2 Among the 1-valent aromatic groups, 1-valent aromatic hydrocarbon groups are preferred, and phenyl groups are more preferred.
From Ar 1 And Ar 2 The 1-valent aromatic group may have a substituent. The substituent is not particularly limited, and is preferably a non-aromatic substituent, and examples thereof include the above-mentioned substituent W.
L 1 Represents a single bond, a 2-valent aliphatic hydrocarbon group or a compound represented by the following general formula (L) A ) A linker having a valence of 2.
[ chemical formula 2]
The above general formula (L) A ) In, R 1 Represents an aromatic group having a valence of 1 which may have a substituent.
In the general formula (1), R 1 Meaning of (a) and m 1 Ar when represents 1 1 And Ar 2 (that is, an aromatic group having a valence of 1 which may have a substituent) has the same meaning, and the preferable embodiment is also the same.
As a result of L 1 The aliphatic hydrocarbon group having a valence of 2 may be any of a saturated aliphatic hydrocarbon group having a valence of 2 and an unsaturated aliphatic hydrocarbon group having a valence of 2. The polymer may be linear, branched, or cyclic. The number of carbon atoms of the 2-valent aliphatic hydrocarbon group is not particularly limited, and is, for example, 1 to 10, preferably 1 to 6, more preferably 1 to 4, and further preferably 1 or 2. The aliphatic hydrocarbon group having a valence of 2 includes an alkylene group, an alkenylene group and an alkynylene group, and is preferably an alkylene group. And, in the above-mentioned 2-valent aliphatic hydrocarbon group, a carbon atom may be substituted by ≧ C ═ CH 2 The 2-valent group represented.
As L 1 Among them, a single bond or a 2-valent aliphatic hydrocarbon group is preferable.
[ chemical formula 3]
In the general formula (1A), L 11 Represents a single bond or a 2-valent aliphatic hydrocarbon group.
As a result of L 11 The 2-valent aliphatic hydrocarbon group has the same meaning as that of L in the general formula (1) 1 The meaning of the 2-valent aliphatic hydrocarbon group is the same, and the preferred embodiment is the same.
R 11 And R 12 Each independently represents a non-aromatic substituent.
As a group consisting of R 11 And R 12 The non-aromatic substituent is not particularly limited, but is preferably a 1-valent aliphatic hydrocarbon group, and specifically, the non-aromatic substituent is preferably bonded to the substituent W represented by R A The 1-valent aliphatic hydrocarbon group is the same as the non-aromatic substituent. Among the 1-valent aliphatic hydrocarbon groups, an alkyl group having 1 to 4 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable.
n 11 And n 12 Each independently represents an integer of 0 to 5. n is 11 And n 12 Preferably an integer of 0 to 2. Among them, n is preferable 11 And n 12 Either one represents 1 or 2 and the other represents 0 or 1.
In addition, n 11 And n 12 When an integer of 2 or more is represented, a plurality of R's are present 11 R being mutually and multiply 12 May be the same as or different from each other.
Specific examples of the solvent represented by the general formula (1A) include 1, 2-dimethyl-4- (1-phenylethyl) benzene, 1, 3-dimethyl-4- (1-phenylethyl) benzene, 1, 4-dimethyl-2- (1-phenylethyl) benzene, 1- (ethylphenyl) -1-phenylethane, isopropylbiphenyl (e.g., 4-isopropylbiphenyl), diisopropylbiphenyl (e.g., 4, 4' -isopropylbiphenyl), and α -methylstyrene dimer.
[ chemical formula 4]
In the general formula (1B), L 21 Represents a single bond, an oxysulfonyl group (. 1 -SO 2 -O-* 2 ) Or sulfonyloxy (.) 1 -O-SO 2 -* 2 ). In addition, a 1 Represents a bonding position with a phenyl group represented by the general formula (1B) 2 Is represented by the formula 22 The bonding position of (2).
R 21 Represents a non-aromatic substituent. From R 21 The meaning of the non-aromatic substituent is as defined in the general formula (1A) with R 11 The non-aromatic substituents are the same as those shown, and the preferred embodiments are also the same.
n 21 Represents an integer of 0 to 5. n is a radical of an alkyl radical 21 Preferably an integer of 0 to 2.
In addition, n 21 When an integer of 2 or more is represented, a plurality of R's are present 21 May be the same as or different from each other.
R 22 Represents a 1-valent aliphatic hydrocarbon group. As a group consisting of R 22 The 1-valent aliphatic hydrocarbon group represented by (A) includes the group represented by R in the above-mentioned substituent W A The 1-valent aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group represented.
Specific examples of the solvent represented by the general formula (1B) include a benzenesulfonic acid methyl group, a p-toluenesulfonic acid methyl group, and a linear alkyl benzene having 1 to 15 carbon atoms.
[ chemical formula 5]
In the general formula (1C), R 31 、R 32 And R 33 Each independently represents a non-aromatic substituent.
From R 31 、R 32 And R 33 The meaning of the non-aromatic substituent is as defined in the general formula (1A) with R 11 The non-aromatic substituent is the same as the meaning of the substituent, and the preferable mode is also the same.
n 31 、n 32 And n 33 Each independently represents an integer of 0 to 5. n is 31 、n 32 And n 33 Preferably, each independently represents an integer of 0 to 2.
In addition, n 31 、n 32 And n 33 When an integer of 2 or more is represented, a plurality of R's are present 31 R's being present in plural numbers 32 R being mutually and multiply 33 May be the same as or different from each other.
Specific examples of the solvent represented by the general formula (1C) include trixylenyl phosphate and tricresyl phosphate.
From the viewpoint of more excellent storage stability at low temperatures and the viewpoint of more excellent color development intensity, it is preferable that any one of the specific solvents contained in the aromatic group-containing solvent is selected from the solvents represented by the above general formula (1A).
The specific solvent to be encapsulated in the specific microcapsule is 2 or more, preferably 3 or more, and more preferably 4 or more. Examples of the combination of 4 or more types of specific solvents to be encapsulated in the specific microcapsule include a combination of 1, 2-dimethyl-4- (1-phenylethyl) benzene, 1, 3-dimethyl-4- (1-phenylethyl) benzene, 1, 4-dimethyl-2- (1-phenylethyl) benzene and 1- (ethylphenyl) -1-phenylethane.
The specific microcapsule preferably further contains a solvent containing an aliphatic structure as a solvent having a boiling point of 100 ℃ or higher. The solvent containing an aliphatic structure can contribute to the formation of the capsule wall as described later.
The term "containing an aliphatic structure" means that a nonaromatic hydrocarbon group is contained in the molecule. In the above non-aromatic hydrocarbon group, the carbon atom in the hydrocarbon group may be substituted with a heteroatom, a carbonyl carbon, or the like. The hydrocarbon group may have a substituent.
In addition, the solvent containing an aliphatic structure does not contain an aromatic group. In other words, the solvent containing an aliphatic structure does not contain an aromatic ring in the molecule. Therefore, a solvent including an aromatic group and an aliphatic structure is classified as a solvent including an aromatic group.
The solvent containing an aliphatic structure is not particularly limited, and examples thereof include aliphatic hydrocarbons such as diethyl succinate, methyl laurate, and isoalkane (for example, isoalkane having 10 or more carbon atoms); natural animal and vegetable oils such as soybean oil, corn oil, cottonseed oil, rapeseed oil, olive oil, coconut oil, castor oil and fish oil, and natural high-boiling fractions such as mineral oil.
The aliphatic structure-containing solvent may be used alone in 1 kind or in a mixture of 2 or more kinds.
When the specific microcapsule contains a solvent containing an aliphatic structure as a solvent having a boiling point of 100 ℃ or higher, the content of the specific solvent is preferably 50.0 to 90.0% by mass based on the total mass of the solvent containing an aliphatic structure and the specific solvent, and more preferably 75.0 to 90.0% by mass from the viewpoint of more excellent color development density, from the viewpoint of more excellent storage stability at low temperatures and from the viewpoint of more excellent color development density.
In the specific microcapsule, the mass ratio of the solvent having a boiling point of 100 ℃ or higher to the color former (mass of the solvent having a boiling point of 100 ℃ or higher/mass of the color former) is preferably in the range of 98/2 to 30/70, and more preferably in the range of 97/3 to 40/60, from the viewpoint of further excellent color development density.
The specific microcapsules may contain 1 or more additives such as a light stabilizer, an antioxidant, paraffin, and an odor inhibitor, as necessary, in addition to the above components.
The specific microcapsule may contain a color former that does not contain a solvent having a boiling point of less than 100 ℃ (for example, ketones such as methyl ethyl ketone, esters such as ethyl acetate, and alcohols such as isopropyl alcohol) and an aromatic group, as long as the effect of the present invention is not inhibited.
(method for producing specific microcapsule)
The method for producing the specific 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 coacervation method. Among them, the interfacial polymerization method is preferable.
The interfacial polymerization method will be described below by taking as an example a method for producing specific microcapsules having a capsule wall made of polyurea or polyurethaneurea.
The interfacial polymerization method is preferably an interfacial polymerization method including a step (emulsification step) of preparing an emulsion by dispersing an oil phase containing a color former, a solvent having a boiling point of 100 ℃ or higher, and a capsule wall material (for example, a raw material containing at least 1 selected from the group consisting of a polyisocyanate, a polyol, and a polyamine) in an aqueous phase containing an emulsifier when the polyisocyanate is reacted with water to produce the polyamine in a reaction system, and a step (encapsulation step) of polymerizing the capsule wall material at the interface between the oil phase and the aqueous phase to form a capsule wall and form a microcapsule containing the color former.
The mass ratio of the total amount of the polyol and the polyamine to the amount of the polyisocyanate in the raw material (total amount of the polyol and the polyamine/amount of the polyisocyanate) is not particularly limited, but is preferably 0.1/99.9 to 30/70, and more preferably 1/99 to 25/75.
In the emulsification step, the solvent having a boiling point of 100 ℃ or higher preferably contains at least a specific solvent and a solvent containing an aliphatic structure. In addition, the solvent containing an aliphatic structure easily precipitates polyisocyanate which is a raw material of the capsule wall, and can contribute to the formation of the capsule wall.
The type of the 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.
Layer 1 contains the specific microcapsules described above.
The content of the specific microcapsules in the layer 1 is not particularly limited, and is preferably 60 to 98% by mass, more preferably 75 to 95% by mass, based on the total mass of the layer 1.
The content of the color former in the 1 st layer is not particularly limited, but is preferably 0.1 to 2.0g/m 2 More preferably 0.2 to 1.0g/m 2 。
Layer 1 may contain other ingredients in addition to the specific microcapsules described above.
Examples of the other components include a polymer binder, an inorganic filler (e.g., colloidal silica), a fluorescent whitening agent, a defoaming agent, a penetrant, an ultraviolet absorber, a surfactant, and a preservative.
Mass per unit area (solid content coating amount) of the 1 st layer (g/m) 2 ) Is not particularly limited, and is, for example, 0.5 to 20.0g/m 2 More preferably 0.5 to 10.0g/m 2 。
< method for forming layer 1 >
The method for forming the layer 1 is not particularly limited, and known methods can be used.
For example, a method in which a composition for forming the layer 1 containing specific microcapsules and a solvent having a boiling point of 100 ℃ or higher is applied to the support 1 and the coating film is dried as necessary is exemplified.
The composition for forming the layer 1 contains at least a specific microcapsule and a solvent having a boiling point of preferably 100 ℃ or higher. In addition, the microcapsule dispersion obtained by the interfacial polymerization method described above may also be used as the composition for forming the 1 st layer.
The composition for forming the layer 1 may contain other components that may be contained in the layer 1.
The method for coating the composition for forming layer 1 is not particularly limited, and examples of a coater used for coating include an air knife coater, a bar coater, a curtain coater, a gravure coater, a squeeze coater, a die coater, a slide bead coater, and a blade coater.
After the 1 st layer forming composition is applied to the 1 st support, the coating film may be dried as necessary. The drying treatment may be a heating treatment.
In addition, although the method of forming the 1 st layer on the 1 st support has been described above, the method is not limited to the above-described embodiment, and for example, the 1 st layer may be formed on the temporary support and then the temporary support may be peeled off to form the 1 st sheet composed of the 1 st layer.
The temporary support is not particularly limited as long as it is a releasable support.
< other Components >
The 1 st sheet may have other members than the 1 st support and the 1 st layer described above.
For example, the 1 st sheet may have an easy-adhesion layer between the 1 st support and the 1 st layer for improving adhesion therebetween.
The thickness of the easy adhesion layer is not particularly limited, but is preferably 0.005 to 0.2. mu.m, and more preferably 0.01 to 0.1. mu.m.
The arithmetic average roughness Ra of the 1 st sheet is preferably 3.0 to 7.0 μm from the viewpoint of further improving color density and image quality (resolution). The arithmetic average roughness Ra of the 1 st sheet is an arithmetic average roughness Ra of the surface of the 1 st sheet on the side facing (contacting) the 2 nd sheet when the pressure-measuring sheet set is used. In the case where the 1 st layer is positioned on the outermost surface of the 1 st sheet on the side facing the 2 nd sheet, the arithmetic average roughness Ra corresponds to the arithmetic average roughness Ra of the surface on the side opposite to the 1 st support side of the 1 st layer.
In addition, the arithmetic average roughness Ra of the 1 st sheet in the present specification means JIS B0681-6: 2014 the arithmetic average roughness Ra. In addition, as a measuring apparatus, a scanning type white light interferometer using a light interference system (specifically, New View5020 manufactured by Zygo corporation: Stich mode; Objective lens X50 times; intermediate lens X0.5 times) was used.
When the arithmetic average roughness Ra of the 1 st sheet is 3.0 μm or more, the amount of the color former is often sufficient, and therefore, a higher color density tends to be produced. On the other hand, when the arithmetic average roughness Ra of the 1 st sheet is 7.0 μm or less, the 2 nd layer of the 2 nd sheet can appropriately absorb the solvent flowing out together with the color former by the disintegration of the specific microcapsule in the pressurized region, and therefore, a good image quality with less penetration can be obtained.
In addition, as for the arithmetic average roughness Ra of the 1 st sheet, it can be controlled by adjusting the solid content coating amount of the 1 st layer forming composition and adjusting the amount of the specific microcapsule in the 1 st layer of the 1 st sheet.
< 2 nd sheet >
The 2 nd sheet 22 shown in fig. 1 includes a 2 nd support 18 and a 2 nd layer 20 containing a color developer and disposed on the 2 nd support 18.
Hereinafter, each member will be described in detail.
< No. 2 support >
The 2 nd support is a member for supporting the 2 nd layer. In addition, in the case of being able to be handled by the 2 nd layer itself, the 2 nd sheet may not have the 2 nd support.
The mode of the 2 nd support body is the same as that of the 1 st support body described above, and therefore, the description thereof is omitted.
< layer 2 >
The 2 nd layer is a layer containing a developer.
The developer is a compound which does not have a color-developing function but has a property of developing a color of a color-developing agent by contacting the color-developing agent. The developer is preferably an electron-accepting compound.
The color-developer includes inorganic compounds and organic compounds, and preferably includes inorganic compounds and organic compounds described in WO2009/8248[0055] to [0056 ]. From the viewpoint of further improving the color development density and the image quality after color development, acid clay, activated clay, or a metal salt of an aromatic carboxylic acid is preferable.
The content of the color developer in the 2 nd layer is not particularly limited, but is preferably 50 to 95% by mass, more preferably 70 to 90% by mass, based on the total mass of the 2 nd layer.
The color-developing agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the color-developing agent in the 2 nd layer is not particularly limited, but is preferably 1.0 to 40g/m 2 . When the color-developing agent is an inorganic compound, the content of the color-developing agent is preferably 2.0 to 30g/m 2 More preferably 3.0 to 20g/m 2 。
The 2 nd layer may contain other components than the above-described developer.
Examples of the other components include a polymer binder, a pigment, a fluorescent whitening agent, an antifoaming agent, a penetrant, an ultraviolet absorber, a surfactant, and a preservative.
Examples of the polymer binder include synthetic polymers and natural polymers such as styrene-butadiene copolymers, polyvinyl acetate, polyacrylates, polyvinyl alcohol, polyacrylic acid, maleic anhydride-styrene copolymers, olefin resins, modified acrylate copolymers, starch, casein, gum arabic, gelatin, carboxymethyl cellulose or salts thereof, and methyl cellulose.
Examples of the pigment include ground calcium carbonate, light calcium carbonate, talc, and titanium dioxide.
The thickness of the 2 nd layer is not particularly limited, but is preferably 0.5 to 30 μm, and more preferably 3.5 to 30 μm.
And the mass per unit area (solid content coating amount) of the 2 nd layer (g/m) 2 ) Is not particularly limited, and is, for example, 0.5 to 30.0g/m 2 More preferably 3.5 to 30.0g/m 2 。
< method for forming layer 2 >
The method for forming the 2 nd layer is not particularly limited, and a known method can be used.
For example, a method may be mentioned in which the layer-forming composition for layer 2 containing a color-developer is applied to the support for layer 2 and, if necessary, dried.
The composition for forming the 2 nd layer may be a dispersion liquid in which a developer is dispersed in water or the like. In the case where the developer is an inorganic compound, a dispersion liquid in which the developer is dispersed can be prepared by mechanically dispersing the inorganic compound in water. When the developer is an organic compound, the developer can be prepared by mechanically dispersing the organic compound in water or dissolving the organic compound in an organic solvent.
The composition for forming the layer 2 may contain other components that may be contained in the layer 2.
The method of applying the composition for forming the 2 nd layer is not particularly limited, and a method using a coater used in applying the composition for forming the 1 st layer is exemplified.
After the composition for forming the layer 2 is applied to the support 2, the coating film may be dried as necessary. The drying treatment may be a heating treatment.
In addition, although the method of forming the 2 nd layer on the 2 nd support has been described above, the method is not limited to the above embodiment, and for example, the 2 nd layer may be formed on the temporary support and then the temporary support may be peeled off to form the 2 nd sheet composed of the 2 nd layer.
The temporary support is not particularly limited as long as it is a releasable support.
< other Components >
The 2 nd sheet may have other members than the 2 nd support and the 2 nd layer described above.
For example, the 2 nd sheet may have an easy-adhesion layer between the 2 nd support and the 2 nd layer for improving adhesion therebetween.
Examples of the easy adhesion layer include those which the above-mentioned 1 st sheet may have.
As described above, the 1 st sheet and the 2 nd sheet are used by laminating the 1 st sheet and the 2 nd sheet so that the 1 st layer of the 1 st sheet and the 2 nd layer of the 2 nd sheet face each other to obtain a laminate, and pressing the laminate.
From the viewpoint of further excellent color development intensity, the oil absorption of the specific solvent to the 2 nd sheet is preferably 2.0 to 20.0g/m 2 . The oil absorption of the specific solvent to the No. 2 sheet was 2.0g/m 2 In the above case, in the pressurized region, the solution containing the color former and the specific solvent, which flows out due to the disintegration of the specific microcapsule, is easily absorbed by the layer 2 of the 2 nd sheet, and a higher color density is easily generated. On the other hand, the oil absorption of the specific solvent with respect to the 2 nd sheet was 20.0g/m 2 In the following cases, in the pressurized region, the solution containing the color former and the specific solvent, which has flowed out due to the disintegration of the specific microcapsule, cannot reach the deep part of the 2 nd layer of the 2 nd sheet, and as a result, the amount of the color former present in the surface layer region of the 2 nd layer is large, and a higher color density is likely to occur.
Further, the oil absorption amount of the specific solvent with respect to the 2 nd sheet was obtained by obtaining the difference between the weight of the 2 nd sheet before the specific solvent was absorbed and the weight of the 2 nd sheet after the specific solvent was absorbed, and converting the difference into a unit area.
The arithmetic average roughness Ra of the 2 nd sheet is preferably 1.2 μm or less from the viewpoint of further excellent color development density and from the viewpoint of further excellent image quality (resolution). The arithmetic average roughness Ra of the 2 nd sheet is the arithmetic average roughness Ra of the surface of the 2 nd sheet on the side (side in contact with) facing the 1 st sheet when the pressure measurement sheet set is used. When the 2 nd layer is positioned on the outermost surface of the 2 nd sheet on the side facing the 1 st sheet, the arithmetic average roughness Ra corresponds to the arithmetic average roughness Ra of the surface on the side opposite to the 2 nd support side of the 2 nd layer.
In addition, the arithmetic average roughness Ra of the No. 2 sheet in the present specification means JIS B0681-6: 2014 the arithmetic average roughness Ra. In addition, as a measuring apparatus, a scanning type white light interferometer using a light interference system (specifically, NewView5020 manufactured by Zygo corporation: Micro mode; Objective lens X50 times; intermediate lens X0.5 times) was used.
Method for manufacturing sheet set for pressure measurement
The method of manufacturing the 1 st sheet and the 2 nd sheet provided as the pressure measurement sheet set is as described above. The method for producing the pressure-measuring sheet set preferably includes the steps of applying a 1 st layer-forming composition containing microcapsules each containing a solvent having a boiling point of 100 ℃ or higher and a color former, and drying the obtained coating film to form the 1 st layer.
The method for forming the 1 st layer using the 1 st layer forming composition is as described in embodiment 1.
[2 nd embodiment ]
Fig. 3 is a cross-sectional view of an embodiment of a pressure-measuring sheet.
The pressure-measuring sheet 30 includes a support 32, a 2 nd layer 20 containing a developer, and a 1 st layer 14 containing specific microcapsules 13 in this order.
When the pressure-measuring sheet 30 is used, the specific microcapsules 13 are ruptured in the pressurized region by pressurizing from at least one of the support 32 side and the 1 st layer 14 side, and the color former contained in the specific microcapsules 13 comes out of the specific microcapsules 13, thereby performing a color development reaction with the color developer in the 2 nd layer 20. As a result, color development proceeds in the pressurized region.
As described later, the pressure-measuring sheet 30 may have the 1 st layer 14 and the 2 nd layer 20, or may not have the support 32.
In fig. 3, the support 32 and the 2 nd layer 20 are directly laminated, but the present invention is not limited to this embodiment, and another layer (for example, an easy adhesion layer) may be disposed between the support 32 and the 2 nd layer 20 as described later.
Further, although the pressure measurement sheet 30 having the support 32, the 2 nd layer 20, and the 1 st layer 14 in this order is disclosed in fig. 3, the present invention is not limited to this embodiment, and a pressure measurement sheet having the support 32, the 1 st layer 14, and the 2 nd layer 20 in this order may be used.
The 1 st layer 14 and the 2 nd layer 20 in the pressure-measuring sheet 30 are the same members as the 1 st layer 14 and the 2 nd layer 20 described in the above-described embodiment 1, and therefore, description thereof is omitted.
Hereinafter, the support 32 will be mainly described in detail.
Support
The support is a member for supporting the 1 st and 2 nd layers. In the case where the pressure measurement sheet can be handled by the laminate itself of the 1 st and 2 nd layers, the pressure measurement sheet may not have a support.
The preferred embodiment of the support is the same as that of the above-described 1 st support, and therefore, the description thereof is omitted.
Method for producing pressure measuring sheet
The method for producing the pressure-measuring sheet is not particularly limited, and known methods can be used.
The method for producing a pressure-measuring sheet preferably includes the steps of applying a composition for forming layer 1 containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former, and if necessary, drying the obtained coating film to form layer 1.
As a specific example of the method for producing the pressure-measuring sheet, the following method can be mentioned: after a 2 nd layer is formed on a support by applying a 2 nd layer forming composition containing a developer to the support and, if necessary, drying the composition, a 1 st layer forming composition containing specific microcapsules and a solvent having a boiling point of 100 ℃ or higher is further applied to the 2 nd layer and, if necessary, the coating film is dried to form a 1 st layer.
The method for forming the 1 st layer using the 1 st layer forming composition is as described in embodiment 1. The method for forming the 2 nd layer using the composition for forming the 2 nd layer is also as described in embodiment 1.
Other parts
The pressure-measuring sheet may include other members besides the support, the 2 nd layer, and the 1 st layer.
For example, the pressure-measuring sheet may have an easy-adhesion layer between the support and the 2 nd layer for improving adhesion therebetween.
Examples of the easy adhesion layer include those which the above-mentioned 1 st sheet may have.
As described above, the pressure measurement sheet is used by pressing the surface thereof.
From the viewpoint of further excellent color development intensity, the oil absorption of the specific solvent in the 2 nd layer is preferably 2.0 to 20.0g/m 2 . The oil absorption of the specific solvent in the 2 nd layer was 2.0g/m 2 In the above case, in the pressurized region, the solution containing the color former and the specific solvent flowing out due to the disintegration of the specific microcapsule is easily absorbed by the layer 2, and a higher color density is easily generated. On the other hand, the oil absorption of the specific solvent to the 2 nd layer was 20.0g/m 2 In the following cases, in the pressurized region, the solution containing the color former and the specific solvent which flows out due to the disintegration of the specific microcapsule is absentAs a result, the amount of the color former present in the surface layer region of the 2 nd layer is large, and a higher color density is likely to occur.
The pressure measurement sheet set and the application of the pressure measurement sheet of the present invention are not particularly limited, and examples thereof include pressure measurement during the production of electronic components (pressure measurement in a bonding step of a liquid crystal panel, confirmation of pressure distribution in a solder printing step of a printed circuit board, confirmation of pressure distribution in a pressure bonding step of an integrated circuit or a wiring, and the like), and pressure measurement during the production of automobiles (cylinder gasket surface pressure measurement of an engine, pressure measurement of flange surfaces of various sealing portions, and ground contact pressure confirmation of tires).
[ 3 rd embodiment ]
As embodiment 3, there is exemplified a dispersion (hereinafter, also simply referred to as "1 st dispersion") (dispersion for pressure measurement layer formation) for forming a layer used in combination with a layer containing a color developer for pressure measurement, and containing microcapsules containing a solvent and a color former having a boiling point of 100 ℃ or higher.
In the 1 st dispersion, the solvent having a boiling point of 100 ℃ or higher contains 2 or more kinds of solvents containing an aromatic group, and the color former contains 2 or more kinds of color formers containing an aromatic group.
Details of the components contained in the dispersion 1 are as described above.
The 1 st dispersion may be the 1 st layer-forming composition.
The 1 st dispersion liquid usually contains a solvent for dispersing the microcapsules (a solvent not included in the microcapsules). The kind of the solvent contained in the 1 st dispersion is not particularly limited, and water and an organic solvent may be mentioned. The organic solvent may be, for example, a solvent having a boiling point of 100 ℃ or higher used in the preparation of the 1 st dispersion.
The 1 st dispersion was used for forming a layer for pressure measurement (corresponding to the 1 st layer) in the same manner as the 1 st layer-forming composition.
The 1 st dispersion may be used in combination with a dispersion used for forming a layer containing a developer (hereinafter, also simply referred to as "2 nd dispersion"). That is, the 1 st dispersion and the 2 nd dispersion may be used as a set (dispersion set).
The 2 nd dispersion is a dispersion containing a color developer.
The 2 nd dispersion liquid may be the above-mentioned 2 nd layer forming composition.
Examples of the form of the developer contained in the 2 nd dispersion liquid include a form of the developer contained in the 2 nd layer forming composition.
The 2 nd dispersion usually contains a solvent. The kind of the solvent contained in the 2 nd dispersion is not particularly limited, and water and an organic solvent may be mentioned.
The 1 st dispersion preferably does not contain coarse particles for the reason that it can be applied to a curved surface without irregularities and does not clog in a coating method such as spraying.
For the same reason as described above, the average particle diameter of the microcapsules is preferably 1 to 50 μm.
For the same reason as described above, the 2 nd dispersion preferably does not contain coarse particles.
For the same reason as described above, the developer contained in the 2 nd dispersion is preferably an organic compound. The organic compound is preferably a metal salt of an aromatic carboxylic acid, more preferably a metal salicylate, and still more preferably a zinc salicylate.
The dispersion 1 can be applied to an object that is difficult to measure pressure in sheets such as a pressure measurement sheet set and a pressure measurement sheet. More specifically, the pressure measurement can be performed by applying a desired amount of the 1 st dispersion to a region of the object to be pressure-measured, without being affected by the surface shape of the object to be pressure-measured, and forming a layer containing the microcapsules in the region. In particular, the present invention can be preferably applied to a case where the pressure in a curved surface is measured. More specifically, the layer containing microcapsules was formed by applying the 1 st dispersion to a curved surface portion, and pressure measurement was performed.
As described above, the layer formed from the 1 st dispersion was used in combination with the layer containing the color developer for pressure measurement. Therefore, as in the case of using the 1 st dispersion, the pressure measurement can be performed by applying a required amount of the 2 nd dispersion to a region of the object to be pressure-measured where pressure measurement is required, and disposing a layer containing the developer and a layer containing the microcapsule adjacent to each other.
In addition, although the layer containing the microcapsules and the layer containing the developer are generally disposed in a stacked manner in a region of the object to be pressure-measured where pressure measurement is required, either layer may be disposed on the object side. In other words, in the region of the object to be pressure-measured where pressure measurement is required, either the 1 st dispersion liquid or the 2 nd dispersion liquid may be applied first.
As described above, by pressing the surface coated with the 1 st dispersion and the 2 nd dispersion from the other side, the microcapsule is broken in the pressed region and the color former contained in the microcapsule comes out of the microcapsule, and comes into contact with the developer to perform a color development reaction with the developer. As a result, color development proceeds in the pressurized region.
The method of applying the 1 st dispersion and the 2 nd dispersion is not particularly limited, and roll coating, spray coating, brush coating, and dip coating may be mentioned.
The application of the 1 st dispersion and the 2 nd dispersion may be performed directly on the measurement surface of the object to be measured, or may be performed via a film, paper, or the like.
The amount of the 1 st dispersion and the 2 nd dispersion to be applied can be set according to the measurement application, but is preferably 2 to 40g/m in terms of solid content, for example, from the viewpoint of obtaining a good color development and color development distribution 2 。
[ 4 th embodiment ]
As embodiment 4, there is exemplified a dispersion liquid (hereinafter, also simply referred to as "dispersion liquid for forming a pressure measurement layer") containing microcapsules containing a solvent and a color former having a boiling point of 100 ℃ or higher and a color developer, the dispersion liquid being used for forming a layer for pressure measurement.
In the 3 rd dispersion, the solvent having a boiling point of 100 ℃ or higher contains 2 or more kinds of solvents containing an aromatic group, and the color former contains 2 or more kinds of color formers containing an aromatic group.
Examples of the form of the microcapsule contained in the 3 rd dispersion include a form of the microcapsule contained in the composition for forming the 1 st layer.
Examples of the form of the developer contained in the 3 rd dispersion liquid include a form of the developer contained in the 2 nd layer forming composition.
The 3 rd dispersion liquid usually contains a solvent for dispersing the microcapsules (a solvent not included in the microcapsules). The kind of the solvent contained in the 3 rd dispersion is not particularly limited, and water and an organic solvent may be mentioned.
Examples of the 3 rd dispersion include a system in which the developer is mixed in the 1 st layer forming composition described above and a system in which the 2 nd layer forming composition described above is mixed in the 1 st layer forming composition described above.
The 3 rd dispersion preferably does not contain coarse particles for the reason that it can be applied to a curved surface without irregularities and does not clog in a coating method such as spraying.
For the same reason as described above, the average particle diameter of the microcapsules is preferably 1 to 50 μm.
For the same reason as described above, the developer contained in the 3 rd dispersion liquid is preferably an organic compound. The organic compound is preferably a metal salt of an aromatic carboxylic acid, more preferably a metal salicylate, and still more preferably a zinc salicylate.
Since the 3 rd dispersion contains the color former-containing microcapsules and the color developer, the pressure measurement can be performed only by the layer formed by applying the 3 rd dispersion.
That is, the 1 st dispersion and the 2 nd dispersion and the 3 rd dispersion can be applied to objects that are difficult to measure pressure in sheets such as a pressure measurement sheet set and a pressure measurement sheet. More specifically, the pressure measurement can be performed by applying a desired amount of the 3 rd dispersion to a region of the object to be pressure-measured, without being affected by the surface shape of the object to be pressure-measured, and forming a layer in the region.
Examples of the method and conditions for applying the 3 rd dispersion include the methods and conditions for applying the 1 st dispersion and the 2 nd dispersion described above.
The 1 st dispersion, the 2 nd dispersion and the 3 rd dispersion can be used for various purposes.
Examples of the confirmation include confirmation of pressure distribution in molding processing of various components and bodies or in assembling processing of components in manufacturing of vehicles such as automobiles and aircrafts, confirmation of pressure distribution in assembling processing of building materials, confirmation of pressure distribution in processes such as curved surface processing of electronic products, confirmation of impact force applied to goods accompanying transportation, confirmation of each mold in manufacturing of metal products, confirmation of each mold in molding processing of resin products, confirmation of pressure distribution in tablet in medical products, confirmation of pressure distribution in furniture surface such as sofa seat surface, confirmation of grip force applied to writing instruments and the like, confirmation of impact force applied to sports goods such as balls made of elastic materials, and confirmation of gaps (clearances) between upper and lower teeth in dental goods.
Examples
The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the order of the processes, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.
[ production of sheet set for pressure measurement ]
[ example 1]
< preparation of microcapsules containing color former therein >
3 ', 6' -bis (diethylamino) -2- (4-nitrophenyl) spiro [ isoindole-1, 9 '-xanthen ] -3-one (manufactured by Hodgaya Chemical Co., Ltd., Pink-DCF)3 parts, 6' - (diethylamino) -1 ', 3' -dimethylfluoran precursor (Hodgaya Chemical Co., Ltd., ltd. manufacture, Orange-DCF)4 parts, thereby obtaining solution a. Next, 13 parts of N, N' -tetrakis (2-hydroxypropyl) ethylenediamine (ADEKA CORPORATION, ADEKA polymer EDP-300) dissolved in synthetic isoalkane (Idemitsu Kosan co., ltd., IP Solvent 1620) and 2.5 parts of methyl ethyl ketone were added to the stirred solution a, thereby obtaining a solution B. Furthermore, 2.5 parts of a trimethylolpropane adduct of toluene diisocyanate (DIC CORPORATION, BURNOCK D-750) dissolved in 6 parts of ethyl acetate were added to the stirred solution B to obtain a solution C. Then, the solution C was added to a solution prepared by dissolving 7 parts of polyvinyl alcohol (PVA-217E, Kuraray co., Ltd.) in 140 parts of water, and emulsified and dispersed. To the emulsified liquid after the emulsion dispersion, 200 parts of water was added, and the mixture was heated to 70 ℃ while stirring, and then cooled after stirring for 1 hour. Further, water was added to adjust the concentration, thereby obtaining a microcapsule liquid containing a color former with a solid content concentration of 20 mass%.
The average particle diameter of the obtained microcapsules containing a color former was 20 μm. The average particle diameter was measured by an optical microscope and by the method described above.
< production of sheet set for pressure measurement >
(preparation of the 1 st sheet)
The obtained microcapsule liquid containing a color former inside, 10 parts of water, 1.8 parts of colloidal silica (Nissan Chemical Industries, ltd., SNOWTEX 30, solid content 30%), 2 parts of a 1% aqueous solution of sodium carboxymethylcellulose (DKS co.ltd., SEROGEN 5A), 4.5 parts of a 1% aqueous solution of sodium carboxymethylcellulose (DKS co.ltd., SEROGEN EP), 1 part of a 15% aqueous solution of a side chain alkylbenzenesulfonic acid amine salt (DKS co.ltd., NEOGEN T), 0.2 parts of a 1% aqueous solution of polyoxyethylene polyoxypropylene lauryl ether (DKS co.ltd., nonogen LP-70), and 0.2 parts of a 1% aqueous solution of sodium-bis (3,3,4,4,5,5,6,6, 6-nonafluorohexyl) -2-sulfonyloxyoctanoic acid (fujim film, W-AHE) were mixed to obtain a 1% aqueous solution for forming a layer, and a composition for a 1 st.
The obtained composition for forming the 1 st layer was applied to a polyethylene terephthalate (PET) sheet having a thickness of 75 μm by a bar coater so that the dried mass became 6.0g/m 2 . Subsequently, the obtained coating film was dried at 80 ℃ to form a 1 st layer, thereby producing a 1 st sheet.
(preparation of No. 2 sheet)
100 parts of activated clay (Mizusawa Industrial Chemicals, Ltd., Shilton F-242), 0.5 part of Na hexametaphosphate (Nippon Chemical Industry Co., Ltd., sodium hexametaphosphate), 15 parts of 10% aqueous sodium hydroxide solution, 240 parts of water, 30 parts of olefin resin (ARAKAWA CHEMICAL INDUSTRIES, LTD., Polymaron482, solid content concentration 25 mass%) mixed with the obtained dispersion, 35 parts of modified acrylate copolymer (Zeon Corporation, Nippon LX814, solid content concentration 46 mass%), 80 parts of sodium carboxymethylcellulose (DKS Co. Ltd., SEROGEN EP), 18 parts of alkylbenzenesulfonic acid Na (DKS Co. Ltd., NEOGEN) 15% aqueous solution, polyoxyethylene polyoxypropylene ether (DKS Co. Ltd., NOIGEN-70) 1% aqueous solution, 3-4% sodium bis (3, 3-4, 5,6, 6-5, 6-hexyl oxy-6, 6, 6-5-6-nona-5 mass%) as a developer, and 1% aqueous solution of sodium octoate, W-AHE) was added to 20 parts of a 1% aqueous solution to prepare a coating liquid containing a developer.
The coating liquid containing a developer was applied to a polyethylene terephthalate (PET) sheet having a thickness of 75 μm so that the amount of solid matter applied was 7.0g/m 2 . Next, the obtained coating film was dried to form a 2 nd layer, thereby obtaining a 2 nd sheet.
[ example 2]
< preparation of microcapsules containing color former therein >
A microcapsule containing a color former was prepared in the same manner as in example 1 except that 50 parts of SRS-101 (manufactured by taijijin chemical Corporation) was changed to 50 parts of a mixture of 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 3-trimethylbenzene, cumene and xylene (manufactured by ENEOS Corporation, Hysol 100).
< production of sheet set for pressure measurement >
A pressure measurement sheet set of example 2 was produced in the same manner as in example 1, except that the obtained microcapsules containing a color former therein were used.
[ example 3]
< preparation of microcapsules containing color former therein >
Microcapsules containing a color former were prepared in the same manner as in example 1, except that 3 parts of Pink-DCF (manufactured by Hodogaya Chemical co., ltd.) and 4 parts of Orange-DCF (manufactured by Hodogaya Chemical co., ltd.) were changed to 4 parts of the compound represented by the following structure (a) (YAMADA CHEMICAL co., ltd., Red500) and 4 parts of the compound represented by the following structure (B) (YAMADA CHEMICAL co., ltd., Red 520).
A compound represented by the structure (A)
[ chemical formula 6]
A compound represented by the structure (B)
[ chemical formula 7]
< production of sheet set for pressure measurement >
A pressure measurement sheet set of example 3 was produced in the same manner as in example 1, except that the obtained microcapsules containing a color former therein were used.
[ examples 4 to 7]
< preparation of microcapsules containing a color former therein >
A microcapsule containing a color former was prepared in the same manner as in example 1 except that 50 parts of SRS-101 (manufactured by taijinzhengjinzhengjinji chemical corporation) was changed to 50 parts of the solvent described in the column of "solvent containing aromatic group" in table 1 (in the column of "kind of solvent containing aromatic group" in table 1, the numerical value in parentheses simultaneously described in the kind of solvent represents the mixing ratio (mass basis)).
< production of sheet set for pressure measurement >
Pressure measurement sheet sets of examples 4 to 7 were produced in the same manner as in example 1, except that the obtained color former-containing microcapsules were used.
[ example 8 ]
< production of sheet set for pressure measurement >
In the production of the No. 1 sheet, the obtained composition for forming the No. 1 layer was applied to a polyethylene terephthalate (PET) sheet having a thickness of 75 μm by a bar coater so that the dried mass became 12.0g/m 2 A pressure measurement sheet set of example 8 was produced in the same manner as in example 1, except that the obtained coating film was dried at 80 ℃ to form the 1 st layer.
[ example 9]
< production of sheet set for pressure measurement >
In the preparation of the No. 2 sheet, a coating liquid containing a developer was applied to a polyethylene terephthalate (PET) sheet having a thickness of 75 μm so that the amount of solid matter applied was 3.5g/m 2 A pressure measurement sheet set of example 9 was produced in the same manner as in example 1, except that the obtained coating film was dried to form the 2 nd layer.
[ example 10 ]
< production of sheet set for pressure measurement >
In the preparation of the No. 2 sheet, a coating liquid containing a developer was applied to a polyethylene terephthalate (PET) sheet having a thickness of 75 μm so that the amount of solid matter applied was 1.8g/m 2 A pressure measurement sheet set of example 10 was produced in the same manner as in example 1, except that the obtained coating film was dried to form the 2 nd layer.
[ example 11 ]
< preparation of microcapsules containing color former therein >
Microcapsules containing a color former were prepared in the same manner as in example 1, except that 50 parts of SRS-101 (manufactured by taijinzhengjinzheng fine chemical corporation) was changed to 47 parts, and 13 parts of IP Solvent 1620 (manufactured by Idemitsu Kosan co., ltd.) was changed to 16 parts.
< production of pressure-measuring sheet set >
A pressure measurement sheet set of example 11 was produced in the same manner as in example 1, except that the obtained microcapsules containing a color former therein were used.
[ comparative example 1]
< preparation of microcapsules containing color former therein >
Microcapsules containing a color former were prepared in the same manner as in example 1, except that 50 parts of SRS-101 (manufactured by taijinzhengjinzheng fine chemical corporation) was changed to 47 parts of 4-isopropylbiphenyl and 13 parts of IP Solvent 1620 (manufactured by Idemitsu Kosan co., ltd.) was changed to 16 parts of it.
< production of sheet set for pressure measurement >
A pressure measurement sheet set of comparative example 1 was produced by the same method as in example 1, except that the obtained microcapsules containing a color former therein were used.
[ comparative example 2]
< preparation of microcapsules containing color former therein >
Microcapsules containing a color former were produced in the same manner as in example 4 except that 3 parts of Pink-DCF (manufactured by Hodogaya Chemical co., ltd.) and 4 parts of Orange-DCF (manufactured by Hodogaya Chemical co., ltd.) were changed to 7 parts of Pink-DCF (manufactured by Hodogaya Chemical co., ltd.) in each example.
< production of sheet set for pressure measurement >
A pressure measurement sheet set of comparative example 1 was produced by the same method as in example 4, except that the obtained microcapsules containing a color former therein were used.
[ measurement and evaluation ]
[ oil absorption (g/m) of aromatic group-containing solvent with respect to the No. 2 sheet 2 ) Measurement of (2)〕
After the aromatic group-containing solvent (for example, "SRS-101" in example 1) was permeated throughout the 2 nd sheet, the aromatic group-containing solvent which overflowed without being absorbed into the sheet was wiped off. Then, the weight of the 2 nd sheet before the infiltration of the solvent containing an aromatic group was subtracted from the weight of the 2 nd sheet after the infiltration of the solvent containing an aromatic group, and the weight per 1m of the 2 nd sheet was calculated 2 Oil absorption of (4).
[ measurement of arithmetic mean roughness Ra of sheet No. 1 and sheet No. 2]
The measurement methods of the arithmetic average roughness Ra of the 1 st sheet (corresponding to the arithmetic average roughness Ra of the surface opposite to the PET sheet side of the 1 st layer) and the arithmetic average roughness Ra of the 2 nd sheet (corresponding to the arithmetic average roughness Ra of the surface opposite to the PET sheet side of the 2 nd layer) were as described above.
[ evaluation of color development Density ]
< measurement of concentration (DA) of color-emitting portion formed on No. 2 sheet >
Using the 1 st sheet and the 2 nd sheet prepared in each example and comparative example, evaluation of the pressure measurement sheet set was performed. Specifically, the 1 st sheet and the 2 nd sheet cut to a size of 5cm × 5cm were stacked so that the surface of the 1 st layer of the 1 st sheet and the surface of the 2 nd layer of the 2 nd sheet were in contact with each other, to obtain a laminate. Subsequently, the laminate was pressed by a press (DSF-C1-A, AIDA ENGINEERING, LTD.) under a pressure of 1.0MPa to develop color. Thereafter, the 1 st and 2 nd sheets constituting the laminate were peeled off, and the concentration (DA) of the color-emitting portion formed on the 2 nd sheet was measured from the support (PET sheet) surface side via the support using a densitometer RD-19 (manufactured by X-Rite Inc).
< calculation of color development concentration Δ D1 >
Separately from this, the initial concentration (DB) of the unused 2 nd sheet was measured from the support (PET sheet) surface side with the support interposed therebetween using a concentration meter RD-19 (manufactured by X-Rite Inc). Then, color development concentration Δ D1 was obtained by subtracting initial concentration DB from concentration DA, and evaluated according to the following evaluation criteria. "B" is a range that can be practically allowed.
The results are shown in table 1.
< evaluation Standard >
"A": Δ D1 was 0.7 or more (color development was clearly observed).
"B": Δ D1 was 0.2 or more and less than 0.7 (slightly color development was observed).
"C": Δ D1 was less than 0.2 (little color development was observed).
[ evaluation of storage stability ]
After the 1 st sheet was stored at-30 ℃ for 1 week, the temperature was returned to normal temperature, and the concentration (DA') of the color-forming part formed on the 2 nd sheet was measured by the same method as the above-described measurement of the concentration (DA) of the color-forming part formed on the 2 nd sheet.
Separately from this, the initial concentration (DB) of the unused 2 nd sheet was measured from the support (PET sheet) surface side with the support interposed therebetween using a concentration meter RD-19 (manufactured by X-Rite Inc). Then, the initial concentration DB was subtracted from the concentration DA 'to obtain color development concentration Δ D1'.
Then, color development concentration Δ D1' was subtracted from color development concentration Δ D1, and color development concentration difference Δ D2 before and after storage was obtained. The obtained value of Δ D2 was evaluated according to the following evaluation criteria. "B" is a range that can be practically allowed.
The results are shown in table 1.
< evaluation Standard >
"A": Δ D2 was 0.1 or less (no change was observed).
"B": Δ D2 exceeded 0.1 and was 0.3 or less (slight change was observed).
"C": Δ D2 exceeded 0.3 (a large change was observed).
[ image quality (resolution) evaluation ]
The surface of the 1 st layer of the unused 1 st sheet was observed by an optical microscope to determine the average particle diameter of the microcapsules (microcapsule diameter D (μm)). The method for measuring the average particle diameter of the microcapsules is as described above.
Then, the surface of the layer 2 of the 2 nd sheet after color development was observed with an optical microscope to determine the average dot diameter of the color-developed dots (color-developed dot diameter D' (μm)). From the obtained values, the diameter D' (μm) of the color-developing dots relative to the diameter D (μm) of the microcapsule was obtained, and the evaluation was performed according to the following evaluation criteria.
The specific method for measuring the diameter D' (μm) of the color-forming spot is as follows.
For color point diameter D' (μm): the image of the surface of layer 2 of the 2 nd sheet after color development from the surface of layer 2 was analyzed by an optical microscope (OLYMPUS BX60, size of field: 320. mu. m.times.450. mu.m), and the major axes of 30 color development points were measured sequentially from the maximum color development point, and the average value was obtained by arithmetically averaging these. This operation was performed at arbitrary 5 sites (5 fields) on layer 2, and the average of the average values obtained at each site was obtained, and the obtained value was set as the average dot diameter of the color dots (color dot diameter D' (μm)). The long diameter is the longest diameter when observing the color point.
The results are shown in table 1.
< evaluation Standard >
"A": D'/D is less than 50 (high image quality).
"B": D'/D is 50 or more and less than 300 (medium picture quality).
"C": D'/D is 300 or more (low image quality).
Table 1 is shown below.
In the "kind" in the column of "solvent containing aromatic group" in table 1, the numerical values in parentheses shown together in the kind of solvent represent the mixing ratio (mass basis). For example, example 4 shows that 50/50 mass ratio of 4-isopropylbiphenyl and 4, 4' -diisopropylbiphenyl was contained as the aromatic group-containing solvent.
In table 1, "SRS-101" in the column of "solvent containing aromatic group" is a mixture of 1, 2-dimethyl-4- (1-phenylethyl) benzene, 1, 3-dimethyl-4- (1-phenylethyl) benzene, 1, 4-dimethyl-2- (1-phenylethyl) benzene and 1- (ethylphenyl) -1-phenylethane (manufactured by taijin chemical co. That is, 4 kinds of solvents containing 2 aromatic groups are contained in the molecule.
In Table 1, "Hysol 100" in the column of "aromatic group-containing solvent" is a mixture of 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 3-trimethylbenzene, cumene and xylene (manufactured by ENEOS Corporation). That is, 3 kinds of solvents containing 1 aromatic group are contained in the molecule.
In table 1, "Pink-DCF" and "Orange-DCF" (both manufactured by Hodogaya Chemical co., ltd.) and "Red 500" and "Red 520" (both manufactured by YAMADA CHEMICAL co., ltd.) in the column of "color former" correspond to color formers including aromatic groups.
In table 1, "the content (%) of the aromatic group-containing solvent" means the content (%) of the aromatic group-containing solvent with respect to the total mass of the aromatic group-containing solvent and the aliphatic structure-containing solvent.
In table 1, "presence or absence of a solvent containing 2 aromatic groups in a molecule" indicates that "a" indicates that the solvent containing an aromatic group contains a solvent containing 2 aromatic groups in a molecule, and "B" indicates that the solvent containing an aromatic group does not contain a solvent containing 2 aromatic groups in a molecule.
In table 1, "the content (%) of the solvent containing 2 aromatic groups in the molecule" means the content (%) of the solvent containing 2 aromatic groups in the molecule with respect to the total mass of the solvent containing aromatic groups.
As is clear from the results in table 1, the pressure measurement sheet set of the examples is excellent in storage stability at low temperature. Further, it is also found that the color development density of the pressure measurement sheet set of the example is high.
Further, from the comparison between example 1 and example 2, it was confirmed that when the aromatic group-containing solvent is a solvent containing 2 aromatic groups in the molecule, the storage stability at low temperature is more excellent and the color development intensity is also more excellent.
Further, from the comparison of examples 1, 5,6 and 7, it was confirmed that when the content of the solvent containing 2 aromatic groups in the molecule was 50 mass% or more based on the total mass of the solvents containing aromatic groups, the storage stability at low temperature was more excellent and the color development intensity was more excellent.
Further, from comparison between example 1 and example 8, it was confirmed that the mass per unit area (g/m) of the 1 st layer of the 1 st sheet was 2 ) (refer to "coating weight of solid component g/m" in Table 1 2 Column) was adjusted to 10.0g/m 2 Hereinafter, when the arithmetic average roughness Ra of the 1 st sheet is 3.0 to 7.0 μm, the image quality (resolution) of the color portion formed on the 2 nd sheet is further excellent.
Further, from the comparison of examples 1,9 and 10, it was confirmed that the mass per unit area (g/m) of the 2 nd layer of the 2 nd sheet was formed 2 ) (refer to "coating weight of solid component g/m" in Table 1 2 Column) was adjusted to 3.5g/m 2 As described above, the oil absorption (g/m) of the aromatic group-containing solvent with respect to the 2 nd sheet was determined 2 ) Set to be 2.0 to 20.0g/m 2 In the above case, the image quality (resolution) of the color-formed portion formed on the 2 nd sheet is further excellent.
Further, from the comparison between example 1 and example 11, it was confirmed that the color development intensity was more excellent when the content of the solvent containing 2 aromatic groups in the molecule was 75.0 mass% or more with respect to the total mass of the solvents containing aromatic groups.
As is clear from the results in table 1, the pressure-measuring sheet set of the comparative example does not satisfy the desired requirements.
In addition, although the above description shows the mode using the pressure measuring sheet set having the 1 st and 2 nd sheets, the pressure measuring sheets having the 2 nd and 1 st layers stacked in this order on the support were produced, and the same test results as those of the above were obtained, and the same results as those of the examples were obtained. For example, the same results as in example 1 were obtained as a result of performing the above evaluations (color development intensity evaluation, storage stability evaluation, and image quality (resolution) evaluation) on the pressure-measuring sheet having the support, the 2 nd layer, and the 1 st layer, which was prepared in example 1, disposed in this order on a polyethylene terephthalate sheet.
[ example 12 ]
The dispersion liquid set was spray-coated on a curved surface member, and evaluation of storage stability and evaluation of color development concentration were performed.
Specifically, the microcapsule liquid containing a color former prepared in example 1 was prepared as a 1 st dispersion liquid, and the dispersion liquid containing a developer prepared in example 1 was prepared as a 2 nd dispersion liquid.
< evaluation of storage stability and evaluation of color development concentration >
The 1 st dispersion was applied to a metal plate (concave/convex mirror (R: 100mm) made of stainless steel (SUS 304)) as an object to be coated by a brush coater, and dried for 24 hours to form a 1 st layer, and then the 2 nd dispersion was applied to the 1 st layer by a brush coater to form a 2 nd layer. The same metal plate was placed from above the coated side so as to cover the coating area, and pressurization based on a pressure of 10Mpa was performed for 120 seconds by a press (product name: H1F35-1, manufactured by Komatsu ltd.). After the completion of the pressing, the metal plate placed on the upper part was removed, and the color development and color development distribution in the coated region were confirmed by visual observation, and it was confirmed that the color development was performed at a sufficient concentration to be visually recognizable and that the color development distribution was visually recognizable with a sufficient difference in color development concentration.
After the 1 st dispersion was stored at-30 ℃ for 1 week, the temperature was returned to normal temperature, and the color development and color development distribution in the coated area were visually confirmed by coloring the coated area by a press treatment using a metal plate in the same manner as described above. As a result, almost no change in color development was observed as compared with the case where the film was not stored at low temperature.
[ example 13 ]
Storage stability and color development concentration were evaluated in the same manner as in example 12, except that the color developer-containing dispersion prepared in example 1 was changed to a 3, 5-bis (. alpha. -methylbenzyl) zinc salicylate dispersion diluted with water (SANKO CO., LTD., LR-220, solid content concentration 41 mass%) so that the solid content concentration became 20 mass%, and the brush coater was changed to spray coating. As a result, in the same manner as in example 12, it was confirmed that color was formed at a sufficient density that can be visually recognized, color distribution was visually recognized at a sufficient difference in color density, and little change in color was observed compared with the case where the storage was not performed at low temperature.
[ example 14 ]
The evaluation of color development intensity was carried out in the same manner as in example 13 except that the order of application of the 1 st dispersion and the 2 nd dispersion was changed, and it was confirmed that color development was carried out at a sufficient intensity to be visually recognized and a color development distribution was visually recognized at a sufficient difference in color development intensity in the same manner as in example 13.
[ example 15 ]
The results of evaluation of color emission intensity were carried out in the same manner as in example 13 except that the 1 st dispersion and the 2 nd dispersion were mixed in advance to prepare a 3 rd dispersion, and a specific position was applied using the 3 rd dispersion, and it was confirmed that color emission was carried out at a sufficient intensity that can be visually recognized and a color emission distribution was visually recognized at a sufficient difference in color emission intensity in the same manner as in example 13.
[ comparative example 3]
Storage stability and color development concentration were evaluated in the same manner as in example 12, except that the first dispersion was the microcapsule liquid containing a color developing agent prepared in comparative example 1. As a result, it was confirmed that the color was developed at a sufficient density that can be visually recognized and the color distribution was visually recognized with a sufficient difference in color density, but the color development was insufficient compared to the case where the storage was not performed at low temperature.
Description of the symbols
10-set of sheets for pressure measurement, 12-support 1, 13-specific microcapsules, 14-layer 1, 16-sheet 1, 18-support 2, 20-layer 2, 22-sheet 2, 30-sheet for pressure measurement, 32-support.
Claims (21)
1. A pressure measurement sheet set is provided with:
a 1 st sheet having a 1 st layer containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former; and
a 2 nd sheet having a 2 nd layer containing a color developer,
the solvent having a boiling point of 100 ℃ or higher contains 2 or more kinds of solvents containing an aromatic group, and
the color former contains 2 or more kinds of color formers containing aromatic groups.
2. The set of pressure-measuring sheets according to claim 1,
the aromatic group-containing solvent includes a solvent containing 2 aromatic groups in a molecule.
3. The set of pressure-measuring sheets according to claim 2,
the content of the solvent containing 2 aromatic groups in the molecule is 50% by mass or more with respect to the total mass of the solvents containing aromatic groups.
4. The set of pressure-measuring sheets according to any one of claims 1 to 3,
the solvent having a boiling point of 100 ℃ or higher contains 4 or more of the aromatic group-containing solvents.
5. The set of sheets for pressure measurement according to any one of claims 1 to 4,
the solvent having a boiling point of 100 ℃ or higher further comprises a solvent containing an aliphatic structure,
the content of the aromatic group-containing solvent is 50 to 90% by mass based on the total mass of the aromatic group-containing solvent and the aliphatic structure-containing solvent.
6. The set of sheets for pressure measurement according to any one of claims 1 to 5,
the oil absorption of the aromatic group-containing solvent with respect to the 2 nd sheet was 2.0g/m 2 ～20.0g/m 2 。
7. The set of sheets for pressure measurement according to any one of claims 1 to 6,
the 1 st sheet has an arithmetic average roughness Ra of 3.0 to 7.0 [ mu ] m.
8. The set of sheets for pressure measurement according to any one of claims 1 to 7,
the arithmetic average roughness Ra of the 2 nd sheet is 1.2 [ mu ] m or less.
9. The set of sheets for pressure measurement according to any one of claims 1 to 8,
the 1 st and 2 nd sheets further have a support,
the support is a resin film.
10. A pressure-measuring sheet comprising:
a first layer 1 containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former; and
a 2 nd layer disposed on the 1 st layer and containing a color developer,
the solvent having a boiling point of 100 ℃ or higher contains 2 or more kinds of solvents containing an aromatic group, and,
the color former contains 2 or more kinds of color formers containing aromatic groups.
11. The pressure-measuring sheet according to claim 10,
the aromatic group-containing solvent includes a solvent containing 2 aromatic groups in a molecule.
12. The pressure-measuring sheet according to claim 11,
the content of the solvent containing 2 aromatic groups in the molecule is 50% by mass or more with respect to the total mass of the solvents containing aromatic groups.
13. The sheet for pressure measurement according to any one of claims 10 to 12,
the solvent having a boiling point of 100 ℃ or higher contains 4 or more of the aromatic group-containing solvents.
14. The sheet for pressure measurement according to any one of claims 10 to 13,
the solvent having a boiling point of 100 ℃ or higher further comprises a solvent containing an aliphatic structure,
the content of the aromatic group-containing solvent is 50 to 90% by mass based on the total mass of the aromatic group-containing solvent and the aliphatic structure-containing solvent.
15. The sheet for pressure measurement according to any one of claims 10 to 14,
the oil absorption of the aromatic group-containing solvent with respect to the 2 nd layer was 2.0g/m 2 ～20.0g/m 2 。
16. The sheet for pressure measurement according to any one of claims 10 to 15, further comprising a support,
the support is a resin film.
17. A method for manufacturing the pressure measurement sheet set according to any one of claims 1 to 9, comprising:
a layer 1 forming composition containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former is applied, and the obtained coating film is dried to form a layer 1.
18. A method for producing the pressure-measuring sheet according to any one of claims 10 to 16, comprising the steps of:
a layer 1 forming composition containing microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former is applied, and the obtained coating film is dried to form a layer 1.
19. A dispersion liquid which is used for measuring pressure and forming a layer used for combining with a layer containing a developer, and which comprises microcapsules containing a solvent having a boiling point of 100 ℃ or higher and a color former,
the solvent having a boiling point of 100 ℃ or higher contains 2 or more kinds of solvents containing an aromatic group, and,
the color former contains 2 or more kinds of color formers containing aromatic groups.
20. The dispersion liquid according to claim 19,
the solvent having a boiling point of 100 ℃ or higher contains 4 or more of the aromatic group-containing solvents.
21. A microcapsule comprises solvent with boiling point above 100 deg.C and color former,
the solvent having a boiling point of 100 ℃ or higher contains 2 or more kinds of solvents containing an aromatic group, and,
the color former contains 2 or more kinds of color formers containing aromatic groups.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-225447 | 2019-12-13 | ||
| JP2019225447 | 2019-12-13 | ||
| PCT/JP2020/043972 WO2021117494A1 (en) | 2019-12-13 | 2020-11-26 | Pressure measurement sheet set and production method therefor, pressure measurement sheet and production method therefor, dispersion liquid, and microcapsules |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114902026A true CN114902026A (en) | 2022-08-12 |
| CN114902026B CN114902026B (en) | 2024-05-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080085210.9A Active CN114902026B (en) | 2019-12-13 | 2020-11-26 | Sheet set for pressure measurement and method for producing same, sheet for pressure measurement and method for producing same, dispersion liquid, and microcapsule |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7163514B2 (en) |
| CN (1) | CN114902026B (en) |
| TW (1) | TW202124137A (en) |
| WO (1) | WO2021117494A1 (en) |
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| JPH0247085A (en) * | 1988-08-09 | 1990-02-16 | Nippon Petrochem Co Ltd | Pressure sensitive copy material |
| EP0596510A1 (en) * | 1992-11-05 | 1994-05-11 | Fuji Photo Film Co., Ltd. | Process for producing microcapsules |
| JPH06328837A (en) * | 1993-05-20 | 1994-11-29 | Fuji Photo Film Co Ltd | Self color-developing pressure-sensitive recording sheet |
| JPH07214896A (en) * | 1994-01-27 | 1995-08-15 | Nippon Petrochem Co Ltd | Pressure-sensitive copy material and manufacture of color developer microcapsule used therefor |
| JPH0976632A (en) * | 1995-09-18 | 1997-03-25 | Fuji Photo Film Co Ltd | Recording material |
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| WO2018164080A1 (en) * | 2017-03-10 | 2018-09-13 | 富士フイルム株式会社 | Material for measuring pressure, material set for measuring pressure, method for measuring pressure, and liquid set for measuring pressure |
| WO2019003838A1 (en) * | 2017-06-30 | 2019-01-03 | 富士フイルム株式会社 | Pressure measurement material |
| CN109374165A (en) * | 2018-10-09 | 2019-02-22 | 东莞市亚马电子有限公司 | A kind of pressure detecting paper and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2607924B2 (en) | 1988-08-09 | 1997-05-07 | 日本石油化学株式会社 | Pressure-sensitive copying material |
| JP4986750B2 (en) | 2007-07-11 | 2012-07-25 | 富士フイルム株式会社 | Material for pressure measurement |
-
2020
- 2020-11-26 JP JP2021563843A patent/JP7163514B2/en active Active
- 2020-11-26 CN CN202080085210.9A patent/CN114902026B/en active Active
- 2020-11-26 WO PCT/JP2020/043972 patent/WO2021117494A1/en active Application Filing
- 2020-12-10 TW TW109143551A patent/TW202124137A/en unknown
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| JPH0247085A (en) * | 1988-08-09 | 1990-02-16 | Nippon Petrochem Co Ltd | Pressure sensitive copy material |
| EP0596510A1 (en) * | 1992-11-05 | 1994-05-11 | Fuji Photo Film Co., Ltd. | Process for producing microcapsules |
| JPH06328837A (en) * | 1993-05-20 | 1994-11-29 | Fuji Photo Film Co Ltd | Self color-developing pressure-sensitive recording sheet |
| JPH07214896A (en) * | 1994-01-27 | 1995-08-15 | Nippon Petrochem Co Ltd | Pressure-sensitive copy material and manufacture of color developer microcapsule used therefor |
| JPH0976632A (en) * | 1995-09-18 | 1997-03-25 | Fuji Photo Film Co Ltd | Recording material |
| JPH115026A (en) * | 1997-06-17 | 1999-01-12 | Fuji Photo Film Co Ltd | Color developer containing microcapsule and recording material using the same |
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| JP2002292665A (en) * | 2001-03-29 | 2002-10-09 | Dainippon Ink & Chem Inc | Method for manufacturing lactic acid polymer sheet |
| JP2009063512A (en) * | 2007-09-07 | 2009-03-26 | Fujifilm Corp | Material for pressure measurement |
| WO2018164080A1 (en) * | 2017-03-10 | 2018-09-13 | 富士フイルム株式会社 | Material for measuring pressure, material set for measuring pressure, method for measuring pressure, and liquid set for measuring pressure |
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| CN109374165A (en) * | 2018-10-09 | 2019-02-22 | 东莞市亚马电子有限公司 | A kind of pressure detecting paper and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021117494A1 (en) | 2021-06-17 |
| JPWO2021117494A1 (en) | 2021-06-17 |
| CN114902026B (en) | 2024-05-07 |
| TW202124137A (en) | 2021-07-01 |
| JP7163514B2 (en) | 2022-10-31 |
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