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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/333—Colour developing components therefor, e.g. acidic compounds
  • B41M5/3333—Non-macromolecular compounds
• • 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/305—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers with reversible electron-donor electron-acceptor compositions
• • 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/333—Colour developing components therefor, e.g. acidic compounds
  • B41M5/3333—Non-macromolecular compounds
  • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/50—Sympathetic, colour changing or similar inks
• • 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
  • B41M5/333—Colour developing components therefor, e.g. acidic compounds
  • B41M5/3333—Non-macromolecular compounds
  • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
  • B41M5/3336—Sulfur compounds, e.g. sulfones, sulfides, sulfonamides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/16—Writing inks
  • C09D11/17—Writing inks characterised by colouring agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
  • C09K9/02—Organic tenebrescent materials

Definitions

• the present invention relates to a reversible thermochromic composition, a writing instrument containing the reversible thermochromic composition, and a toy containing the reversible thermochromic composition.
• the reversible thermochromic composition includes a basic (electron-donating) leuco dye (hereinafter sometimes abbreviated as “leuco dye”), an electron-accepting color developer (hereinafter sometimes abbreviated as “developer” ), and discoloration temperature control agent as main components.
• the discoloration temperature adjuster reversibly causes an electron transfer reaction between the leuco dye and the developer in a specific temperature range, thereby adjusting the switching between the decoloring state and the coloring state (for example, Patent Document 1). .
• Examples of the developer contained in the reversible thermochromic composition include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)-1,1,1, Compounds mainly having a bisphenol structure such as 3,3,3-hexafluoropropane (bisphenol AF) are often used.
• bisphenol A 2,2-bis(4-hydroxyphenyl)propane
• bisphenol AF 2,2-bis(4-hydroxyphenyl)-1,1,1,
• bisphenol AF 2,2-bis(4-hydroxyphenyl)-1,1,1
• Patent Documents 2, 3 and 4 disclose reversible thermochromic compositions containing diphenylurea and diphenylthiourea as color developers that do not have a bisphenol structure or a phenol structure.
• the present inventor prepared a reversible color-changing composition using the color developer disclosed in Patent Documents 2 to 4 and evaluated the color development sensitivity and color erasability. did not show gender. That is, the object of the present invention is a reversible thermochromic composition having a non-phenolic structure with low load on the human body and the environment and achieving both excellent color development sensitivity and color erasability, and the reversible thermochromic composition. and a toy containing the reversible thermochromic composition.
• the gist of the present invention is as follows.
• a reversible thermochromic composition comprising a color developer containing a compound represented by the following formula (1), a leuco dye, and a color change temperature adjuster.
• a, a', b, A, A', and X are as follows.
• a is an integer selected from 0 to 5
• a' is an integer selected from 0 to 5
• b is 0 or 1
• a and A' are each independently an electron-withdrawing group or a hydrogen-bonding group
• Y is O or S;
• the benzene ring in the above formula (1) may have a substituent other than A or A'.
• At least one A or A' is a halogen atom, a nitrile group, a carboxyl group, an alkyl group having at least one fluoro group, and an optionally substituted oxycarbonyl group , a carbonyl group, an aminocarbonyl group, an aminosulfonyl group, a sulfinyl group, and a sulfonyl group, the reversible thermochromic composition according to [1].
• At least one A or A′ is an electron-withdrawing selected from a fluoro group, an alkyl group having at least one fluoro group, and an oxycarbonyl group optionally having a substituent
• at least one A or A' is a hydrogen bonding selected from a carboxyl group, an optionally substituted amino group, a carbonylamino group, a urea group, and a sulfonylamide group
• thermochromic composition according to any one of [1] to [5], wherein b is 1 in formula (1).
• a toy comprising the reversible thermochromic composition according to any one of [1] to [7] or the microcapsule pigment according to [8].
• thermochromic composition excellent in color developing sensitivity and decoloring property
• writing utensil containing the reversible thermochromic composition
• toy containing the reversible thermochromic composition
• a reversible thermochromic composition according to one embodiment of the present invention contains a color developer containing a compound represented by the following formula (1), a leuco dye, and a color change temperature adjuster.
• the compound represented by Formula (1) may be called "compound (1).”
• a, a', b, A, A', and X are as follows.
• a is an integer selected from 0 to 5
• a' is an integer selected from 0 to 5
• b is 0 or 1
• a and A' are each independently an electron-withdrawing group or a hydrogen-bonding group
• Y is O or S;
• the benzene ring in the above formula (1) may have a substituent other than A or A'.
• the reversible thermochromic composition according to the embodiment of the present invention exhibits a remarkable effect of being excellent in color developing sensitivity and decoloring property when heat is applied. It is presumed that the reversible thermochromic composition exhibits such excellent effects for the following reasons. That is, in the above formula (1), by having A and/or A′ and at least one A or A′ being an electron-withdrawing group or a hydrogen-bonding group, the crystallinity is appropriately reduced, It is believed that the sensitivity to color development is increased by improving the reactivity and compatibility with the leuco dye. In addition, it is believed that the improved compatibility with the discoloration temperature adjuster also improves the discoloration property.
• the developer contained in the reversible thermochromic composition according to this embodiment contains the compound represented by the above formula (1).
• a is an integer selected from 0 to 5, preferably 4 or less, more preferably 3 or less. It is thought that when a is large, the molecules become difficult to move, resulting in a decrease in color developing sensitivity and decoloring property.
• a' is an integer selected from 0 to 5, preferably 4 or less, more preferably 3 or less. When a' is large, it is thought that the molecules become difficult to move, resulting in a decrease in color developing sensitivity and decoloring property. However, the sum of a and a' is 1 or more.
• the crystallinity is moderately reduced, and the reactivity and compatibility with the leuco dye are improved, thereby increasing the color development sensitivity, while the color change agent and temperature control agent are compatible with each other.
• the decoloring property can be improved.
• b is 0 or 1, preferably 1.
• b 1
• the number of proton-donating hydrogen atoms contributing to the color development of the leuco formula increases, thereby increasing the reactivity with the leuco dye, thereby improving the color development sensitivity and the color development state in a temperature range lower than the color erasing temperature.
• a is preferably 1 or more. It is believed that when a is 1 or more, the reactivity with the leuco dye is enhanced.
• Y is preferably O because it has excellent reactivity with the leuco dye, and S is preferable because it has particularly excellent compatibility with the leuco dye.
• an electron-withdrawing group is a substituent having electron-withdrawing properties.
• An electron-withdrawing group as used herein is a substituent having a Hammett substituent constant (para-position, ⁇ p) of greater than zero. Hammett's substituent constant is described, for example, in Ryoji Noyori et al., "Graduate Lectures on Organic Chemistry", 1st Edition, Vol. I, Tokyo Kagaku Dojin Co., Ltd., June 1999, p.175.
• Electron-withdrawing groups include, but are not limited to, halogen atoms, nitrile groups, carboxyl groups, alkyl groups having at least one fluoro group, and optionally substituted oxycarbonyl groups, carbonyl groups, amino Carbonyl groups, aminosulfonyl groups, sulfinyl groups, and sulfonyl groups are included.
• a hydrogen-bonding group is a substituent having an active proton site or a substituent having a site capable of donating a hydrogen bond.
• the hydrogen-bonding group includes, but is not limited to, a hydrogen-bonding group selected from a carboxyl group, an optionally substituted amino group, a carbonylamino group, a urea group, or a sulfonylamide group.
• the benzene ring in formula (1) above may have a substituent other than A or A'.
• Substituents that may be present in addition to A or A′ are not limited, but may be substituted alkyl groups, aryl groups, heteroaryl groups, ether groups, thioether groups, carbonyloxy groups. or a sulfonyloxy group.
• the halogen atom includes a fluoro group, a chloro group, a bromo group, and an iodine group, and a fluoro group, a chloro group, or a bromo group is preferable because it increases the reactivity with the leuco dye, and improves the light resistance.
• a fluoro group or a chloro group is particularly preferred, and a fluoro group is more preferred, because it is easy to use.
• the alkyl group is preferably a linear or branched alkyl group having 1 to 22 carbon atoms which may have a substituent.
• the alkyl group enhances the compatibility with the discoloration temperature adjusting agent, and can improve the decoloring property. If the number of carbon atoms is too large, the melting point will be too low and the storage stability of the colored state will be low, or the color developability will be lowered. Therefore, the number of carbon atoms is preferably 12 or less, more preferably 6 or less, particularly preferably 4 It is below.
• Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, 1-ethyl pentyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, eicosyl group, A henicosyl group and a docosyl group can be mentioned.
• the alkyl group may have a substituent, and a preferable substituent is a halogen atom because the electron-withdrawing property increases the reactivity with the leuco dye.
• a fluoro group, a chloro group or a bromo group is preferred, and a fluoro group is particularly preferred.
• a and/or A' is particularly preferably an alkyl group having at least one fluoro group.
• a and/or A' has at least one fluoro group, its electron-withdrawing property can enhance color development sensitivity.
• a perfluoroalkyl group is preferable because a large number of fluoro groups enhances the electron-withdrawing property and the reactivity with the leuco dye.
• a trifluoromethyl group is particularly preferred because its strong electron-withdrawing property increases the reactivity with the leuco dye and imparts appropriate compatibility.
• the aryl group or heteroaryl group is an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an aromatic heterocyclic group having 2 to 20 carbon atoms which may have a substituent.
• aromatic hydrocarbon groups include phenyl, naphthyl, phenanthryl, biphenyl, anthryl, pyrenyl, fluorenyl, azulenyl, acenaphthenyl, fluoranthenyl, naphthacenyl, perylenyl, and pentacenyl groups. , a triphenylenyl group and a quarterphenyl group. Among these, a phenyl group or a naphthyl group is preferable.
• aromatic heterocyclic groups include pyridyl, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyrazinyl, pyrimidinyl, pyrazolyl, imidazolyl, benzothienyl, dibenzofuryl group, dibenzothienyl group, phenylcarbazolyl group, phenoxathienyl group, xanthenyl group, benzofuranyl group, thianthrenyl group, indolizinyl group, phenoxazinyl group, phenothiazinyl group, acridinyl group, phenanthridinyl group, phenanthroli Nil group, quinolyl group, isoquinolyl group, indolyl group, quinoxalinyl group and the like.
• pyridyl, pyrazinyl, pyrimidinyl, pyrazolyl, quinolyl, isoquinolyl, imidazolyl, acridinyl, phenanthridinyl, phenanthrolinyl, quinoxalinyl, dibenzofuryl, dibenzothienyl , phenylcarbazolyl, xanthenyl and phenoxazinyl groups are preferred.
• aromatic hydrocarbon groups are preferred, and among them, phenyl groups, because they tend to improve color development sensitivity and decoloring properties by improving compatibility with leuco dyes and discoloration temperature adjusting agents. is preferred.
• the ether group is represented by the following formula (2).
• R 1 is an optionally substituted alkyl group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic group having 2 to 10 carbon atoms. It is a heterocyclic group. Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group is preferred.
• * is a site
• Alkyl groups include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group and dodecyl group. If the chain length is too long, the compatibility with the discoloration temperature regulator becomes too high, and the stability of the coloring state tends to decrease.
• n-butyl group isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group or decyl group.
• aromatic hydrocarbon groups include phenyl, naphthyl, phenanthryl, biphenyl, anthryl, pyrenyl, fluorenyl, azulenyl, acenaphthenyl, fluoranthenyl, naphthacenyl, perylenyl, and pentacenyl groups. , a triphenylenyl group and a quarterphenyl group. Among these, a phenyl group or a naphthyl group is preferable.
• aromatic heterocyclic groups include pyridyl, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, oxadiazolyl, thiadiazolyl, pyrazinyl, pyrimidinyl, pyrazolyl, imidazolyl, benzothienyl, dibenzofuryl group, dibenzothienyl group, phenylcarbazolyl group, phenoxathienyl group, xanthenyl group, benzofuranyl group, thianthrenyl group, indolizinyl group, phenoxazinyl group, phenothiazinyl group, acridinyl group, phenanthridinyl group, phenanthroli Nil group, quinolyl group, isoquinolyl group, indolyl group, quinoxalinyl group and the like.
• pyridyl, pyrazinyl, pyrimidinyl, pyrazolyl, quinolyl, isoquinolyl, imidazolyl, acridinyl, phenanthridinyl, phenanthrolinyl, quinoxalinyl, dibenzofuryl, dibenzothienyl , a phenylcarbazolyl group, a xanthenyl group or a phenoxazinyl group are preferred.
• a thioether group is represented by the following formula (3).
• R 2 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• * is a site
• An oxycarbonyl group is represented by the following formula (4).
• R 3 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and/or A' is an oxycarbonyl group, its electron-withdrawing property can increase the reactivity with the leuco dye, and at the same time, improve the compatibility with the discoloration temperature adjusting agent to improve the decoloring property. can be made
• * is a site
• a carbonyloxy group is represented by the following formula (5).
• R 4 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• * is a site
• a carbonyl group is represented by the following formula (6).
• R 5 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and / or A' is a carbonyl group, its electron withdrawing property can increase the reactivity with the leuco dye, and at the same time, improve the compatibility with the discoloration temperature adjusting agent to improve the decoloring property. be able to.
• * is a site
• An amino group is represented by the following formula (7).
• R6 is the same as R1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and/or A' is an amino group, the number of hydrogen atoms that contribute to the reaction with the leuco dye is increased, and at the same time it is possible to increase the color development sensitivity and at the same time improve the compatibility with the discoloration temperature adjusting agent. can be improved to improve decolorization.
• R 6 is particularly preferably an aromatic hydrocarbon group or an aromatic heterocyclic group, particularly preferably an aromatic hydrocarbon group, because it can enhance the proton donating ability of A and/or A'.
• * is a site
• a carbonylamino group is represented by the following formula (8).
• R7 is the same as R1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and / or A ' is a carbonylamino group, the number of hydrogen atoms that contribute to the reaction with the leuco dye increases, and at the same time it is possible to increase the color sensitivity and compatibility with the color change temperature adjusting agent can be improved to improve decolorization.
• * is a site
• An aminocarbonyl group is represented by the following formula (9).
• R 8 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and / or A' is an aminocarbonyl group, the electron withdrawing property can increase the reactivity with the leuco dye, and at the same time, improve the compatibility with the discoloration temperature adjusting agent to improve the decoloring property.
• * is a site
• a urea group is represented by the following formula (10).
• R9 is the same as R1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and / or A' is a urea group, the number of hydrogen atoms that contribute to the reaction with the leuco dye increases, and at the same time it is possible to increase the color development sensitivity and at the same time improve the compatibility with the color change temperature adjusting agent. can be improved to improve decolorization.
• * is a site
• a sulfonylamide group is represented by the following formula (11).
• R 10 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and / or A ' is a sulfonylamide group, the number of hydrogen atoms that contribute to the reaction with the leuco dye increases, and at the same time it is possible to increase the color development sensitivity and compatibility with the discoloration temperature adjusting agent can be improved to improve decolorization.
• * is the site that binds to A.
• An aminosulfonyl group is represented by the following formula (12).
• R 11 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and/or A' is an aminosulfonyl group, its electron-withdrawing property can increase the reactivity with the leuco dye, and at the same time, improve the compatibility with the discoloration temperature adjusting agent to improve the decoloring property.
• * is the site that binds to A.
• a sulfinyl group is represented by the following formula (13).
• R 12 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and/or A' is a sulfinyl group, its electron-withdrawing property can increase the reactivity with the leuco dye, and at the same time, improve the compatibility with the discoloration temperature adjusting agent to improve the decoloring property. be able to.
• * is the site that binds to A.
• a sulfonyl group is represented by the following formula (14).
• R 13 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• a and/or A' is a sulfonyl group, its electron-withdrawing property can increase the reactivity with the leuco dye, and at the same time, improve the compatibility with the discoloration temperature adjusting agent to improve the decoloring property. be able to.
• * is the site that binds to A.
• a sulfonyloxy group is represented by the following formula (15).
• R 14 is the same as R 1 .
• Alkyl groups are preferred because lowering the crystallinity increases compatibility with the discoloration temperature adjuster and improves discoloration, and improves compatibility with the discoloration temperature adjuster to improve discoloration. Therefore, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable.
• * is the site that binds to A.
• a and A' are an alkyl group, an aryl group, a heteroaryl group, an ether group, a thioether group, an oxycarbonyl group, a carbonyloxy group, a carbonyl group, an amino group, a carbonylamino group, and an aminocarbonyl group.
• a urea group, a sulfonylamide group, an aminosulfonyl group, a sulfinyl group, a sulfonyl group, and a sulfonyloxy group may further have an arbitrary substituent.
• At least one A or A' is an electron-withdrawing group selected from a fluoro group, an alkyl group having at least one fluoro group, and an oxycarbonyl group optionally having a substituent, or A hydrogen-bonding group selected from a carboxyl group, a carbonylamino group, a urea group and a sulfonylamido group is preferred.
• the reactivity with the leuco dye is increased, the color development sensitivity is easily improved, and compatibility with the discoloration temperature adjusting agent is improved. can be improved.
• a fluoro group or an alkyl group having at least one fluoro group is preferable because it is easy to achieve both improvement in reactivity with the leuco dye due to its strong electron-withdrawing property and improvement in compatibility with the leuco dye.
• Methyl groups are preferred.
• At least one A or A' is preferably bound to the * position described in formula (1).
• the steric hindrance and electronic repulsion moderately reduce the stability of the colored state reacted with the leuco dye. Therefore, it is considered that the decoloring property when heat is applied can be effectively improved.
• At least one A or A' bonded to the * position is preferably a hydrogen-bonding group. Since the hydrogen-bonding group is bonded to the * position, intramolecular hydrogen bonding is facilitated between adjacent NH groups, and intermolecular hydrogen bonding is weakened, so crystallinity can be suppressed and the melting point is high. It can suppress excessive formation and improve compatibility with leuco dyes. At the same time, it is thought that since it can participate in the reaction with the leuco dye, the sensitivity to color development can be effectively enhanced.
• At least one A or A' is preferably a hydrogen-bonding group bonded to the * position described in formula (1).
• a is 1 or more, at least one A is bonded to the * position described in formula (1), and the A bonded to the * position is more preferably a hydrogen bonding group. preferable.
• the compound of the above formula (1) is obtained by a known method (e.g., Japanese Patent No. 2679459, Japanese Patent No. 4601174, Japanese Patent No. 5887423, literature (Journal of American Chemical Society 2016, Vol. 138 (No. 40), pp. 13314-13325) , and literature (Org. Lett., 2016, 18, 3726-3729)) or a modified method thereof.
• a known method e.g., Japanese Patent No. 2679459, Japanese Patent No. 4601174, Japanese Patent No. 5887423, literature (Journal of American Chemical Society 2016, Vol. 138 (No. 40), pp. 13314-13325) , and literature (Org. Lett., 2016, 18, 3726-3729)
• a reversible thermochromic composition according to an embodiment of the present invention comprises a leuco dye.
• Leuco dyes are generally basic, and all known leuco dyes can be used. Specific examples of leuco dyes include conventionally known diphenylmethanephthalides, phenylindolylphthalides, indolylphthalides, diphenylmethaneazaphthalides, phenylindolylazaphthalides, fluoranes, and stilinoquinolines. , diazarhodamine lactones and the like. These leuco dyes (leuco dye precursors) may be used alone or in combination of two or more. Also, the developer is preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, per 1 part by weight of the leuco dye.
• leuco dyes are given below. 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)phthalide, 3,3 -bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3-[2-ethoxy-4-( N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3,6-diphenylaminofluorane, 3,6-dimethoxyfluorane, 3,6-di -n-butoxyfluorane, 2-methyl-6-(N-ethyl-Np-tolylamino)fluorane, 3-chloro
• the reversible thermochromic composition of the present embodiment contains a color change temperature adjusting agent.
• a discoloration temperature adjusting agent is a substance that reversibly causes an electron transfer reaction between a color developer and a leuco dye.
• Known discoloration temperature regulators can be used. Specifically, chain hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, ethers, acids Amides can be mentioned. Among these, those having 8 or more carbon atoms are preferred, and those having 10 or more carbon atoms are more preferred. Moreover, 30 or less carbon atoms are preferable.
• ester examples include compounds represented by the following formulas (16) to (19) (hereinafter sometimes referred to as compounds (16) to (19)).
• X 1 is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom;
• m is independently an integer of 1 to 3;
• n is 1; is an integer between ⁇ 8.
• Compound (16) includes a diester of malonic acid and 2-[4-(4-chlorobenzyloxy)phenyl)]ethanol, a diester of succinic acid and 2-(4-benzyloxyphenyl)ethanol, a diester of succinic acid and 2-[4-(3-methylbenzyloxy)phenyl)]ethanol diester, glutaric acid and 2-(4-benzyloxyphenyl)ethanol diester, glutaric acid and 2-[4-(4-chlorobenzyl oxy)phenyl)]ethanol, diesters of adipic acid with 2-(4-benzyloxyphenyl)ethanol, diesters of pimelic acid with 2-(4-benzyloxyphenyl)ethanol, suberic acid with 2-( 4-benzyloxyphenyl)ethanol, diester of suberic acid with 2-[4-(3-methylbenzyloxy)phenyl)]ethanol, suberic acid with 2-[4-(4-chlorobenzyloxy)
• R 15 is a hydrogen atom or a methyl group
• r is an integer of 0 to 2
• either one of X 2 and X 3 is —(CH 2 ) n OCOR 16 or —(CH 2 ) n COOR 16 , the other is a hydrogen atom
• n is an integer of 0 to 2
• R 16 is an alkyl or alkenyl group having 4 or more carbon atoms
• Y 2 and Y 3 are each independently hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom
• p and q are each independently an integer of 1 to 3.
• R 15 when R 15 is a hydrogen atom, it is preferable because a reversible thermochromic composition having a wider hysteresis width can be obtained, and R 15 is a hydrogen atom and m is 0. It is more suitable.
• R 16 is an alkyl or alkenyl group having 7 or more carbon atoms, preferably an alkyl group having 9 to 24 carbon atoms, more preferably an alkyl group having 9 to 20 carbon atoms.
• R 17 is an alkyl or alkenyl group having 7 or more carbon atoms
• s and t are each independently an integer of 1 to 3
• X 4 and Y 4 are each independently hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.
• Compound (19) includes 1,1-diphenylmethyl octanoate, 1,1-diphenylmethyl nonanoate, 1,1-diphenylmethyl decanoate, 1,1-diphenylmethyl undecanoate, and 1,1-diphenyl dodecanoate. methyl, 1,1-diphenylmethyl tridecanoate, 1,1-diphenylmethyl tetradecanoate, 1,1-diphenylmethyl pentadecanoate, 1,1-diphenylmethyl hexadecanoate, 1,1-diphenylmethyl heptadecanoate, 1 octadecanoate , 1-diphenylmethyl.
• These discoloration temperature adjusting agents may be used alone or in combination of two or more.
• the discoloration temperature adjuster is preferably used in an amount of 1 to 800 parts by weight, more preferably 5 to 200 parts by weight, per 1 part by weight of the leuco dye.
• the coloring state caused by the electron transfer reaction between the leuco dye and the developer can be changed to a decoloring state.
• the reversible thermochromic composition according to the present embodiment comprises a color developer other than compound (1) (hereinafter sometimes referred to as "other color developer"), a sensitizer, a stabilizer, a cross-linking agent, a pigment, It may contain a lubricant or the like.
• the reversible thermochromic composition may contain other color developers as long as the effects of the present invention are not impaired.
• color developers all known ones can be used, and although they are not particularly limited, electron-accepting color developers are preferred.
• Other color developers may be used singly or in combination of two or more.
• the amount used is preferably 1 to 5000 parts by weight, more preferably 5 parts by weight, per 100 parts by weight of the color developer containing the compound represented by formula (1). It is up to 1000 parts by weight, more preferably 10 to 500 parts by weight.
• color developers include monophenols and polyphenols. These may further have alkyl groups, aryl groups, acyl groups, alkoxycarbonyl groups, carboxy groups and their esters, amide groups, and halogen groups as substituents. Further, bis-type or tris-type phenol, phenol-aldehyde condensed resin and the like are included. It may also be a metal salt of a compound having a phenolic hydroxyl group.
• R 18 is an alkyl group having 1 to 8 carbon atoms.
• Examples of the compound having at least three or more benzene rings and having a phenolic hydroxyl group with a molecular weight of 250 or more include 4,4′,4′′-methylidenetrisphenol, 2,6-bis[(2-hydroxy -5-methylphenol)methyl]-4-methylphenol, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 4,4' , 4′′-ethylidene tris[2-methylphenol], 4,4′-[(2-hydroxyphenyl)methylene]bis[2,3,6-triphenylphenol], 2,2-methylenebis[6-[( 2-hydroxy-5-methylphenyl)methyl]-4-methylphenol], 2,4,6-tris(4-hydroxyphenylmethyl)1,3-benzenediol, 4,4′,4′′-ethylidenetrisphenol , 4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylphenol
• Examples of the compound having a phenolic hydroxyl group represented by the formula (20) include bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4-hydroxyphenyl), bis(3-ethyl- 4-hydroxyphenyl)sulfide, bis(3,5-diethyl-4-hydroxyphenyl)sulfide, bis(3-propyl-4-hydroxyphenyl)sulfide, bis(3,5-dipropyl-4-hydroxyphenyl)sulfide, Bis (3-t-butyl-4-hydroxyphenyl) sulfide, bis (3,5-t-butyl-4-hydroxyphenyl) sulfide, bis (3-pentyl-4-hydroxyphenyl) sulfide, bis (3-hexyl) -4-hydroxyphenyl)sulfide, bis(3-heptyl-4-hydroxyphenyl)sulfide, bis(5-octyl-2-hydroxypheny
• the compound having a phenolic hydroxyl group can exhibit the most effective thermochromic properties, but other color developers include aromatic carboxylic acids and aliphatic carboxylic acids having 2 to 5 carbon atoms, carboxylic acid metal salts, Compounds selected from acidic phosphates and metal salts thereof, 1,2,3-triazoles and derivatives thereof, and the like may also be used.
• the reversible thermochromic composition according to the embodiment of the present invention may be used as a microcapsule pigment by being encapsulated in microcapsules.
• their functions do not deteriorate even when they come into contact with chemically active substances such as acidic substances, basic substances, peroxides, or other solvent components.
• heat stability can be maintained, and the composition of the reversible thermochromic composition can be kept the same under various conditions of use, and the same effect can be obtained.
• microcapsule pigment are not particularly limited, and reference can be made, for example, to Japanese Patent No. 6851787.
• known interfacial polymerization method, in situ polymerization method, in-liquid curing coating method, phase separation method from aqueous solution, phase separation method from organic solvent, melting dispersion cooling method, air suspension coating method, spray It can be produced by a drying method or the like.
• the average particle size of the microcapsule pigment is preferably 0.1 to 100 ⁇ m, more preferably 3 to 30 ⁇ m.
• the particle size and particle size distribution are measured using a laser diffraction/scattering particle size distribution analyzer [manufactured by Horiba, Ltd.; LA-300]. It can be calculated on a volume basis.
• the reversible thermochromic composition and microcapsule pigment according to the embodiment of the present invention can be used, for example, in printing inks, writing inks and paints.
• printing inks writing inks and paints.
• screen printing offset printing, gravure printing, coater, tampo printing, printing means such as transfer, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc.
• coating means a reversible thermochromic layer can be formed on any support or dispersed in the support.
• a writing instrument containing the above reversible thermochromic composition or microcapsule pigment may also be used.
• the writing instrument includes a barrel housing a reversible thermochromic composition or microcapsule pigment and a pen body for leading out the reversible thermochromic composition or microcapsule pigment in the barrel.
• Pen bodies include marking pen bodies, ballpoint pen bodies, brush pen bodies, and the like. Marking pen bodies include marking tips such as fiber tips, felt tips, and plastic tips. Ball-point pen bodies include ball-point pen tips.
• a toy containing the reversible thermochromic composition or microcapsule pigment may also be used.
• the above toys include dolls or animal-shaped toys, hair for dolls or animal-shaped toys, doll houses and furniture, clothes, hats, bags, shoes and other doll accessories, accessory toys, stuffed animals, drawing toys, Picture books for toys, puzzle toys such as jigsaw puzzles, block toys, block toys, clay toys, fluid toys, spinning tops, kites, musical instrument toys, cooking toys, gun toys, capture toys, background toys, vehicles, animals, plants, buildings, A toy imitating food or the like can be exemplified.
• thermochromic composition or microcapsule pigment there is no particular limitation on the mode containing the reversible thermochromic composition or microcapsule pigment.
• a reversible thermochromic composition or microcapsule pigment can be dispersed therein.
• the method of using the toy is not particularly limited, but for example, the reversible thermochromic composition can be discolored by contacting the toy with warm water or cold water.
• the melting point was 172-173°C.
• the chemical shift ( ⁇ ppm) in the proton NMR spectrum (400 MHz) measured in heavy DMSO solvent was as follows. ⁇ : 7.32-7.34 (m, 2H), 7.53-7.55 (m, 2H), 7.65-7.71 (m, 2H), 7.92 (d, 1H), 8.03 (s, 1H), 8.17 (s, 1H)
• a target product was obtained by the same operation.
• the melting point was 167-168°C.
• ⁇ Comparative Example 1 1 part of 2'-(2-chloroanilino)-6'-(dibutylamino)fluorane as a leuco dye, 4 parts of 1,3-diphenylurea (purchased from Tokyo Kasei Co., Ltd.) as a color developer, and caprin as a discoloration temperature adjusting agent A reversible thermochromic composition was obtained by mixing 25 parts of 4-benzyloxyphenylethyl acid.
• thermochromic composition was obtained in the same manner as in Comparative Example 1, except that 4 parts of 1,3-diphenylthiourea (purchased from Tokyo Kasei Co., Ltd.) was used as a developer.
• Example 1 1 part of 2'-(2-chloroanilino)-6'-(dibutylamino)fluorane as a leuco dye, 4 parts of 1,3-di(3-(trifluoromethyl)phenyl)urea as a developer, color change temperature adjustment A reversible thermochromic composition was obtained by mixing 25 parts of 4-benzyloxyphenylethyl caprate as an agent.
• Example 2 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 2 was used as the developer.
• Example 3 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 3 was used as the developer.
• thermochromic composition was prepared in the same manner as in Example 1, except that 4 parts of 1,3-bis[4-(trifluoromethyl)phenyl]thiourea (purchased from Tokyo Kasei Co., Ltd.) was used as a color developer. Obtained.
• Example 5 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 4 was used as the developer.
• Example 6 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 5 was used as the developer.
• Example 7 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 6 was used as the developer.
• Example 8 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 7 was used as the developer.
• Example 9 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 8 was used as the developer.
• Example 10 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 9 was used as the developer.
• Example 11 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 10 was used as the developer.
• Example 12 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 11 was used as the developer.
• Example 13 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 12 was used as the developer.
• Example 14 A reversible thermochromic composition was obtained in the same manner as in Example 1, except that the compound obtained in Synthesis Example 13 was used as the developer.
• the compounds of Examples 1 to 14 have at least one electron-withdrawing group or hydrogen-bonding group on the benzene ring adjacent to the NH group of the urea, thiourea, and sulfamide structures.
• the reactivity between the NH group and the leuco dye is increased, and sufficient color development sensitivity is exhibited.
• the reactivity with the leuco dye is not too strong, and the releasability (that is, decolorization property) is good.
• the compounds described in the present application can be used as color developers for non-phenolic reversible thermochromic compositions having both excellent color-developing sensitivity and decoloring properties. Moreover, as is clear from Table 2, when the discoloration temperature adjusting agent is not contained, it can be seen that the discoloration property is not exhibited.

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