Color-changing liquid composition and color-changing laminate including the same

Abstract

To provide a color-changing liquid composition that is applicable to a substrate composed of a 4-methyl-1-pentene polymer and can form a color-changing layer that undergoes color change due to heat and light, offers superior adhesion to the substrate, and exhibits superior followability to deformation, and to provide a color-changing laminate that protects a color-changing layer from peeling and cracking, even when its shape is deformed, and can retain the function of allowing the entire color-changing layer to change color uniformly.SOLUTION: A color-changing liquid composition is used for a substrate that is composed of a 4-methyl-1-pentene polymer (A), wherein there is at least one temperature within the range of 10-100°C that indicates a maximum loss tangent determined by dynamic viscoelasticity at a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, and the maximum loss tangent is 0.5-3.5. The color-changing liquid composition comprises a color-changing material, and a vehicle comprising at least a 4-methyl-1-pentene polymer (B) and a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a color-changing liquid composition and a color-changing laminate using the same. More specifically, the present invention relates to a color-changing liquid composition capable of forming a color-changing layer that has excellent adhesion to a substrate and good followability to deformations such as expansion, contraction, and bending, and a color-changing laminate having a color-changing layer made of the liquid composition provided on a substrate. [Background technology]

[0002] Conventionally, an elastomer laminate has been disclosed in which a colored layer is laminated on the surface of a support made of a molded product of a specific block copolymer elastomer. The colored layer contains a microcapsule pigment that encapsulates a reversible thermochromic composition composed of three components: an electron-donating color-forming organic compound, an electron-accepting compound, and an organic compound medium that reversibly induces a color reaction, in a block copolymer elastomer having the same composition as the support (see, for example, Patent Document 1). The elastomer laminate has high elongation and strength, allowing it to be deformed, and exhibits reversible color change due to heat. Furthermore, since the colored layer (reversible thermochromic layer) does not peel off even after stretching the laminate, it can be used in a variety of fields, such as toys.

[0003] As a support that can be deformed in shape like the support made of the above-mentioned elastomer molded product, a sheet made of a 4-methyl-1-pentene polymer having 4-methyl-1-pentene as a constituent monomer has been disclosed (see, for example, Patent Document 2). The above sheet has flexibility within a specific temperature range, and is capable of deforming and retaining the deformed shape. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-160989 [Patent Document 2] International Publication No. 2018 / 143411 Brochure Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention is applicable to substrates composed of the above-mentioned 4-methyl-1-pentene polymer. As a result of investigations into color-changing liquid compositions that change color in response to heat or light, the present inventors have discovered a color-changing liquid composition that, by using a vehicle containing a specific compound, can form a color-changing layer that has excellent adhesion to substrates and good followability to deformations such as expansion, contraction, and bending, without affecting the color-changing properties of the color-changing material. [Means for solving the problem]

[0006] The present invention provides A color-changing liquid composition for use on a substrate, which is composed of a 4-methyl-1-pentene polymer (A), and which has at least one temperature in the range of 10 to 100°C at which it exhibits a maximum value of loss tangent as determined by dynamic viscoelasticity measurement under conditions of a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, and which has a maximum value of loss tangent of 0.5 to 3.5, a color-changing material; a vehicle containing at least a 4-methyl-1-pentene polymer (B) and a solvent; The present invention requires a color-changing liquid composition comprising: Further requirements are that the 4-methyl-1-pentene polymer (B) comprises a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene, that the vehicle further comprises a styrene-based oligomer, that the color-changing material is a reversible thermochromic material or a reversible photochromic material, that the reversible thermochromic material is a reversible thermochromic microcapsule pigment encapsulating a reversible thermochromic composition comprising at least (a) an electron-donating color-forming organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color-changing reactions of (a) and (b), and that the liquid composition is selected from the group consisting of printing ink, paint, inkjet ink, and ultraviolet-curable ink. The present invention also requires a color-changing laminate comprising a substrate that is made of a 4-methyl-1-pentene polymer (A), that has at least one temperature in the range of 10 to 100°C at which the loss tangent, as determined by dynamic viscoelasticity measurement under conditions of a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, exhibits a maximum value of the loss tangent as determined at a temperature of 0.5 to 3.5, and that has a color-changing layer formed of the liquid composition on the substrate. Furthermore, the present invention requires that an adhesion-suppressing layer be provided on the surface of the substrate opposite to the surface on which the discoloration layer is provided, and that the adhesion-suppressing layer be made of a liquid composition containing at least an adhesion suppressant, the 4-methyl-1-pentene polymer (B), and the solvent. Furthermore, the present invention provides a color-changing and deformable article using the laminate, and the color-changing and deformable article is a toy. [Effects of the Invention]

[0007] The present invention provides a color-changing liquid composition that can be applied to a substrate made of a 4-methyl-1-pentene polymer, and that can form a color-changing layer that changes color in response to heat or light, has excellent adhesion to the substrate, and has good followability to deformations such as expansion, contraction, bending, etc. Furthermore, a color-changing laminate in which a color-changing layer formed from this color-changing liquid composition is provided on a substrate does not peel off or break even when the shape is deformed, and the entire color-changing layer continues to maintain its function of changing color uniformly, thereby providing a color-changing laminate that can be applied to a variety of fields that require flexibility in deformation and color-changing properties, such as the fields of toys, industry, stationery, decoration, and design. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a graph illustrating the hysteresis characteristics in the color density-temperature curve of a reversibly thermochromic composition that is heat-discolorable. [Figure 2] 1 is a graph illustrating the hysteresis characteristics in the color density-temperature curve of a heat-discolorable, reversible thermochromic composition having color memory properties. [Figure 3] 1 is a graph illustrating the hysteresis characteristics in the color density-temperature curve of a reversibly thermochromic composition that develops color over time. [Figure 4] 1 is an example of a color-changing laminate using a liquid composition according to the present invention. [Figure 5] 10 is another example of a color-changing laminate using a liquid composition according to the present invention. [Figure 6] This is an example of application of a color-changing laminate using the liquid composition of the present invention. [Figure 7] This is another application example of the color-changing laminate using the liquid composition of the present invention. [Figure 8] This is another application example of the color-changing laminate using the liquid composition of the present invention. [Figure 9] 9 is a cross-sectional view taken along line XX in FIG. 8. DETAILED DESCRIPTION OF THE INVENTION

[0009] The color-changing liquid composition according to the present invention (hereinafter sometimes referred to as "liquid composition") is composed of a 4-methyl-1-pentene polymer (A) and is used for a substrate that satisfies the requirement (i) described below. The substrate for which the liquid composition according to the present invention is used will be described below.

[0010] The substrate made of 4-methyl-1-pentene polymer (A) for which the liquid composition according to the present invention is used (i) has at least one temperature in the range of 10 to 100°C at which the loss tangent shows a maximum value as determined by dynamic viscoelasticity measurement under conditions of a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, and the maximum value of the loss tangent is 0.5 to 3.5.

[0011] The temperature at which the loss tangent obtained by dynamic viscoelasticity measurement of a substrate that satisfies the above condition (i) shows a maximum value is the so-called glass transition temperature (Tg). Polymers such as 4-methyl-1-pentene polymers generally have a high elastic modulus and exhibit rigid properties in the temperature range below the glass transition temperature, and a low elastic modulus and exhibit viscous properties in the temperature range above the glass transition temperature. In other words, the substrate has temperature sensitivity, in which the elastic modulus changes with temperature, and its flexibility changes across the glass transition temperature.

[0012] The substrate's modulus of elasticity decreases with increasing temperature and it no longer exhibits rigid properties. That is, the substrate exhibits flexibility with increasing temperature, and can be deformed into any shape by applying external stress (hereinafter sometimes referred to as "external force") in a temperature range above the glass transition temperature, and thus has shape deformability. Furthermore, after the substrate has been deformed into any shape by applying external force, by cooling it to a temperature range below the glass transition temperature while the external force is still being applied, the modulus of elasticity increases again and it exhibits rigid properties. That is, the substrate loses flexibility with decreasing temperature and can retain the deformed shape even after the external force is removed, and therefore has shape retention.

[0013] When the temperature at which the loss tangent of the substrate made of the 4-methyl-1-pentene polymer (A) shows a maximum value falls within a specific range, and the maximum value of the loss tangent falls within a specific range, the substrate can have an excellent balance of temperature sensitivity, shape deformability, and shape retention.

[0014] The loss tangent (tanδ) determined by dynamic viscoelasticity measurement can be measured, for example, by cutting a substrate into a test piece measuring 30 mm in length and 15 mm in width, using a dynamic viscoelasticity measuring device (DMA) or a rheometer under the following conditions: chuck distance 20 mm, frequency 1.59 Hz, strain amount 0.1%, heating rate 4°C / min, and tension mode.

[0015] The temperature at which the loss tangent shows a maximum value is preferably at least one in the range of 10 to 80°C, more preferably at least one in the range of 10 to 60°C, even more preferably at least one in the range of 10 to 50°C, and particularly preferably at least one in the range of 15 to 40°C. The maximum value of the loss tangent is preferably 0.8 or more, more preferably 1.0 or more, and even more preferably 1.2 or more. The maximum value of the loss tangent is preferably 3.0 or less, and more preferably 2.8 or less. By ensuring that the temperature at which the loss tangent reaches its maximum value and the maximum value of the loss tangent satisfy these ranges, the substrate's temperature sensitivity, shape deformability, and shape retention performance balance can be improved. Here, the larger the maximum value of the loss tangent, the stronger the viscous properties of the substrate, meaning that more energy is absorbed when the substrate deforms. When the viscous properties of the substrate are stronger, more of the force (mechanical energy) applied when deforming the substrate is converted into heat (thermal energy) and dissipated, and the rate at which the substrate returns to its original shape when the force applied to the substrate is removed slows. Therefore, it is believed that the substrate's temperature sensitivity, shape deformability, and shape retention performance balance can be achieved at the same time.

[0016] When the temperature at which the loss tangent shows a maximum value is between 15 and 40°C (preferably between 20 and 40°C, more preferably between 25 and 38°C), the substrate exhibits flexibility at ambient temperatures (e.g., 25°C). Furthermore, because the flexibility changes at temperatures close to human body temperature, the substrate can be easily deformed, for example, by applying an external force to the substrate with a human hand. The substrate deformed by the external force retains the deformed shape for a certain period of time and then gradually returns to its original shape.

[0017] The 4-methyl-1-pentene polymer (A) (hereinafter sometimes referred to as "polymer (A)") is not particularly limited, and examples thereof include a 4-methyl-1-pentene-α-olefin copolymer (a) (hereinafter sometimes referred to as "copolymer (a)") containing a structural unit (a1) derived from 4-methyl-1-pentene and a structural unit (a2) derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene. Here, unless otherwise specified, "α-olefin having 2 to 20 carbon atoms" does not include 4-methyl-1-pentene. 4-Methyl-1-pentene·α-olefin copolymer can achieve a high degree of balance between the temperature sensitivity, shape deformability, and shape retention properties of the substrate, and is therefore suitable as a material for constituting the substrate to which the liquid composition of the present invention is applied.

[0018] In the 4-methyl-1-pentene·α-olefin copolymer (a), the blending ratio of the structural unit (a1) and the structural unit (a2) is not particularly limited. In order to improve the temperature sensitivity, shape deformability, and shape retention of the substrate, it is preferable that the structural unit (a1) accounts for 10 to 90 mol % and the structural unit (a2) accounts for 10 to 90 mol %, assuming the total of the structural unit (a1) and the structural unit (a2) to be 100 mol %. In order to achieve even better temperature sensitivity, shape deformability, and shape retention of the substrate, when the total of the structural units (a1) and (a2) is taken as 100 mol%, it is more preferable that the structural units (a1) account for 30 to 90 mol% and the structural units (a2) account for 10 to 70 mol%, it is even more preferable that the structural units (a1) account for 50 to 90 mol% and the structural units (a2) account for 10 to 50 mol%, it is particularly preferable that the structural units (a1) account for 60 to 90 mol% and the structural units (a2) account for 10 to 40 mol%, and it is most preferable that the structural units (a1) account for 65 to 90 mol% and the structural units (a2) account for 10 to 35 mol%.

[0019] Examples of the α-olefin having 2 to 20 carbon atoms used in the 4-methyl-1-pentene·α-olefin copolymer (a) include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and functionalized vinyl compounds.

[0020] The linear α-olefin preferably has 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 or 3 carbon atoms. Examples of linear α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferred, and ethylene or propylene is more preferred.

[0021] The branched α-olefin preferably has 5 to 20 carbon atoms, and more preferably 5 to 15 carbon atoms. Examples of branched α-olefins include 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl-1-pentene.

[0022] The cyclic olefin has 3 to 20 carbon atoms, and preferably 5 to 15 carbon atoms. Examples of cyclic olefins include cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.

[0023] Examples of aromatic vinyl compounds include mono- or polyalkylstyrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene.

[0024] The conjugated diene has 4 to 20 carbon atoms, and preferably 4 to 10 carbon atoms. Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, and 1,3-octadiene.

[0025] Examples of functionalized vinyl compounds include hydroxyl group-containing olefins such as linear or branched α-olefins having 2 to 20 carbon atoms and having terminal hydroxyl groups; halogenated olefins such as linear or branched halogenated α-olefins having 2 to 20 carbon atoms and having an atom of Group 17 of the periodic table; (meth)acrylic acid, propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, and 10-undecenoic acid. Examples of the unsaturated carboxylic acid include unsaturated carboxylic acids such as benzoic acid; unsaturated amines such as allylamine, 5-hexenamine, and 6-heptenamine; succinic anhydrides such as (2,7-octadienyl)succinic anhydride and pentapropenylsuccinic anhydride; unsaturated carboxylic acid anhydrides such as anhydrides obtained from the above unsaturated carboxylic acids; unsaturated carboxylic acid halides such as halides obtained from the above unsaturated carboxylic acids; unsaturated epoxy compounds; and ethylenically unsaturated silane compounds.

[0026] The α-olefins can be used alone or in combination of two or more.

[0027] The α-olefin is preferably a linear α-olefin having 2 to 10 carbon atoms. Ethylene or propylene is more preferred, and propylene is even more preferred, as this allows for a better balance of the temperature sensitivity, shape deformability, and shape retention of the substrate.

[0028] The blending ratio of 4-methyl-1-pentene and α-olefin in the 4-methyl-1-pentene-α-olefin copolymer (a) is, for example, 13 It can be measured by C NMR.

[0029] The 4-methyl-1-pentene·α-olefin copolymer (a) preferably satisfies the requirements (ii) and (iii) described below.

[0030] The 4-methyl-1-pentene-α-olefin copolymer (a) (ii) has an intrinsic viscosity [η] in decalin at 135°C of preferably 0.01 to 5.0 dL / g, more preferably 0.1 to 4.0 dL / g, even more preferably 0.5 to 3.0 dL / g, and particularly preferably 1.0 to 2.8 dL / g. By having the intrinsic viscosity [η] within the above range, the substrate can achieve a good balance of temperature sensitivity, shape deformability, and shape retention. The intrinsic viscosity [η] can be adjusted by the amount of hydrogen added in the polymerization step when preparing the copolymer (a). The intrinsic viscosity [η] is a value measured at 135° C. using decalin, and can be measured by the following method.

[0031] (Method for measuring intrinsic viscosity) Approximately 20 mg of 1,4-methyl-1-pentene·α-olefin copolymer was dissolved in 15 ml of decalin to prepare a decalin solution, and the specific viscosity (η sp ) is measured. 2. Add 5 ml of decalin to the decalin solution to dilute it, and measure the specific viscosity (η sp ) is measured in the same manner. The increase in viscosity per unit concentration (C) of 3.4-methyl-1-pentene·α-olefin copolymer, i.e., the reduced viscosity (η red =η sp / C). 4. Plot the relationship between concentration and reduced viscosity, and calculate the intrinsic viscosity [η] from the intercept when the concentration (C) is extrapolated to 0. Alternatively, calculate the intrinsic viscosity [η] using the following formula (I).

number

[0032] The 4-methyl-1-pentene-α-olefin copolymer (a) preferably has a density of 0.81 to 0.85 g / cm as measured by ASTM D 1505 (water displacement method). 3 , more preferably 0.82 to 0.85 g / cm 3 , and more preferably 0.83 to 0.85 g / cm 3 The density can be adjusted by the type of α-olefin having 2 to 20 carbon atoms or the blending ratio of 4-methyl-1-pentene and α-olefin having 2 to 20 carbon atoms in the copolymer (a).

[0033] The method for producing the 4-methyl-1-pentene-α-olefin copolymer (a) is not particularly limited, and it can be produced by various methods. For example, it can be produced by polymerizing 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms in the presence of a polymerization catalyst.

[0034] If necessary, various additives may also be added to the base material. Examples of additives include foaming agents, heat stabilizers, antioxidants, ultraviolet absorbers, dyes, pigments, antistatic agents, copper inhibitors, flame retardants, neutralizing agents, plasticizers, nucleating agents, weather stabilizers, light stabilizers, antioxidants, fatty acid metal salts, softeners, dispersants, colorants, lubricants, natural oils, synthetic oils, waxes, etc. Among these, the type or amount of plasticizer, softener, natural oil, or synthetic oil can be used to adjust the temperature at which the loss tangent shows its maximum value and the maximum value of the loss tangent.

[0035] The shape of the substrate is not particularly limited, but a sheet shape is preferred. When the substrate is in the form of a sheet, the thickness is preferably in the range of 0.1 to 30 mm, more preferably 0.2 to 20 mm, and even more preferably 0.3 to 12 mm. By having the thickness within the above range, the substrate is lightweight and easy to handle, has a good appearance and feel, and can achieve a good balance of performance such as temperature sensitivity, shape deformability, shape retention, moldability, and moisture resistance.

[0036] The method for producing the sheet-like substrate is not particularly limited. For example, the substrate can be produced by molding a resin composition containing the 4-methyl-1-pentene polymer (A) by a conventional molding method.

[0037] Examples of molding methods include general-purpose extrusion molding, inflation molding, calendering molding, etc. Among these, extrusion molding is preferred. When the substrate has a multi-layer structure, molding means such as co-extrusion molding, which is extrusion molding using a multi-die, or various lamination methods can be used. When the substrate is a foam, the foam can be produced by, for example, foam-molding a resin composition containing a foaming agent into a specific shape. The foam produced in this manner has excellent tactile properties, such as a pleasant feel to the touch.

[0038] The liquid composition according to the present invention comprises a color-changing material and a vehicle, and the vehicle contains at least a 4-methyl-1-pentene polymer (B) and a solvent. Each material constituting the liquid composition according to the present invention will be described below.

[0039] The color-changing materials applicable to the present invention include thermochromic materials that change color with temperature changes and photochromic materials that change color with light irradiation, and these color changes may be reversible or irreversible. Since they can repeatedly exhibit color changes with temperature changes or light irradiation, reversible thermochromic materials and reversible photochromic materials are suitable as color-changing materials.

[0040] Examples of reversible thermochromic materials include reversible thermochromic compositions comprising at least (i) an electron-donating color-forming organic compound, (ii) an electron-accepting compound, and (iii) a reaction medium that determines the temperature at which the color-forming reaction of components (i) and (ii) occurs.

[0041] Examples of reversible thermochromic compositions include those described in Japanese Patent Publication Nos. 51-44706, 51-44707, and 1-29398, which have a relatively small hysteresis width (ΔH) (ΔH = 1 to 7°C). "Thermal decolorization" refers to a composition that decolorizes upon heating and develops color upon cooling. These reversible thermochromic compositions undergo color changes around a specific temperature (the color change point). They exhibit a decolorized state above the high-temperature color change point and a colored state below the low-temperature color change point. Only one of these two states exists at room temperature. The other state is maintained while the heat or cold required to achieve that state is applied, but returns to the normal state once the heat or cold is removed (see Figure 1).

[0042] The reversible thermochromic composition may also be a heat-discolorable reversible thermochromic composition having a large hysteresis width (ΔH=8 to 80°C), as described in JP-B-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936, JP-A-2005-1369, etc. "Heat-discolorable" means that the composition is discolored by heating and recolors by cooling. This reversible thermochromic composition changes color along a curve plotting the change in color density with temperature, which follows a path that is significantly different when the temperature is increased from a lower temperature than the color-changing temperature range than when the temperature is decreased from a higher temperature than the color-changing temperature range.The colored state occurs in a temperature range below the complete color-changing temperature t1, and the colorless state occurs in a high-temperature range above the complete color-changing temperature t4, and the composition has color memory in a specific temperature range [the temperature range between the color-changing onset temperature t2 and the color-fading onset temperature t3 (a temperature range where two phases are essentially maintained)] (see Figure 2).

[0043] Components (a), (b) and (c) will be specifically explained below.

[0044] Component (A), that is, the electron-donating organic color-forming compound, is the component that determines the color, and is a compound that donates electrons to component (B), which is the color developer, to develop color.

[0045] Examples of the electron-donating color-forming organic compound include a phthalide compound, a fluoran compound, a styrinoquinoline compound, a diazarhodamine lactone compound, a pyridine compound, a quinazoline compound, and a bisquinazoline compound. Examples of the phthalide compound include a diphenylmethane phthalide compound, a phenylindolyl phthalide compound, an indolyl phthalide compound, a diphenylmethane azaphthalide compound, a phenylindolyl azaphthalide compound, and derivatives thereof. Among these, the phenylindolyl azaphthalide compound and derivatives thereof are preferred. Examples of fluoran compounds include aminofluoran compounds, alkoxyfluoran compounds, and derivatives thereof.

[0046] Examples of compounds that can be used as component (a) are given below. 3,3-bis(4-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-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(2-n-hexyloxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-[2-ethoxy-4-(N-ethylanilino)phenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide, 3-(2-acetamido-4-diethylaminophenyl)-3-(1-propyl-2-methylindol-3-yl)-4-azaphthalide, 3,6-bis(diphenylamino)fluoran, 3,6-bis(N-phenyl-Np-tolylamino)fluoran, 3,6-dimethoxyfluoran, 3,6-di-n-butoxyfluorane, 2-methyl-6-(N-ethyl-Np-tolylamino)fluoran, 3-chloro-6-cyclohexylaminofluoran, 2-methyl-6-cyclohexylaminofluoran, 2-chloroamino-6-di-n-butylaminofluoran, 2-(2-chloroanilino)-6-di-n-butylaminofluoran, 2-(3-trifluoromethylanilino)-6-diethylaminofluoran, 2-(3-trifluoromethylanilino)-6-di-n-pentylaminofluoran, 2-dibenzylamino-6-diethylaminofluoran, 2-N-methylanilino-6-(N-ethyl-Np-tolylamino)fluoran, 1,3-dimethyl-6-diethylaminofluoran, 2-chloro-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methoxy-6-diethylaminofluoran, 2-anilino-3-methyl-6-di-n-butylaminofluoran, 2-anilino-3-methoxy-6-di-n-butylaminofluoran, 2-xylidino-3-methyl-6-diethylaminofluoran, 2-anilino-3-methyl-6-(N-ethyl-Np-tolylamino)fluoran, 6-diethylamino-1,2-benzofluoran, 6-(N-ethyl-N-isobutylamino)-1,2-benzofluoran, 6-(N-ethyl-N-isopentylamino)-1,2-benzofluoran, 2-(3-methoxy-4-dodecoxystyryl)quinoline, 2-diethylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-di-n-butylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-diethylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-(N-ethyl-N-isoamylamino)-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 2-di-n-butylamino-8-di-n-pentylamino-4-methylspiro[5H-[1]benzopyrano[2,3-d]pyrimidin-5,1′(3′H)-isobenzofuran]-3′-one, 4,5,6,7-tetrachloro-3-(4-dimethylamino-2-methoxyphenyl)-3-(1-n-butyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-ethoxyphenyl)-3-(1-n-pentyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 4,5,6,7-tetrachloro-3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-1(3H)-isobenzofuranone, 3',6'-bis[phenyl(2-methylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 3',6'-bis[phenyl(3-methylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthene]-3-one, 3',6'-bis[phenyl(3-ethylphenyl)amino]spiro[isobenzofuran-1(3H),9'-[9H]xanthen]-3-one, 2,6-bis(2′-ethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2,6-bis(2′,4′-diethyloxyphenyl)-4-(4′-dimethylaminophenyl)pyridine, 2,6-bis(2,4-diethyloxyphenyl)-4-[4-bis(4-methyloxyphenyl)aminophenyl]pyridine, 2-(4′-dimethylaminophenyl)-4-methoxyquinazoline, 4,4'-Ethylenedioxy-bis[2-(4-diethylaminophenyl)quinazoline]

[0047] In addition, fluorans may be compounds having a substituent on the phenyl group forming the xanthene ring, or may be compounds that have a substituent on the phenyl group forming the xanthene ring and also have a substituent on the phenyl group forming the lactone ring (for example, an alkyl group such as a methyl group, or a halogen atom such as a chlorine atom), and that exhibit a blue or black color.

[0048] Component (b), ie, the electron accepting compound, is a compound that accepts electrons from component (a) and functions as a developer for component (a). The electron-accepting compound may be selected from the group consisting of compounds having an active proton, pseudo-acidic compounds (compounds that are not acids but act as acids in the reversible thermochromic composition to cause the color of component (A)), and compounds having an electron vacancy. Among the above-mentioned component (B), compounds selected from the group consisting of compounds having an active proton are preferred.

[0049] Examples of compounds having an active proton include compounds having a phenolic hydroxy group and derivatives thereof, carboxylic acids and derivatives thereof, acidic phosphate esters and derivatives thereof, azole compounds and derivatives thereof, 1,2,3-triazole and derivatives thereof, cyclic carbosulfimides, halohydrins having 2 to 5 carbon atoms, sulfonic acids and derivatives thereof, and inorganic acids. Preferred examples of carboxylic acids and derivatives thereof include aromatic carboxylic acids and derivatives thereof, or aliphatic carboxylic acids having 2 to 5 carbon atoms and derivatives thereof. Examples of the pseudo-acidic compounds include metal salts of compounds having a phenolic hydroxy group, metal salts of carboxylic acids, metal salts of acidic phosphate esters, metal salts of sulfonic acids, aromatic carboxylic acid anhydrides, aliphatic carboxylic acid anhydrides, mixed anhydrides of aromatic carboxylic acids and sulfonic acids, cycloolefin dicarboxylic acid anhydrides, urea and its derivatives, thiourea and its derivatives, guanidine and its derivatives, and halogenated alcohols. Compounds having electron vacancies include borates, borate esters, and inorganic salts.

[0050] Among the above-mentioned components (ii), compounds having a phenolic hydroxy group are preferred because they can more effectively exhibit thermochromic properties. Compounds having a phenolic hydroxy group include a wide range of compounds, from monophenol compounds to polyphenol compounds, and further include bisphenol compounds, trisphenol compounds, phenol-aldehyde condensation resins, etc. The compound having a phenolic hydroxy group preferably has at least two benzene rings. In addition, the compound having a phenolic hydroxy group may have a substituent such as an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carboxy group and its ester or amide group, or a halogen atom.

[0051] Examples of metals contained in metal salts of compounds having a phenolic hydroxy group include sodium, potassium, calcium, zinc, zirconium, aluminum, magnesium, nickel, cobalt, tin, copper, iron, vanadium, titanium, lead, and molybdenum.

[0052] Examples of compounds that can be used as component (b) are given below. Phenol, o-cresol, 4-np-nonylphenol, 4-n-octylphenol, 4-n-dodecylphenol, 4-n-stearylphenol, 4-chlorophenol, 4-bromophenol, 2-phenylphenol, n-butyl 4-hydroxybenzoate, n-octyl 4-hydroxybenzoate, resorcinol, 4-tert-butylcatechol, 2,4-dihydroxy-4′-tert-butylbenzophenone, dodecyl gallate, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane, 1,1-bis(4-hydroxyphenyl)n-pentane, 1,1-bis(4-hydroxyphenyl)n-hexane, 1,1-bis(4-hydroxyphenyl)n-heptane, 1,1-bis(4-hydroxyphenyl)n-octane, 1,1-bis(4-hydroxyphenyl)n-nonane, 1,1-bis(4-hydroxyphenyl)n-decane, 1,1-bis(4-hydroxyphenyl)n-dodecane, 1,1-bis(4-hydroxyphenyl)-2-methylpropane, 1,1-bis(4-hydroxyphenyl)n-methylpropane 1,1-bis(4-hydroxyphenyl)-3-methylbutane, 1,1-bis(4-hydroxyphenyl)-3-methylpentane, 1,1-bis(4-hydroxyphenyl)-2,3-dimethylpentane, 1,1-bis(4-hydroxyphenyl)-2-ethylbutane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-3,7-dimethyloctane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1-phenyl-1,1-bi bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)n-butane, 2,2-bis(4-hydroxyphenyl)n-pentane, 2,2-bis(4-hydroxyphenyl)n-hexane, 2,2-bis(4-hydroxyphenyl)n-heptane, 2,2-bis(4-hydroxyphenyl)n-octane, 2,2-bis(4-hydroxyphenyl)n-nonane, 2,2-bis(4-hydroxyphenyl)n-decane, 2,2-bis(4-hydroxyphenyl)n-dodecane, 2,2-bis(4-hydroxyphenyl)ethyl propionate, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 2,2-bis(4-hydroxyphenyl)-4-methylhexane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)butane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis[2-(4-hydroxyphenyl) -2-propyl]benzene, bis(2-hydroxyphenyl)methane, 4,4'-dihydroxydiphenyl sulfone, 4-isopropoxy-4'-hydroxydiphenyl sulfone, bis(4-hydroxyphenyl) sulfide, 1,1,1-tris(4-hydroxyphenyl)ethane, 4,4'-[1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene]bisphenol, 4,4'-[4-(4-hydroxyphenyl)-sec-butylidene]bis(2-methylphenol),

[0053] The component (c) of the reaction medium that reversibly induces an electron donor-acceptor reaction between the components (a) and (b) in a specific temperature range will now be described. Examples of the component (c) include alcohols, esters, ketones, ethers, and acid amides. When the reversible thermochromic composition of the present invention is applied to microencapsulation and secondary processing, compounds having a carbon number of 10 or more are preferably used in order to stably retain them in the capsules, since low molecular weight compounds will evaporate out of the capsules when subjected to high heat treatment.

[0054] As the alcohol, aliphatic monohydric saturated alcohols having 10 or more carbon atoms are effective.

[0055] As the esters, esters having 10 or more carbon atoms are effective, and examples thereof include esters obtained from any combination of a monocarboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring; esters obtained from any combination of a polycarboxylic acid having an aliphatic and alicyclic or aromatic ring and a monohydric alcohol having an aliphatic and alicyclic or aromatic ring; and esters obtained from any combination of a monocarboxylic acid having an aliphatic and alicyclic or aromatic ring and a polyhydric alcohol having an aliphatic and alicyclic or aromatic ring.

[0056] Also effective are esters of saturated fatty acids and branched fatty alcohols, esters of unsaturated fatty acids or branched or substituted saturated fatty acids and branched fatty alcohols or fatty alcohols having 16 or more carbon atoms, and ester compounds selected from cetyl butyrate, stearyl butyrate, and behenyl butyrate.

[0057] Furthermore, in order to change color while exhibiting large hysteresis characteristics in the color density-temperature curve and to impart color memory depending on temperature changes, carboxylic acid ester compounds having a ΔT value (melting point-cloud point) of 5°C or more and less than 50°C, as described in Japanese Patent Publication No. 4-17154, can be exemplified.

[0058] Also effective are fatty acid ester compounds obtained from an odd-numbered aliphatic monohydric alcohol having 9 or more carbon atoms and an even-numbered aliphatic carboxylic acid, and fatty acid ester compounds having a total of 17 to 23 carbon atoms obtained from n-pentyl alcohol or n-heptyl alcohol and an even-numbered aliphatic carboxylic acid having 10 to 16 carbon atoms.

[0059] As the ketones, aliphatic ketones having a total carbon number of 10 or more are effective, and examples thereof include aryl alkyl ketones having a total carbon number of 12 to 24.

[0060] As the ethers, aliphatic ethers having a total of 10 or more carbon atoms are effective.

[0061] Examples of the above alcohols, esters, ketones, ethers, and acid amides include the compounds described in JP-A-2020-100710.

[0062] Furthermore, the component (iii) may be a compound represented by the following formula (1). [ka] [wherein R1 represents a hydrogen atom or a methyl group, m represents an integer of 0 to 2, and either X1 or X2 represents -(CH2) n OCOR2 or -(CH2) n COOR2, the other represents a hydrogen atom; n represents an integer of 0 to 2; R2 represents an alkyl or alkenyl group having 4 or more carbon atoms; Y1 and Y2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom; and r and p each independently represent an integer of 1 to 3. Among the compounds represented by formula (1), when R1 is a hydrogen atom, a reversible thermochromic composition having a wider hysteresis width can be obtained, which is preferable, and it is even more preferable that R1 is a hydrogen atom and m is 0. Among the compounds represented by formula (1), the compound represented by the following formula (2) is more preferred. [ka] (In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms, and more preferably an alkyl group having 12 to 22 carbon atoms.)

[0063] Furthermore, the component (iii) may be a compound represented by the following formula (3). [ka] (In the formula, R represents an alkyl group or alkenyl group having 8 or more carbon atoms, m and n each independently represent an integer of 1 to 3, and X and Y each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom.)

[0064] Furthermore, the component (iii) may be a compound represented by the following formula (4). [ka] (wherein X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, or a halogen atom; m represents an integer of 1 to 3; and n represents an integer of 1 to 20).

[0065] Furthermore, the component (iii) may be a compound represented by the following formula (5). [ka] (wherein R represents an alkyl or alkenyl group having 1 to 21 carbon atoms, and n represents an integer of 1 to 3).

[0066] Furthermore, the component (iii) may be a compound represented by the following formula (6). [ka] (wherein X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; m represents an integer of 1 to 3; and n represents an integer of 1 to 20).

[0067] Furthermore, the component (iii) may be a compound represented by the following formula (7). [ka] (In the formula, R represents an alkyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, a cycloalkyl group, or an alkenyl group having 4 to 22 carbon atoms; X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom; and n represents 0 or 1.)

[0068] Furthermore, the component (iii) may be a compound represented by the following formula (8). [ka] (wherein R represents an alkyl group having 3 to 18 carbon atoms or an aliphatic acyl group having 3 to 18 carbon atoms; X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom; Y represents a hydrogen atom or a methyl group; and Z represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, or a halogen atom).

[0069] Furthermore, the component (iii) may be a compound represented by the following formula (9). [ka] (In the formula, R represents an alkyl group having 4 to 22 carbon atoms, an alkenyl group having 4 to 22 carbon atoms, a cycloalkylalkyl group, or a cycloalkyl group; X represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; Y represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom; and n represents 0 or 1.)

[0070] Furthermore, the component (iii) may be a compound represented by the following formula (10). [ka] (In the formula, R represents any one of an alkyl group having 3 to 18 carbon atoms, a cycloalkylalkyl group having 6 to 11 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, and an alkenyl group having 3 to 18 carbon atoms; X represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and a halogen atom; and Y represents any one of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, and a halogen atom.)

[0071] Furthermore, the component (iii) may be a compound represented by the following formula (11). [ka] (wherein R represents a cycloalkyl group having 3 to 8 carbon atoms or a cycloalkylalkyl group having 4 to 9 carbon atoms, and n represents an integer of 1 to 3).

[0072] Furthermore, the component (iii) may be a compound represented by the following formula (12). [ka] (In the formula, R represents an alkyl group having 3 to 17 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a cycloalkylalkyl group having 5 to 8 carbon atoms; X represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, or a halogen atom; and n represents an integer of 1 to 3.)

[0073] Examples of the compounds represented by formulas (2) to (12) include the compounds described in JP-A-2020-100710.

[0074] The reversible thermochromic composition may be a heat-coloring type reversible thermochromic composition using a gallic acid ester, as described in JP-B No. 51-44706, JP-A No. 2003-253149, etc. The heat-coloring type means that the color develops when heated and disappears when cooled (see FIG. 3).

[0075] The reversible thermochromic composition is a compatible solution containing the above components (A), (B), and (C) as essential components. The proportions of each component depend on the concentration, discoloration temperature, discoloration form, and type of each component, but the component ratios that generally provide the desired properties are 1 part of component (A) to 0.1 to 100, preferably 0.1 to 50, more preferably 0.5 to 20, of component (B), and 1 to 800, preferably 5 to 200, more preferably 5 to 100, and even more preferably 10 to 100, of component (C) (all of the above proportions are in parts by mass).

[0076] Examples of reversible photochromic materials include photochromic compounds such as conventionally known spirooxazine derivatives, spiropyran derivatives, and naphthopyran derivatives that develop color when irradiated with sunlight, ultraviolet light, or blue light with a peak emission wavelength in the range of 400 to 495 nm, and lose color when the irradiation is stopped. For example, compounds described in JP 2021-120493 A and WO 2020 / 137469 A can be cited.

[0077] Furthermore, a photochromic compound having optical memory properties (color memory photochromism) can also be used. Examples of such photochromic compounds include diarylethene derivatives, such as those described in JP-A-2021-120493.

[0078] As the reversible photochromic material, a reversible photochromic composition in which the above photochromic compound is dissolved in various oligomers can also be used. Examples of the oligomer include styrene-based oligomers, acrylic-based oligomers, terpene-based oligomers, and terpene-phenol-based oligomers. By dissolving the photochromic compound in various oligomers, it is possible to improve the light resistance and color density, and further to adjust the color change sensitivity.

[0079] The styrene-based oligomer preferably has a mass-average molecular weight of 200 to 6000, more preferably 200 to 4000. If the mass-average molecular weight exceeds 6000, color retention occurs upon light irradiation, the color density tends to decrease, and it becomes difficult to adjust the color change sensitivity. On the other hand, if the mass-average molecular weight is less than 200, the amount of contained monomer increases, resulting in a lack of stability and a tendency to impair lightfastness. Styrene oligomers are compounds having a styrene skeleton or hydrogenated products thereof, and examples thereof include low-molecular-weight polystyrene, styrene-α-methylstyrene copolymer, α-methylstyrene polymer, and α-methylstyrene-vinyltoluene copolymer.

[0080] The acrylic oligomer preferably has a mass-average molecular weight of 12,000 or less, more preferably 1,000 to 8,000, and even more preferably 1,500 to 6,000. If the mass-average molecular weight exceeds 12,000, it becomes difficult to adjust the discoloration sensitivity. On the other hand, if the mass-average molecular weight is less than 1,000, the amount of contained monomer increases, resulting in a lack of stability, which tends to result in a low color density and a loss of lightfastness. Examples of the acrylic oligomer include acrylic acid ester copolymers.

[0081] The terpene oligomer preferably has a mass-average molecular weight of 250 to 4000, more preferably 300 to 4000. If the mass-average molecular weight exceeds 4000, color retention occurs upon light irradiation, the color density tends to decrease, and it becomes difficult to adjust the color change sensitivity. On the other hand, if the mass-average molecular weight is less than 250, the amount of contained monomer increases, resulting in a lack of stability and a tendency to impair lightfastness. The terpene oligomer is a compound having a terpene skeleton, and examples thereof include α-pinene polymer, β-pinene polymer, and d-limonene polymer.

[0082] The terpene phenol oligomer preferably has a mass-average molecular weight of 200 to 2000, more preferably 500 to 1200. If the mass-average molecular weight of the terpene phenol oligomer exceeds 2000, it becomes difficult to adjust the discoloration sensitivity. On the other hand, if the mass-average molecular weight is less than 200, the amount of contained monomer increases, resulting in a lack of stability and a tendency for the color density to decrease. Terpene-phenol oligomers are compounds obtained by copolymerizing cyclic terpene monomers with phenols or their hydrogenated products, such as α-pinene-phenol copolymers.

[0083] The mass average molecular weight of the above styrene-based oligomer, acrylic-based oligomer, terpene-based oligomer, and terpene-phenol-based oligomer can be measured by gel permeation chromatography (GPC).

[0084] The oligomers can be used alone or in combination of two or more.

[0085] In the reversibly photochromic composition, the mass ratio of the photochromic compound to the styrene-based oligomer or the photochromic compound to the acrylic oligomer is preferably 1:1 to 1:10000, more preferably 1:5 to 1:500. In the reversibly photochromic composition, the mass ratio of the photochromic compound to the terpene oligomer is preferably 1:1 to 1:5000, more preferably 1:5 to 1:500. In the reversibly photochromic composition, the mass ratio of the photochromic compound to the terpene phenol oligomer is preferably 1:1 to 1:50, more preferably 1:2 to 1:30. When the mass ratio of the photochromic compound to the oligomer is within the above range, the photochromic compound satisfies the color-developing and color-decoloring functions and tends to exhibit sufficient color density.

[0086] The reversible thermochromic composition or reversible photochromic composition can be encapsulated in microcapsules to form a reversible thermochromic microcapsule pigment or reversible photochromic microcapsule pigment (hereinafter sometimes referred to as a "microcapsule pigment"), or dispersed in a thermoplastic resin or thermosetting resin to form reversible thermochromic resin particles or reversible photochromic resin particles, and used as a reversible thermochromic material or reversible photochromic material. The reversible thermochromic composition or reversible photochromic composition is preferably encapsulated in microcapsules and used as a microcapsule pigment. This is because encapsulation in microcapsules allows for the formation of a chemically and physically stable pigment, and the reversible thermochromic composition or reversible photochromic composition can maintain the same composition and exhibit the same effects under various usage conditions.

[0087] Microencapsulation can be performed by known methods such as isocyanate-based interfacial polymerization, in situ polymerization such as melamine-formalin polymerization, in-liquid curing coating, phase separation from an aqueous solution, phase separation from an organic solvent, melt-dispersion cooling, air suspension coating, and spray drying, and can be selected appropriately depending on the application.

[0088] Depending on the purpose, a secondary resin film may be provided on the surface of the microcapsules to impart durability or to modify the surface properties for practical use.

[0089] The reversible thermochromic microcapsule pigment or reversible photochromic microcapsule pigment preferably has a mass ratio of inclusions to wall film of 7:1 to 1:1, and by having the mass ratio of inclusions to wall film within the above range, it is possible to prevent a decrease in color density and clarity during color development. More preferably, the mass ratio of inclusions to wall film is 6:1 to 1:1.

[0090] The blending ratio of the color-changing material to the total mass of the liquid composition is not particularly limited, but is preferably 0.5 to 40 mass%, more preferably 1 to 30 mass%, and even more preferably 5 to 15 mass%. If the blending ratio of the color-changing material exceeds 40 mass%, the dispersion stability and processability during dispersion in the vehicle are likely to be lacking, a significant improvement in color density is unlikely to be observed, and residual color is likely to occur in the decolorized state. On the other hand, if the blending ratio is less than 0.5 mass%, it is difficult to achieve the desired color density and the color-changing function is unlikely to be fully achieved.

[0091] Furthermore, by incorporating a non-color-changing colorant such as a general dye or pigment during microencapsulation, the microencapsulated pigment can undergo an alternating color change from color (1) to color (2).

[0092] The average particle size of the reversible thermochromic microencapsulated pigment or reversible photochromic microencapsulated pigment is preferably 0.5 to 10 μm, more preferably 0.5 to 5 μm, and even more preferably 1 to 3 μm for practical use. If the average particle size exceeds 10 μm, the pigment is likely to lack dispersion stability and processability when blended into a liquid composition. On the other hand, if the average particle size is less than 0.5 μm, it becomes difficult to achieve high-concentration color development.

[0093] The average particle diameter was determined by determining the particle region using image analysis particle size distribution measurement software (manufactured by Mountec Co., Ltd., product name: MacView), calculating the diameter of a circle equivalent to the projected area (Heywood diameter) from the area of ​​the particle region, and measuring the average particle diameter of particles equivalent to a sphere of equal volume using this value. Furthermore, if the particle size of all or the majority of particles exceeds 0.2 μm, it is also possible to measure the average particle size of particles equivalent to an equal-volume sphere by the Coulter method using a particle size distribution analyzer (product name: Multisizer 4e, manufactured by Beckman Coulter, Inc.). Furthermore, the volumetric particle size and average particle size may be measured using a calibrated laser diffraction / scattering particle size distribution analyzer (manufactured by HORIBA, Ltd., product name: LA-300) based on values ​​measured using the above software or a measuring device using the Coulter method.

[0094] Since the substrate according to the present invention is thermosensitive, it is preferable to use a thermochromic material that changes color with temperature as the color-changing material. This is because the shape deformability and shape retention of the substrate and the color change of the color-changing layer in the laminate described below can be achieved simply by changing the temperature. Because they can repeatedly change color, the above-mentioned reversible thermochromic material is preferable as the thermochromic material, and reversible thermochromic microcapsule pigments are more preferable.

[0095] The temperature (T) at which the loss tangent shows a maximum value is preferably approximately the same as the complete color development temperature t1 or the complete color disappearance temperature t4 of the reversible thermochromic material (reversible thermochromic composition). This allows the temperature at which the flexibility of the substrate changes to be synchronized with the temperature at which the color-changing layer changes color in the laminate described below, and makes it possible to determine from the color change of the color-changing layer whether the temperature at which the flexibility of the substrate changes has been reached.

[0096] Here, "substantially the same" includes temperatures T and t1, or temperatures T and t4 being exactly the same temperature, and also includes in the present invention that the difference between temperatures T and t1 (Δt1=T-t1) is 2°C or less, or that the difference between temperatures T and t4 (Δt4=t4-T) is 2°C or less. In other words, "substantially the same" in the present invention means that 0≦Δt1≦2 or 0≦Δt4≦2 is satisfied. With respect to Δt1 or Δt4, preferably 0≦Δt1≦1 or 0≦Δt4≦1, more preferably 0≦Δt1<1 or 0≦Δt4<1, and even more preferably Δt1=0 (T=t1) or Δt4=0 (T=t4).

[0097] An example will be given below in which the temperature at which the loss tangent shows its maximum value is the same as the complete color development temperature t1 of the reversibly thermochromic material, that is, Δt1=0 (T=t1). When the laminate in the colored state is heated to a temperature t4 or higher, the laminate changes to a decolored state. At this time, the substrate is flexible, and the laminate can be deformed into any shape by applying an external force. After the laminate is deformed into any shape by applying an external force, if it is cooled below temperature T (temperature t1) while the external force is still applied, the laminate changes to a colored state and can maintain the deformed shape even after the external force is removed. Therefore, the change in flexibility of the laminate and the reaching of a temperature at which the laminate can maintain the deformed shape without the application of an external force can be determined by the change from the decolored state of the laminate to the colored state, i.e., the color change of the color-changing layer.

[0098] An example will be given below in which the temperature at which the loss tangent has a maximum value is the same as the complete decolorization temperature t4 of the reversible thermochromic material, that is, Δt4=0 (T=t4). When the laminate in the colored state is heated to a temperature T (temperature t4) or higher, the laminate changes to a colorless state and can be deformed into any shape by applying an external force. Therefore, the change in flexibility of the laminate and the reaching of a temperature at which the laminate can be deformed into any shape by applying an external force can be determined by the change from the colored state of the laminate to the colorless state, i.e., the color change of the color-changing layer.

[0099] The temperature (T) at which the loss tangent shows a maximum value is between the complete color development temperature t1 and the complete color disappearance temperature t4 of the reversible thermochromic material (reversible thermochromic composition), and preferably satisfies at least one of Δt1 ≧ 5 or Δt4 ≧ 5, and more preferably satisfies Δt1 ≧ 5 and Δt4 ≧ 5. This makes it possible to determine from the color change of the color-changing layer whether the laminate described below has reached a temperature sufficiently higher than the temperature at which the flexibility of the substrate changes, and can be easily deformed into any shape by application of an external force, or whether, after the laminate has been deformed into any shape by application of an external force, it has reached a temperature sufficiently lower than the temperature at which the flexibility of the substrate changes, and the deformed shape is well maintained without application of an external force. With respect to Δt1 or Δt4, it is preferable that Δt1≧10 or Δt4≧10.

[0100] An example is shown below where the temperature at which the loss tangent shows its maximum value is between the complete coloring temperature t1 and the complete decoloring temperature t4 of the reversible thermochromic material, and Δt1≧5 and Δt4≧5 are satisfied. The laminate is in a colored state at temperature T, and when the laminate in this colored state is heated to a temperature t4 or higher, the laminate changes to a decolored state and can be easily deformed into any shape by applying an external force. Therefore, the change from the colored state to the decolored state of the laminate, i.e., the color change of the color-changing layer, can be determined by the fact that the temperature has reached a level sufficiently higher than the temperature at which the flexibility of the base material changes and the laminate can be easily deformed into any shape by applying an external force. After applying an external force to deform the laminate into a desired shape, if the laminate is cooled to a temperature below t1 while the external force is still applied, the laminate will enter a colored state and the deformed shape of the laminate will be well maintained even after the external force is removed. Therefore, it can be determined by the change from the decolored state of the laminate to the colored state, i.e., the color change of the color-changing layer, that the temperature has reached a temperature sufficiently lower than the temperature at which the flexibility of the base material changes and the deformed shape of the laminate will be well maintained without the application of an external force. Here, when a laminate that has been heated to a temperature t4 or higher and deformed into an arbitrary shape is cooled to a temperature range above t1 but below temperature T while applying an external force, the laminate enters a decolorized state and can be maintained in the deformed shape without the application of an external force. Unless cooled to a temperature below t1, the laminate can repeatedly deform into an arbitrary shape and maintain the deformed shape while remaining in the decolorized state. Furthermore, when cooled to a temperature below t1, the laminate enters a colored state. When heated to a temperature range above temperature T but below temperature t4, the laminate enters a colored state and can be deformed into an arbitrary shape by applying an external force. Unless heated to a temperature above t4, the laminate can repeatedly deform into an arbitrary shape and maintain the deformed shape while remaining in the colored state. That is, the laminate can be repeatedly deformed into any shape and maintained in the deformed shape while being selectively maintained in either a colored state or a decolored state.

[0101] The vehicle used in the present invention contains at least a 4-methyl-1-pentene polymer (B) (hereinafter sometimes referred to as "polymer (B)") and a solvent. Here, the 4-methyl-1-pentene polymer (B) functions as a binder resin in the liquid composition according to the present invention. Furthermore, the 4-methyl-1-pentene polymer does not affect the color development, fading, or discoloration of the color-changing material.

[0102] The 4-methyl-1-pentene polymer (A) constituting the substrate and the 4-methyl-1-pentene polymer (B) contained in the vehicle both contain 4-methyl-1-pentene as a constituent monomer. As a result, the properties of the polymer (A) and the polymer (B) are similar, and the liquid composition has high affinity for the substrate. Therefore, by using the liquid composition of the present invention, it is possible to form a color-changing layer that has excellent adhesion to the substrate and good followability to deformations such as expansion, contraction, and bending.

[0103] The 4-methyl-1-pentene polymer (B) is not particularly limited, but examples thereof include a 4-methyl-1-pentene-α-olefin copolymer (b) (hereinafter sometimes referred to as "copolymer (b)") containing a structural unit (b1) derived from 4-methyl-1-pentene and a structural unit (b2) derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene. Here, unless otherwise specified, "α-olefin having 2 to 20 carbon atoms" does not include 4-methyl-1-pentene. 4-Methyl-1-pentene·α-olefin copolymer is preferably used as a material for constituting the liquid composition because it improves the adhesion of the color-changing layer formed from the liquid composition to the substrate and its ability to conform to deformations such as expansion, contraction, and bending.

[0104] In the 4-methyl-1-pentene·α-olefin copolymer (b), the blending ratio of the structural unit (b1) to the structural unit (b2) is not particularly limited. In order to achieve good solubility in the solvents described below and excellent stability of the liquid composition, when the total of the structural units (b1) and (b2) is taken as 100 mol%, it is preferable that the structural unit (b1) accounts for 50 to 95 mol% and the structural unit (b2) accounts for 5 to 50 mol%, and it is even more preferable that the structural unit (b1) accounts for 70 to 90 mol% and the structural unit (b2) accounts for 10 to 30 mol%.

[0105] Examples of the α-olefin having 2 to 20 carbon atoms used in the 4-methyl-1-pentene·α-olefin copolymer (b) include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and functionalized vinyl compounds. As the linear or branched α-olefin, cyclic olefin, aromatic vinyl compound, conjugated diene, and functionalized vinyl compound, the same compounds as those exemplified as the α-olefins having 2 to 20 carbon atoms used in the 4-methyl-1-pentene-α-olefin copolymer (a) can be used.

[0106] The α-olefins can be used alone or in combination of two or more.

[0107] The α-olefin is preferably a linear α-olefin having 2 to 4 carbon atoms, such as ethylene, propylene, 1-butene, etc. Ethylene or propylene is more preferred, and propylene is even more preferred, as these provide excellent copolymerizability and physical properties to the copolymer (b).

[0108] The blending ratio of 4-methyl-1-pentene and α-olefin in the 4-methyl-1-pentene-α-olefin copolymer (b) is, for example, 13 It can be measured by C NMR.

[0109] The 4-methyl-1-pentene·α-olefin copolymer (b) preferably satisfies the requirements (iv) to (vii) described below.

[0110] The 4-methyl-1-pentene-α-olefin copolymer (b) preferably has an intrinsic viscosity [η] in decalin at 135°C of 0.5 to 5.0 dL / g, more preferably 0.6 to 4.0 dL / g, and even more preferably 1.0 to 2.5 dL / g (iv). The intrinsic viscosity [η] within the above range can improve the stability of the liquid composition. The intrinsic viscosity [η] can be adjusted by the amount of hydrogen added in the polymerization step when preparing the copolymer (b). The intrinsic viscosity [η] can be measured by the same method as described above.

[0111] The 4-methyl-1-pentene·α-olefin copolymer (b) preferably has a melting point (Tm) measured by differential scanning calorimetry (DSC) of 200°C or less or substantially no melting point, more preferably a melting point of 110 to 180°C or substantially no melting point, and even more preferably a melting point of less than 160°C or substantially no melting point. The melting point (Tm) can be adjusted by the blending ratio of the α-olefin having 2 to 20 carbon atoms in the copolymer (b). The melting point (Tm) can be measured by differential scanning calorimetry as described below.

[0112] (Differential Scanning Calorimetry) Approximately 5 mg of 1,4-methyl-1-pentene·α-olefin copolymer is placed in an aluminum container, sealed with a lid, and used as the measurement sample. 2. Place the measurement sample in the measuring device, heat it to 290°C at a rate of 10°C / min, hold it at 290°C for 5 minutes, and then cool it to -50°C at a rate of 10°C / min. 3. The melting point (Tm) is determined from the temperature at the apex of the endothermic peak due to melting in the obtained DSC curve.

[0113] In a DSC curve, the area of ​​the endothermic peak is the enthalpy of fusion (ΔH f ) If there is no melting point, no endothermic peak is observed, so the area of ​​the endothermic peak, i.e., the enthalpy of fusion (ΔH f ) is not required. In the present invention, "substantially no melting point" means that there is substantially no melting enthalpy in the DSC curve. f ) may be 0 to 10 J / g, and preferably 0 to 5 J / g.

[0114] The 4-methyl-1-pentene-α-olefin copolymer (b) preferably has a density of 820 to 850 kg / m3 , more preferably 825 to 850 kg / m 3 , more preferably 825 to 845 kg / m 3 , particularly preferably 825 to 840 kg / m 3 The density can be adjusted by the type of α-olefin having 2 to 20 carbon atoms in the copolymer (b) or the blending ratio of 4-methyl-1-pentene and α-olefin having 2 to 20 carbon atoms. The density can be measured by a method in accordance with JIS K7112.

[0115] The 4-methyl-1-pentene-α-olefin copolymer (b) preferably has a molecular weight distribution (Mw / Mn) of 1.0 to 3.5, more preferably 1.3 to 3.0, and even more preferably 1.5 to 2.5, as measured by gel permeation chromatography (GPC). Here, the molecular weight distribution (Mw / Mn) represents the ratio of the mass-average molecular weight (Mw) to the number-average molecular weight (Mn). Having the molecular weight distribution (Mw / Mn) within the above range can improve the solubility in solvents described below. The molecular weight distribution (Mw / Mn) can be adjusted by the type of polymerization catalyst used in preparing the copolymer (b). The molecular weight distribution (Mw / Mn) can be determined by measuring the mass average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography as described below.

[0116] (Gel Permeation Chromatography) 1. The column temperature was set to 140°C, and the mobile phase was o-dichlorobenzene and 0.025% by mass of an antioxidant (dibutylhydroxytoluene), and the flow rate was 1.0 mL / min. The concentration of 2,4-methyl-1-pentene-α-olefin copolymer was adjusted to 15 mg / 10 mL, 500 μL of which was injected, and the sample was detected using a differential refractometer.

[0117] The method for producing the 4-methyl-1-pentene-α-olefin copolymer (b) is not particularly limited, and various methods can be used for production. For example, the copolymer can be produced by polymerizing 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms in the presence of a polymerization catalyst.

[0118] The solvent is not particularly limited as long as it can dissolve the 4-methyl-1-pentene polymer (B) and does not affect the color development, fading, discoloration, etc. of the color-changing material. Examples of the solvent include aliphatic hydrocarbon solvents, aromatic solvents, tetrahydrofuran, thinner, limonene, etc.

[0119] Examples of aliphatic hydrocarbon solvents include alkane solvents such as n-hexane, n-heptane, and n-octane; naphthene solvents such as cyclohexane, methylcyclohexane, ethylcyclohexane, and the Exxol series (manufactured by ExxonMobil Corporation); and isoparaffin solvents such as the IP Solvent series (manufactured by Idemitsu Kosan Co., Ltd.), the MC series (manufactured by Tobu Chemical Co., Ltd.), and the Isopar series (manufactured by ExxonMobil Corporation).

[0120] Examples of aromatic solvents include toluene, xylene, the Solvesso series (manufactured by Exxon Mobil Corp.), the Ipsol series (manufactured by Idemitsu Kosan Co., Ltd.), and mineral spirits.

[0121] The boiling point of the solvent is not particularly limited, but is preferably 20 to 300° C., more preferably 50 to 250° C., even more preferably 70 to 230° C., and particularly preferably 100 to 220° C. If the boiling point is within the above range, the stability and handleability of the liquid composition can be improved.

[0122] The vehicle of the present invention can contain various oligomers to improve the dispersibility of the color-changing material in the liquid composition, thereby making the concentration of the color-changing layer formed from the liquid composition uniform and eliminating the roughness associated with poor dispersion, resulting in a color-changing layer with excellent appearance.

[0123] Examples of oligomers include styrene-based oligomers, acrylic-based oligomers, terpene-based oligomers, silicone-based oligomers, etc. Among these, styrene-based oligomers are preferred because of their excellent compatibility with 4-methyl-1-pentene polymers.

[0124] Among the 4-methyl-1-pentene polymers (B), 4-methyl-1-pentene·α-olefin copolymers are preferred due to their excellent compatibility. By using 4-methyl-1-pentene·α-olefin copolymers in combination with styrene oligomers, the dispersibility of the color-changing material can be improved, resulting in a more excellent appearance of the color-changing layer.

[0125] The styrene oligomer preferably has a mass-average molecular weight of 200 to 6000, more preferably 200 to 4000. When the mass-average molecular weight is within the above range, the dispersibility of the color-changing material can be further improved. The mass-average molecular weight is a value measured by gel permeation chromatography (GPC).

[0126] The styrene oligomer is a compound having a styrene skeleton or a hydrogenated product thereof, and examples thereof include styrene-α-methylstyrene copolymer, α-methylstyrene polymer, and α-methylstyrene-vinyltoluene copolymer.

[0127] Examples of styrene-α-methylstyrene copolymers include Picolastic A-5 (manufactured by Eastman Chemical Company, mass average molecular weight: 317) and Picolastic A-75 (manufactured by Eastman Chemical Company, mass average molecular weight: 917).

[0128] Examples of α-methylstyrene polymers include CRYSTALEX 3085 (manufactured by Eastman Chemical Company, mass average molecular weight: 664), CRYSTALEX 3100 (manufactured by Eastman Chemical Company, mass average molecular weight: 1020), and CRYSTALEX 1120 (manufactured by Eastman Chemical Company, mass average molecular weight: 2420).

[0129] Examples of the α-methylstyrene-vinyltoluene copolymer include Picotex LC (manufactured by Eastman Chemical Company, mass average molecular weight: 950) and Picotex 100 (manufactured by Eastman Chemical Company, mass average molecular weight: 1740).

[0130] The oligomers can be used alone or in combination of two or more.

[0131] In the liquid composition according to the present invention, the mass ratio of the 4-methyl-1-pentene polymer (B) to the styrene oligomer is not particularly limited, but is preferably 1:0.5 to 1:5, and more preferably 1:1 to 1:2. When the mass ratio is within the above range, it becomes easy to improve the dispersibility of the color-changing material.

[0132] The vehicle may also contain various additives as required. Examples of additives include crosslinking agents, curing agents, drying agents, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, antioxidants, light stabilizers, anti-settling agents, smoothing agents, gelling agents, antifoaming agents, matting agents, penetrating agents, pH adjusters, foaming agents, coupling agents, moisturizing agents, lubricants, antifungal agents, preservatives, and rust inhibitors.

[0133] By blending a non-color-changing colorant such as a general dye or pigment into the liquid composition, it is possible to bring about an alternating color change from color (1) to color (2) in the color-changing layer formed by the liquid composition.

[0134] In the liquid composition according to the present invention, the mass ratio of 4-methyl-1-pentene polymer (B) to color-changing material is not particularly limited, but is preferably 1:0.5 to 1:5, more preferably 1:0.5 to 1:2, and even more preferably 1:1 to 1:2. When the mass ratio is within the above range, the color-changing material can be easily and stably dispersed when dispersed in a vehicle, and the color-changing layer formed from the liquid composition can easily exhibit the desired color density.

[0135] The liquid composition according to the present invention can be produced by any conventionally known method. Specifically, the liquid composition can be produced by mixing the required amounts of the above-described components and stirring them with a stirrer such as a propeller stirrer, a homodisper, or a homomixer, or by dispersing them with a disperser such as a bead mill.

[0136] From the viewpoint of the adhesiveness of the color-changing layer formed from the liquid composition to the substrate and its ability to follow deformations such as expansion, contraction, and bending, it is preferable that both polymer (A) and polymer (B) contain structural units derived from an α-olefin having 2 to 20 carbon atoms. It is more preferable that the α-olefin is propylene, that is, both polymer (A) and polymer (B) contain structural units derived from propylene.

[0137] A color-changing material is dispersed in a vehicle containing the 4-methyl-1-pentene polymer (B), a solvent, and, if necessary, various additives, The color-changing liquid composition may be a printing ink used in screen printing, offset printing, process printing, gravure printing, coater printing, pad printing, etc.; a paint used in brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc.; an inkjet ink; or an ultraviolet-curable ink.

[0138] When the liquid composition according to the present invention is used as a printing ink, the blending ratio of the solvent to the total mass of the liquid composition is not particularly limited, but is preferably 50 to 80 mass %, more preferably 60 to 80 mass %. When the liquid composition according to the present invention is used as a coating material, the blending ratio of the solvent to the total mass of the liquid composition is not particularly limited, but is preferably 70 to 90 mass %, more preferably 75 to 85 mass %. By ensuring that the blending ratio of the solvent is within the above range, the stability and handling properties of the liquid composition can be improved.

[0139] The color-changing laminate according to the present invention has a structure in which a color-changing layer formed by volatilizing a solvent from the liquid composition according to the present invention is provided on a substrate composed of the above-mentioned 4-methyl-1-pentene polymer (A). The method for producing the color-changing laminate is not particularly limited, and it can be produced, for example, by printing or coating the liquid composition on the substrate and volatilizing the solvent from the liquid composition to form a color-changing layer.

[0140] The color-changing laminate of the present invention changes color in response to heat or light, and has the temperature sensitivity, shape deformability, and shape retention inherent to the substrate. The color-changing layer also has excellent adhesion to the substrate, and the color-changing layer does not peel off or break when the laminate is deformed by expansion, contraction, bending, or other deformations, resulting in excellent conformability.

[0141] The color-changing layer may be a solid pattern, or may be a shape such as a circle, oval, square, or rectangle, various letters, symbols, patterns, or images (color-changing images) of people, animals, plants, fruits, food products, vehicles, buildings, celestial bodies, etc. The color-changing layer or color-changing image is formed by volatilizing the solvent in the liquid composition and leaving compounds other than the solvent.

[0142] A transparent resin layer may be provided on the color-changing layer of the laminate according to the present invention, which can prevent damage to the color-changing layer due to external factors such as external forces when deforming the laminate or abrasion, thereby improving the durability of the color-changing layer.

[0143] The transparent resin layer is not particularly limited as long as it does not affect the color-developing, color-fading, and color-changing functions of the underlying color-changing layer, allows the color change of the color-changing layer to be visually recognized, and has the ability to follow deformation of the laminate. For example, a liquid composition such as a printing ink or paint containing a transparent resin can be printed or applied onto the color-changing layer by a printing method such as screen printing, offset printing, gravure printing, coater printing, or transfer printing, or by a coating method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, or dip coating, thereby providing the transparent resin layer on the color-changing layer. The transparent resin layer is a layer formed from the transparent resin when volatile components such as the solvent in the liquid composition volatilize.

[0144] The transparent resin is not particularly limited, and a general-purpose transparent resin can be used. From the viewpoints of adhesion to the color-changing layer and adaptability to deformation of the laminate, it is preferable to use a 4-methyl-1-pentene polymer as the transparent resin. The 4-methyl-1-pentene polymer preferably contains structural units derived from 4-methyl-1-pentene and structural units derived from an α-olefin having 2 to 20 carbon atoms, and more preferably the α-olefin is propylene, i.e., the 4-methyl-1-pentene polymer contains structural units derived from 4-methyl-1-pentene and structural units derived from propylene.

[0145] The transparent resin may contain at least one of a light stabilizer and a transparent metallic luster pigment, thereby improving the light resistance of the color-changing layer. Examples of light stabilizers include ultraviolet absorbers, antioxidants, singlet oxygen quenchers, superoxide anion quenchers, and ozone quenchers. Examples of transparent metallic luster pigments include pigments having a core material such as natural mica, synthetic mica, glass flakes, alumina, or transparent film flakes whose surface is coated with a metal oxide such as titanium oxide.

[0146] It is also suitable to use a transparent resin film as the transparent resin layer, which is more effective in preventing damage to the color-change layer due to external factors such as external stress when deforming the laminate or abrasion, and can further improve the durability of the color-change layer. Examples of transparent resin films include films made of general-purpose resins such as polyolefin resins such as polyethylene and polypropylene; cellulose derivatives such as cellulose acetate; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyamide resins; vinyl alcohol resins such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers; vinyl chloride resins; vinylidene chloride resins; acrylic ester resins; polyacrylic acid; rayon; and cupra.

[0147] The thickness of the transparent resin film is not particularly limited, but is preferably 3 to 50 μm, more preferably 5 to 25 μm, and even more preferably 10 to 20 μm. When the thickness of the transparent resin film is within the above range, it is possible to achieve an excellent effect of increasing the durability of the color-changing layer, without impairing the shape deformability or shape retention of the substrate, and to follow deformation of the laminate.

[0148] When a transparent resin film is used as the transparent resin layer, it is preferable to provide an adhesive layer between the transparent resin film and the color-changing layer, or to use a transparent resin film having an adhesive layer.

[0149] In the laminate of the present invention, the substrate exhibits a low modulus of elasticity at temperatures above the glass transition temperature, exhibiting viscous properties and therefore prone to adhesiveness. Therefore, when laminates are brought into direct contact with each other at temperatures near the glass transition temperature, the substrates or the substrate and the color-change layer may adhere to each other (so-called blocking), and the laminate may not return to its original shape when the adhered portions are peeled off. Therefore, it is also preferable to provide an adhesion-suppressing layer on the surface of the substrate opposite the surface on which the color-change layer is provided.

[0150] The adhesion-suppressing layer is not particularly limited as long as it can suppress the adhesion of the substrate. For example, a general-purpose resin film or the like can be used, but since there is a risk of misalignment between the substrate and the resin film during storage of the laminate, an adhesion-suppressing layer formed by printing or applying a liquid composition such as printing ink or paint to the surface of the substrate opposite to the surface on which the color-changing layer is provided, by a printing method such as screen printing, offset printing, gravure printing, coater, or transfer printing, or by a coating method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, or dip coating, is preferred.

[0151] The liquid composition for forming the adhesion-suppressing layer (hereinafter sometimes referred to as the "liquid composition for forming the adhesion-suppressing layer") preferably contains at least an adhesion suppressant, the above-mentioned 4-methyl-1-pentene polymer (B), and a solvent. The 4-methyl-1-pentene polymer (B) contained in the liquid composition for forming an adhesion-suppressing layer and the 4-methyl-1-pentene polymer (A) constituting the substrate both contain 4-methyl-1-pentene as a constituent monomer. As a result, the properties of the polymer (A) and the polymer (B) are similar, and the liquid composition for forming an adhesion-suppressing layer has a high affinity for the substrate. Therefore, by using a liquid composition for forming an adhesion-suppressing layer containing the 4-methyl-1-pentene polymer (B), it is possible to form an adhesion-suppressing layer that has excellent adhesion to the substrate, can suppress the adhesion of the substrate that occurs at temperatures near the glass transition temperature, and has good followability to deformations such as expansion, contraction, and bending.

[0152] The 4-methyl-1-pentene-α-olefin copolymer (b) is preferred as the 4-methyl-1-pentene polymer (B) because it can suppress the tackiness of the substrate while improving adhesion to the substrate and conformability to deformations such as expansion, contraction, and bending. The α-olefin is preferably a linear α-olefin having 2 to 4 carbon atoms, such as ethylene, propylene, 1-butene, etc. Ethylene or propylene is more preferred, and propylene is even more preferred, as these provide excellent copolymerizability and physical properties to the copolymer (b).

[0153] Examples of adhesion inhibitors include waxes such as microcrystalline wax; EO / PO copolymers; fatty acid amides; silicones such as silicone resins and silicone oils; organic pigments; organic substances such as resin particles; silicates such as talc and zeolite; clays such as kaolin and attapulgite; calcium carbonate; diatomaceous earth; silicas such as fumed silica and precipitated silica; and inorganic substances such as inorganic pigments.

[0154] Examples of organic pigments include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, threne pigments, indigo pigments, phthalone pigments, methine azomethine pigments, and metal complex pigments.

[0155] Examples of inorganic pigments include carbon black, titanium oxide, iron black, yellow iron oxide, red iron oxide, and ultramarine.

[0156] Resin particles are particles made from thermoplastic resins such as polystyrene, acrylic resins such as polymethyl methacrylate, ethylene-vinyl acetate copolymers, and styrene-acrylic copolymers, or thermosetting resins such as epoxy resins, guanamine resins, benzoguanamine resins, melamine resins, and urethane resins. Resin particles include solid resin particles with no internal gaps and resin particles with internal voids. Resin particles may also be nonporous resin particles with no pores (fine pores) on the particle surface, or porous resin particles with pores on the particle surface.

[0157] The resin particles may contain dyes, pigments, or color-changing materials such as thermochromic materials and photochromic materials.

[0158] Examples of dyes include acid dyes, basic dyes, direct dyes, oil-soluble dyes, and disperse dyes. Examples of resin particles containing a dye include resin particles in which a dye is homogeneously dissolved or dispersed in the resin particles, and resin particles in which a dye is dyed.

[0159] As the pigment, the above-mentioned organic pigments or inorganic pigments can be used. Examples of resin particles containing a pigment include resin particles in which the pigment is uniformly dispersed, resin particles whose surfaces are coated with a pigment, etc. Here, the pigment may be surface-treated by various conventionally known methods in order to improve dispersibility or adsorption to the resin that constitutes the resin particles.

[0160] As the color-changing material, the above-mentioned thermochromic material or photochromic material can be used. Examples of resin particles containing a thermochromic material or a photochromic material include resin particles in which the thermochromic material is uniformly dispersed in the resin particles, and resin particles in which the photochromic material is uniformly dispersed in the resin particles, and the above-mentioned reversible thermochromic resin particles or reversible photochromic resin particles can also be used.

[0161] The resin particles can be produced by a pulverization method, a spray drying method, or a polymerization method in which polymerization is carried out in an aqueous or oily medium in the presence of a dye, a pigment, or a thermochromic or photochromic material, such as a suspension polymerization method, a suspension polycondensation method, a dispersion polymerization method, or an emulsion polymerization method.

[0162] The shape of the resin particles is not particularly limited, and resin particles can be spherical (e.g., spherical, ellipsoidal, approximately spherical), polygonal, flat, needle-like, fibrous, etc. Of these, spherical resin particles are preferred.

[0163] Since the wall of a microcapsule pigment is made of resin, microcapsule pigments encapsulating a dye or pigment, the above-mentioned reversible thermochromic microcapsule pigments, and reversible photochromic microcapsule pigments can also be used as resin particles.

[0164] The blending ratio of the adhesion suppressant to the total mass of the liquid composition for forming an adhesion-suppressing layer is not particularly limited, but is preferably 0.5 to 40 mass%, more preferably 1 to 30 mass%, and even more preferably 5 to 15 mass%. If the blending ratio of the adhesion suppressant exceeds 40 mass%, the dispersion stability of the adhesion suppressant in the liquid composition tends to deteriorate. On the other hand, if the blending ratio is less than 0.5 mass%, the effect of the adhesion suppressant in suppressing the adhesion of the substrate, which occurs at temperatures near the glass transition temperature, tends to be poor.

[0165] The average particle size of the material used as the adhesion inhibitor is preferably in the range of 10 nm to 15 μm, more preferably 100 nm to 10 μm. When the average particle size is within the above range, the dispersion stability of the adhesion inhibitor in the liquid composition is excellent, and the handleability of the liquid composition is improved. In addition to the above-mentioned measurement method, the average particle size can also be measured by observation using a scanning electron microscope (SEM) or a transmission electron microscope (TEM).

[0166] The solvent is not particularly limited as long as it can dissolve the 4-methyl-1-pentene polymer (B) and does not affect the adhesion inhibitor, and the same solvents as those described above can be used.

[0167] The liquid composition for forming an adhesion-suppressing layer can contain various oligomers to improve the dispersibility of the adhesion suppressant in the liquid composition, thereby obtaining an adhesion-suppressing layer that is even more effective in suppressing the adhesion of the substrate that occurs at temperatures near the glass transition temperature.

[0168] Examples of oligomers include styrene-based oligomers, acrylic oligomers, terpene-based oligomers, silicone-based oligomers, etc. Among these, styrene-based oligomers are preferred because of their excellent compatibility with 4-methyl-1-pentene polymers, especially 4-methyl-1-pentene-α-olefin copolymers. As the styrene-based oligomer, the same ones as those mentioned above can be used.

[0169] The mass ratio of the 4-methyl-1-pentene polymer (B) to the styrene oligomer in the liquid composition for forming an adhesion-suppressing layer is not particularly limited, but is preferably 1:0.5 to 1:5, and more preferably 1:1 to 1:2. When the mass ratio is within the above range, it becomes easy to improve the dispersibility of the adhesion suppressant.

[0170] If necessary, various additives may also be added to the liquid composition for forming an adhesion-suppressing layer. Examples of additives include crosslinking agents, curing agents, drying agents, plasticizers, viscosity modifiers, dispersants, ultraviolet absorbers, antioxidants, light stabilizers, anti-settling agents, smoothing agents, gelling agents, antifoaming agents, matting agents, penetrating agents, pH adjusters, foaming agents, coupling agents, moisturizing agents, lubricants, antifungal agents, preservatives, and rust inhibitors.

[0171] The mass ratio of the 4-methyl-1-pentene polymer (B) to the adhesion suppressant in the liquid composition for forming an adhesion-suppressing layer is not particularly limited, but is preferably 1:0.5 to 1:5, more preferably 1:0.5 to 1:2, and even more preferably 1:1 to 1:2. When the mass ratio is within the above range, it becomes easy to improve the dispersion stability of the adhesion suppressant in the liquid composition.

[0172] The liquid composition for forming an adhesion-suppressing layer can be produced by any conventionally known method. Specifically, it can be produced by mixing the required amounts of the above-mentioned components and stirring them with various stirrers such as a propeller stirrer, a homodisper, or a homomixer, or by dispersing them with various dispersers such as a bead mill.

[0173] From the viewpoints of the adhesion of the adhesion-suppressing layer to the substrate and its ability to follow deformations such as expansion, contraction, and bending, it is preferable that both polymer (A) and polymer (B) contain structural units derived from an α-olefin having 2 to 20 carbon atoms. It is more preferable that the α-olefin is propylene, that is, both polymer (A) and polymer (B) contain structural units derived from propylene.

[0174] By dispersing an adhesion suppressant in a vehicle containing the 4-methyl-1-pentene polymer (B), a solvent, and, if necessary, various additives, The liquid composition for forming an adhesion-suppressing layer may be a printing ink used in screen printing, offset printing, process printing, gravure printing, coater printing, pad printing, etc.; a coating material used in brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating, dip coating, etc.; an inkjet ink; or an ultraviolet-curable ink.

[0175] When the liquid composition for forming an adhesion-suppressing layer is used as a printing ink, the blending ratio of the solvent to the total mass of the liquid composition is not particularly limited, but is preferably 50 to 80 mass %, more preferably 60 to 80 mass %. When the liquid composition for forming an adhesion-suppressing layer is used as a coating material, the blending ratio of the solvent to the total mass of the liquid composition is not particularly limited, but is preferably 70 to 90 mass %, more preferably 75 to 85 mass %. By ensuring that the blending ratio of the solvent is within the above range, the stability and handling properties of the liquid composition can be improved.

[0176] The color-changing laminate according to the present invention may be configured to include a substrate made of the 4-methyl-1-pentene polymer (A) and a color-changing layer formed by volatilizing a solvent from the liquid composition according to the present invention, and to include an adhesion-suppressing layer formed by volatilizing a solvent from an adhesion-suppressing layer-forming liquid composition on the surface of the substrate opposite to the surface on which the color-changing layer is formed. The method for producing such a color-changing laminate is not particularly limited, and the laminate may be produced, for example, by printing or applying a liquid composition on the substrate and volatilizing the solvent from the liquid composition to form a color-changing layer, and then printing or applying a liquid composition for forming an adhesion-suppressing layer to the surface of the substrate opposite to the surface on which the color-changing layer is formed and volatilizing the solvent from the liquid composition to form an adhesion-suppressing layer.

[0177] The laminate of the present invention can be further provided with a member to form a composite, and the member can be endowed with the temperature sensitivity, shape deformability, and shape retention properties of the substrate, as well as the color change property of the color-changing layer. In other words, the composite has both the properties inherent in the laminate and the properties inherent in the member.

[0178] The material is not particularly limited as long as it does not impair the properties of the laminate, such as temperature sensitivity, shape deformability, shape retention, and colorfastness, and examples thereof include paper, synthetic paper, fiber, knitted fabric, woven fabric, nonwoven fabric, and other fabrics, artificial leather, synthetic leather, leather, plastic, elastomer, rubber, foam, mesh structure, glass, ceramic material, metal, wood, stone, ceramic, etc. The material may have an uneven shape, but a sheet-like shape is preferred.

[0179] The method for producing the composite is not particularly limited, and various methods can be used for production, such as by providing an adhesive layer between the laminate and the member to bond them together, or by interposing a heat-sealing film between the laminate and the member and bonding them together by heat and pressure bonding.

[0180] The color-changing laminate or a composite using the color-changing laminate according to the present invention changes color in response to temperature changes or light irradiation, and has shape deformability and shape retention, and therefore can be used as a color-changing and deformable article. Specific examples of color-changing and deformable articles include the following: (1)Toys Dolls and animal-shaped toys; hair for dolls and animal-shaped toys; doll houses and furniture; doll accessories such as clothing, hats, bags, shoes, etc.; accessory toys; stuffed toys; drawing toys; toy picture books; puzzle toys such as jigsaw puzzles; building block toys; building blocks; clay toys; fluid toys; tops; kites; musical instrument toys; cooking toys; gun toys; capture toys; background toys; mask toys; origami; toys imitating vehicles, animals, plants, buildings, food, etc. (2) Clothing Clothing such as T-shirts, sweatshirts, blouses, dresses, swimwear, raincoats, skiwear, etc.; underwear; footwear such as shoes; shoelaces; shoe components such as insoles, outsoles, and midsoles; cloth personal items such as handkerchiefs, towels, and cloth cloths; gloves; ties; hats; sportswear, etc. (3) Mobility equipment Steering wheels, saddles, shift levers, bumpers, seats, seat belts, headrests, armrests, door trim, instrument panels, various supports, various cushions, vibration damping materials, etc. (4) Indoor decorations Carpets, curtains, curtain strings, tablecloths, rugs, cushions, floor cushions, picture frames, artificial flowers, photo frames, etc. (5) Furniture Futons, pillows, mattresses, bedding such as beds, chairs, floor chairs, sofas, lighting equipment, heating and cooling equipment, etc. (6)Electronic equipment Mobile phones, smartphones, smart watches, smart glasses, earphones, headphones, PCs, mice, cameras (for example, grip parts), speakers, games, protective cases for various electronic devices, covers for various electronic devices, etc. (7) Ornaments Rings, bracelets, tiaras, necklaces, earrings, hair clips, false nails, ribbons, scarves, watches (e.g., bands), glasses (e.g., nose pads and ear pads), key chains, etc. (8) Stationery Writing implements (e.g., grips); notebooks, book covers, etc.; adhesive tape, etc. (9)Daily necessities Toiletries such as disposable diapers, bath products, toothbrushes, cooling and heat-retaining bags, hand warmers, thermometers, watering cans, buckets, cleaning tools, masks (e.g., nose fitters), face packs, foundation tape, cosmetics, etc. (10) Kitchen utensils Cookware (e.g. knife handles), lunch boxes, water bottles, cups, plates, chopsticks, spoons, forks, frying pans, coasters, pots, trivets, placemats, etc. (11) Medical and nursing care supplies Supporters, casts, bandages, adhesive plasters, chairs for lower back pain, wheelchairs, health equipment, etc. (12) Other Calendars, labels, cards, recording materials, various printed materials for preventing counterfeiting; picture books and other books; grip tape for tennis rackets, baseball bats, etc., sports equipment such as gloves, protectors, nets, etc.; bags; packaging containers; embroidery thread; fishing tackle; musical instruments; ice packs; wallets and other bags; umbrellas; vehicles; buildings; temperature detection indicators; teaching aids such as picture books and maps; pet supplies, etc. [Example]

[0181] Examples are shown below. Unless otherwise specified, "parts" in the examples refer to "parts by mass."

[0182] Preparation of reversible thermochromic microcapsule pigment A A reversible thermochromic composition consisting of 1.5 parts of 3-(2-ethoxy-4-diethylaminophenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide as component (A), 5 parts of 2,2-bis(4-hydroxyphenyl)hexafluoropropane as component (B), and 50 parts of cyclohexylmethyl stearate as component (C) was added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall material and 50 parts of a cosolvent, and then emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution. After heating and stirring, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. Reversible thermochromic microcapsule pigment A was obtained from the above microcapsule dispersion by centrifugation. Microcapsule pigment A had a complete color development temperature t1 of 13°C and a complete decolorization temperature t4 of 38°C, and reversibly changed from blue to colorless with temperature change.

[0183] Preparation of reversible photochromic microcapsule pigment a A reversible photochromic composition was prepared by uniformly dissolving 1 part of 3,3,9,9-tetraphenyl-3H,9H-naphtho[2,1-b:6,5-b']-dipyrane in 50 parts of styrene-α-methylstyrene copolymer (Eastman Chemical Company, product name: Picolastic A-5) with heating. The resulting solution was added to a mixed solution consisting of 20 parts of aromatic isocyanate prepolymer and 20 parts of ethyl acetate as the wall material, and then emulsified and dispersed in a 15% aqueous gelatin solution. The mixture was heated and stirred to prepare a microcapsule dispersion. Reversible photochromic microcapsule pigment a was obtained from the microcapsule dispersion by centrifugation. Microcapsule pigment a reversibly changed from orange to colorless upon light irradiation.

[0184] Example 1 Preparation of liquid composition A liquid composition (reversible thermochromic liquid composition), which is a printing ink for screen printing, was prepared by uniformly mixing 13 parts of microcapsule pigment A (previously cooled to 13°C or below to develop a blue color) in a vehicle consisting of 9 parts of a 4-methyl-1-pentene polymer (4-methyl-1-pentene·α-olefin copolymer) [manufactured by Mitsui Chemicals, Inc., product name: Absoutomer EP-1001] and 78 parts of a solvent (xylene).

[0185] Fabrication of the laminate (see Figure 4) A white substrate (0.5 mm thick) composed of a 4-methyl-1-pentene polymer exhibited at least one maximum loss tangent temperature between 10 and 100°C, as determined by dynamic viscoelasticity measurements at a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, and a loss tangent maximum of 0.5 to 3.5. The ink was used to print a solid pattern on the surface of the substrate using an 80-mesh screen, followed by drying and curing to form a color-change layer, resulting in a laminate. The 4-methyl-1-pentene polymer constituting the substrate was a 4-methyl-1-pentene-propylene copolymer that met the following requirements: The proportion of 4-methyl-1-pentene-derived structural units is 72 mol%, and the proportion of propylene-derived structural units is 28 mol%. Temperature at which loss tangent shows maximum value: 28℃ Maximum loss tangent: 2.6 ·Intrinsic viscosity [η]: 1.5dL / g ·Density: 0.84g / cm 3

[0186] The laminate of Example 1 had a visible blue solid pattern at ambient temperatures (e.g., 25°C) and was flexible. When the temperature reached 28°C or higher due to human body temperature or the like, the laminate could be deformed into any shape by applying external force. The laminate maintained its colored state unless heated to 38°C or higher, and could be repeatedly deformed into any shape and retain the deformed shape above 28°C. When the laminate was heated to 38°C or higher, the microcapsule pigment A completely disappeared and the solid blue pattern was no longer visible. At this point, the temperature of the laminate was sufficiently higher than the temperature at which the flexibility of the base material changes, and it was possible to determine from the change in the laminate from a colored state to a discolored state that it could be easily deformed into any shape by applying an external force. Next, an external force was applied to the laminate to deform it into a desired shape, and then it was cooled to a temperature below 28°C while the external force was still applied. The laminate maintained its deformed shape even after the external force was removed. The laminate maintained its decolorized state unless cooled to 13°C or below, and could be repeatedly deformed into a desired shape and maintained the deformed shape at 28°C. At ambient temperatures, the laminate maintained its deformed shape for a certain period of time, and then gradually returned to its original shape. When the laminate was cooled to below 13°C, the microcapsule pigment A completely developed color and a solid blue pattern was visible. At this time, the laminate was at a temperature sufficiently lower than the temperature at which the flexibility of the substrate changes, and it was possible to determine from the change of the laminate from a decolorized state to a colored state that the deformed shape was well maintained without the application of external force.

[0187] Examples 2 to 5 and Comparative Example 1 A liquid composition, which is a printing ink used for screen printing, was prepared in the same manner as in Example 1, except that the types and amounts of the materials to be blended were changed to those shown in Table 1 below. The laminate of Example 2 was produced in the same manner as in Example 1. The laminates of Examples 3 to 5 and Comparative Example 1 were produced in the same manner as in Example 1, except that the 80-mesh screen used in Example 1 was changed to a 180-mesh screen.

[0188] Example 6 Preparation of liquid composition A liquid composition (reversible thermochromic liquid composition) for use in spray coating was prepared by uniformly mixing 6.5 parts of microcapsule pigment A (previously cooled to 13°C or below to develop a blue color) in a vehicle consisting of 4.5 parts of a 4-methyl-1-pentene polymer (4-methyl-1-pentene·α-olefin copolymer) [manufactured by Mitsui Chemicals, Inc., product name: Absoutomer EP-1001], 6.5 parts of a styrene oligomer (α-methylstyrene copolymer) [manufactured by Eastman Chemical Company, product name: Picolastic A-5], and 82.5 parts of a solvent (xylene).

[0189] Fabrication of the laminate (see Figure 4) The paint was spray-painted onto the surface of a substrate similar to that used in Example 1, and then dried and cured to provide a color-changing layer, thereby obtaining a laminate.

[0190] Examples 7 to 9 and Comparative Example 2 A liquid composition, which is a paint to be used for spray coating, was prepared in the same manner as in Example 6, except that the types and amounts of the materials to be blended were changed to those shown in Table 1 below. The laminates of Examples 7 to 9 and Comparative Example 2 were produced in the same manner as in Example 6.

[0191] [Table 1]

[0192] The contents of the materials in Table 1 are explained according to the note numbers. (1) Cooled to below 13°C in advance to turn blue (2) 4-Methyl-1-pentene-α-olefin copolymer [Mitsui Chemicals, Inc., product name: Absortomer EP-1001] The proportion of 4-methyl-1-pentene-derived structural units is 72 mol%, and the proportion of propylene-derived structural units is 28 mol%. ·Intrinsic viscosity [η]: 1.4dL / g Melting point (Tm): None ·Density: 840kg / cm3 ·Molecular weight distribution (Mw / Mn): 2.1 (3) 4-Methyl-1-pentene-α-olefin copolymer [Mitsui Chemicals, Inc., product name: Absortomer EP-1013] 4-methyl-1-pentene-derived structural unit ratio: 85 mol%, propylene-derived structural unit ratio: 15 mol% ·Intrinsic viscosity [η]: 1.5dL / g Melting point (Tm): 130℃ ·Density: 838kg / cm 3 ·Molecular weight distribution (Mw / Mn): 2.0 (4) 50% acrylic resin / xylene solution (5) α-methylstyrene copolymer [Eastman Chemical Company, product name: Picolastic A-5 (mass average molecular weight: 317)] (6) Xylene (7) Solvesso 100 (8) Ethyl acetate (9) Methyl isobutyl ketone

[0193] [Dispersibility evaluation] The color-changing layers of the liquid compositions prepared in Examples 1 to 9 and Comparative Examples 1 and 2, and the laminates prepared using the liquid compositions, were visually inspected and the dispersibility of the color-changing material was evaluated according to the following criteria. The evaluation results are shown in Table 2 below. A: No aggregates of the color-changing material were observed in the liquid composition, and the color-changing material was uniformly dispersed. In addition, the concentration of the color-changing layer was uniform and the appearance was good. B: Some aggregates of the color-changing material were observed in the liquid composition, but the uniformity of the concentration and appearance of the color-changing layer were at a level that would not pose a problem in practical use. C: Many aggregates of the color-changing material were observed in the liquid composition, and the color-changing material was not dispersed sufficiently. In addition, the concentration of the color-changing layer was not uniform, and there was roughness due to poor dispersion.

[0194] [Adhesion test] The adhesiveness of the color-changing layer to the substrate in each of the laminates produced in Examples 1 to 9 and Comparative Examples 1 and 2 was evaluated according to the cross-cut method specified in JIS K 5600-5-6, based on the following criteria. The evaluation results are shown in Table 2 below. A: No peeling was observed in the cross-cut portion of the discolored layer. B: Slight peeling was observed in the cross-cut portion of the discolored layer, but it was at a level that did not pose a problem in practical use. C: Large peeling was observed in the cross-cut portion of the discolored layer.

[0195] [Follow-up test] A rectangle measuring 50 mm long x 10 mm wide was cut out from the location where the color-change layer was to be provided of each of the laminates produced in Examples 1 to 9 and Comparative Examples 1 and 2 to prepare a test piece. Both ends of the test piece were attached to a tensile tester so that the distance between the chucks was 30 mm, and a tensile load was applied at a constant rate in a 30°C environment until the distance between the chucks reached 60 mm. The test piece was then removed from the tensile tester and allowed to stand in a 30°C environment to restore its original shape. The conformability of the discoloration layer to deformation was evaluated based on the appearance of the discoloration layer on the test piece after the test using the following criteria. The evaluation results are shown in Table 2 below. A: No peeling or breakage was observed in the discolored layer. B: A small amount of peeling or breakage was observed in the discolored layer, but it was at a level that did not pose a problem in practical use. C: Numerous peelings or breaks were observed in the discolored layer.

[0196] [Table 2]

[0197] Application example 1 Preparation of reversible thermochromic microcapsule pigment B A reversible thermochromic composition consisting of 3 parts of 2-anilino-3-methyl-6-dibutylaminofluoran as component (A), 6 parts of 4,4'-(2-methylpropylidene)bisphenol as component (B), and 25 parts of cetyl alcohol and 25 parts of stearyl caprate as component (C) was added to a mixed solution consisting of 30 parts of an aromatic isocyanate prepolymer as a wall film material and 50 parts of a cosolvent, and then emulsified and dispersed in an 8% aqueous polyvinyl alcohol solution. After continued stirring while heating, 2.5 parts of a water-soluble aliphatic modified amine was added and further stirring was continued to prepare a microcapsule dispersion. Reversible thermochromic microcapsule pigment B was obtained from the above microcapsule dispersion by centrifugation. Microcapsule pigment B had a complete color development temperature t1 of 28°C and a complete decolorization temperature t4 of 30°C, and reversibly changed from black to colorless with temperature change.

[0198] Preparation of liquid composition A liquid composition serving as a printing ink for screen printing was prepared in the same manner as in Example 3, except that the microcapsule pigment A used in Example 3 was changed to the microcapsule pigment B.

[0199] Fabrication of the laminate (see Figure 5) A transparent substrate (0.6 mm thick) composed of a 4-methyl-1-pentene polymer exhibited at least one maximum loss tangent temperature between 10 and 100°C, as determined by dynamic viscoelasticity measurements at a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, and a loss tangent maximum of 0.5 to 3.5. The ink was used to print a dot pattern on the surface of the substrate using a 180-mesh screen, followed by drying and curing to form a color-change layer. A 16 μm-thick transparent PET film with an adhesive layer was then attached to the color-change layer via the adhesive layer to obtain a laminate. The 4-methyl-1-pentene polymer constituting the substrate was a 4-methyl-1-pentene-propylene copolymer that met the following requirements: The proportion of 4-methyl-1-pentene-derived structural units is 72 mol%, and the proportion of propylene-derived structural units is 28 mol%. Temperature at which loss tangent shows maximum value: 28℃ Maximum loss tangent: 2.6 ·Intrinsic viscosity [η]: 1.5dL / g ·Density: 0.84g / cm 3

[0200] The laminate of Application Example 1 had a visible black dot pattern at ambient temperatures (e.g., 25°C), a uniform density of the dot pattern, an excellent appearance, and flexibility. When the temperature reached 30°C or higher due to human body heat or other factors, the laminate could be deformed into any shape by applying an external force. At this time, the microcapsule pigment B completely decolorized, and the black dot pattern was no longer visible. Therefore, it was possible to determine from the change in the laminate from a colored state to a decolored state that the temperature had reached a point where the laminate could be deformed into any shape by applying an external force. Next, the laminate was deformed into a desired shape by applying an external force, and then cooled to below 28°C while the external force was still applied. The deformed shape could be maintained even after the external force was removed. At this time, the microcapsule pigment B completely developed color, revealing a visible black dot pattern. Therefore, the change in flexibility of the laminate from a colorless state to a colored state indicated that it had reached a temperature at which it could maintain the deformed shape without the application of external force. At ambient temperature, the deformed shape was maintained for a certain period of time, after which it gradually returned to its original shape. The laminate had a transparent PET film (transparent resin film) on the color-changing layer, which provided excellent durability of the color-changing layer. Furthermore, the laminate conformed to deformation without impairing the shape-deformability or shape-retaining ability of the substrate.

[0201] Application example 2 Preparation of liquid composition A liquid composition (non-discoloring liquid composition) that is a printing ink for screen printing was prepared by uniformly mixing 9 parts of a pink general pigment (non-discoloring colorant) in a vehicle consisting of 11 parts of 4-methyl-1-pentene-α-olefin copolymer (manufactured by Mitsui Chemicals, Inc., product name: Absortomer EP-1001), 13.5 parts of a styrene oligomer (α-methylstyrene copolymer) (manufactured by Eastman Chemical Company, product name: Picolastic A-5), and 66.5 parts of xylene.

[0202] Fabrication of the laminate (see Figure 6) A dot pattern was printed using the above printing ink with a 180-mesh screen on the surface of the same substrate as that used in Example 1, and the dot pattern was dried and cured to provide a non-color-changing layer. Next, a dot pattern was printed on the non-color-changing layer with the printing ink of Example 4 with a 180-mesh screen so as to overlap the dot pattern on the non-color-changing layer, and the dot pattern was dried and cured to provide a color-changing layer (reversible thermocolor-changing layer), thereby obtaining a laminate.

[0203] The laminate of Application Example 2 had a visible purple dot pattern at ambient temperatures (e.g., 25°C), a uniform density of the dot pattern, excellent appearance, and flexibility. When the laminate reached a temperature of 28°C or higher due to human body temperature or other factors, it could be deformed into any shape by applying an external force. Unless heated to 38°C or higher, the laminate maintained a visible purple dot pattern, and it was possible to repeatedly deform into any shape and maintain the deformed shape above 28°C. When the laminate was heated to 38°C or higher, the microcapsule pigment A completely disappeared and the dot pattern changed from purple to pink. At this point, the laminate was at a temperature sufficiently higher than the temperature at which the flexibility of the base material changes, and it was possible to determine from the color change of the dot pattern on the laminate that it could be easily deformed into any shape by applying an external force. Next, an external force was applied to the laminate to deform it into a desired shape, and when it was cooled to a temperature below 28°C while the external force was still applied, the laminate was able to maintain the deformed shape even after the external force was removed. The pink dot pattern remained visible on the laminate unless it was cooled below 13°C, and it was possible to repeatedly deform it into a desired shape and maintain the deformed shape above 28°C. At ambient temperature, after maintaining the deformed shape for a certain period of time, it gradually returned to its original shape. When the laminate was cooled to below 13°C, the microcapsule pigment A completely developed color and the dot pattern changed from pink to purple. At this point, the laminate was at a temperature sufficiently lower than the temperature at which the flexibility of the substrate changes, and it was possible to determine from the color change in the dot pattern of the laminate that the deformed shape was well maintained without the application of external force.

[0204] Application example 3 Making doll clothes (doll accessories) The laminate of Example 6 was cut and sewn to make doll clothes.

[0205] When the clothing of Application Example 3 was cooled to 13°C or below, the microencapsulated pigment A completely developed its color, exhibiting the blue color due to the microencapsulated pigment A, and this state was maintained unless the clothing was heated to 38°C or above. Furthermore, when the clothing was heated to 38°C or above, the microencapsulated pigment A completely lost its color, exhibiting the white color due to the base material, and this state was maintained unless the clothing was cooled to 13°C or below. Thus, the color of the clothing could be repeatedly changed by heating or cooling, and it was possible to maintain either state at a living environment temperature (e.g., 25°C). Furthermore, since the clothes can be deformed by external force when they reach a temperature of 28°C or higher due to human body heat, they can be easily put on a doll by warming them with your hands and making them stretch.Furthermore, by warming them with your hands and raising them again to 28°C or higher, they can be easily stretched and made to be easily removed from the doll.

[0206] Application example 4 Making color-changing toys (photochromic origami) The surface of a substrate similar to that used in Application Example 1 was spray-painted with the paint of Example 9, dried and cured to form a color-changing layer, and a laminate was obtained. This laminate was cut into 10 cm squares to create a color-changing toy (photochromic origami).

[0207] When the origami of Application Example 4 was irradiated with light from an irradiator equipped with a blue LED (peak wavelength: 430 nm), the microencapsulated pigment a completely developed its color, exhibiting the orange color of the microencapsulated pigment a, and this state remained as long as the light irradiation was stopped. Furthermore, when the light irradiation was stopped, the microencapsulated pigment a completely lost its color and the origami became transparent, and this state remained as long as the light irradiation was stopped. Therefore, the color of the origami could be repeatedly changed by irradiating it with light or by stopping the light irradiation. Furthermore, since origami can be deformed by external force when it reaches a temperature of 28°C or higher due to human body heat, it was possible to create objects such as cranes, balloons, and shuriken by warming the origami with one's hands and folding it. Furthermore, the origami was able to maintain its original shape at ambient temperatures. Furthermore, by warming the origami with one's hands again and raising it above 28°C, it was possible to restore the origami to its original flat shape, allowing for repeated play with the origami.

[0208] Application example 5 Making writing implements An adhesive layer was provided on the surface of the laminate of Example 7 opposite to the surface on which the color-changing layer was provided. Then, this laminate was brought into a color-developing state and wrapped around the grip of a barrel of a writing implement (ballpoint pen) via the adhesive layer, thereby producing a writing implement with a color-changing grip.

[0209] When holding the grip of the writing instrument of Application Example 5, the heat from the fingertips caused the microcapsule pigment A to discolor in the areas where the fingertips were touching, and the grip changed from blue to white in parts. Even after the fingertips were removed from the brush grip and the writing instrument was left alone, the grip maintained its partially discolored state unless it was cooled to below 13°C. Therefore, only the areas of the writing instrument that were touching the grip changed color, and the color change was maintained at living environment temperatures, so it was possible to confirm from the appearance of the grip color whether the writing instrument was being held correctly. Furthermore, the grip deforms at the point where the fingertips are in contact with it due to heat from the fingertips, so the writing implement has an excellent fit when held in the hand.

[0210] Application example 6 Preparation of liquid composition A liquid composition (reversible thermochromic liquid composition) for use in spray coating was prepared by uniformly mixing 6.5 parts of microencapsulated pigment A (previously cooled to 13°C or below to develop a blue color) and 0.5 parts of a yellow general pigment (non-color-changing colorant) in a vehicle consisting of 4.5 parts of a 4-methyl-1-pentene polymer (4-methyl-1-pentene·α-olefin copolymer) [Mitsui Chemicals, Inc., product name: Absortomer EP-1001], 6.5 parts of a styrene oligomer (α-methylstyrene copolymer) [Eastman Chemical Company, product name: Picolastic A-5], and 82.5 parts of a solvent (xylene).

[0211] Preparation of liquid composition for forming adhesion-suppressing layer Eight parts of titanium oxide were uniformly mixed in a vehicle consisting of 4.5 parts of a 4-methyl-1-pentene polymer (4-methyl-1-pentene·α-olefin copolymer) [manufactured by Mitsui Chemicals, Inc., product name: Absortomer EP-1001], 6.5 parts of a styrene oligomer (α-methylstyrene copolymer) [manufactured by Eastman Chemical Company, product name: Picolastic A-5], and 82.5 parts of a solvent (xylene), to prepare a liquid composition for forming an adhesion-suppressing layer, which is a paint used in spray coating.

[0212] Fabrication of the laminate (see Figure 7) The reversible thermochromic liquid composition was spray-coated on the surface of the same substrate as that used in Application Example 1, and then dried and cured to provide a color-changing layer. Next, the liquid composition for forming an adhesion-suppressing layer was spray-coated on the surface of the substrate opposite to the surface on which the discoloration layer was to be formed, and the composition was dried and hardened to form an adhesion-suppressing layer, thereby obtaining a laminate.

[0213] The laminate of Application Example 6 had a visible green solid pattern at ambient temperatures (e.g., 25°C), a uniform solid pattern density, excellent appearance, and flexibility. When the laminate reached a temperature of 28°C or higher due to human body temperature or other factors, it could be deformed into any shape by applying external force. Unless heated to 38°C or higher, the laminate maintained a visible green solid pattern, and it was possible to repeatedly deform into any shape and maintain the deformed shape above 28°C. When the laminate was heated to 38°C or higher, the microcapsule pigment A completely disappeared and the solid pattern changed from green to yellow. At this point, the laminate was at a temperature sufficiently higher than the temperature at which the flexibility of the base material changes, and it was possible to determine from the color change of the solid pattern on the laminate that it could be easily deformed into any shape by applying an external force. Next, an external force was applied to the laminate to deform it into a desired shape, and when it was cooled to a temperature below 28°C while the external force was still applied, the laminate was able to maintain the deformed shape even after the external force was removed. The yellow solid pattern remained visible on the laminate unless it was cooled below 13°C, and it was possible to repeatedly deform it into a desired shape and maintain the deformed shape above 28°C. Furthermore, under normal temperature conditions, after maintaining the deformed shape for a certain period of time, it gradually returned to its original shape. When the laminate was cooled to below 13°C, the microcapsule pigment A completely developed color and the solid pattern changed from yellow to green. At this point, the laminate was at a temperature sufficiently lower than the temperature at which the flexibility of the substrate changes, and it was possible to determine from the color change of the solid pattern on the laminate that the deformed shape was well maintained without the application of external force. In the above laminate, an adhesion-suppressing layer is provided on the surface of the substrate opposite to the surface on which the color-changing layer is provided, so that the adhesion of the substrate is suppressed, and the laminates do not adhere to each other even when brought into direct contact with each other at a temperature near the glass transition temperature (near 28°C). Furthermore, the adhesion-suppressing layer has excellent dispersibility of the adhesion suppressant, and is even more effective in suppressing the adhesion of the substrate that occurs at temperatures near the glass transition temperature. The color-change layer and the adhesion-suppressing layer each had excellent adhesion to the substrate, and were able to follow deformations of the laminate without impairing the shape deformability or shape retention of the substrate.

[0214] Application example 7 Making doll clothes (doll accessories) The laminate of Application Example 6 was cut and sewn so that the adhesion-suppressing layer was on the inside (the color-changing layer was on the outside) to produce doll clothing (skirt).

[0215] When the skirt of Application Example 7 was cooled to 13°C or below, the microencapsulated pigment A completely developed its color, presenting a green color that was a mixture of the blue from the microencapsulated pigment A and the yellow from the general pigment, and this state was maintained unless heated to 38°C or above. Furthermore, when heated to 38°C or above, the microencapsulated pigment A completely lost its color, presenting the yellow from the general pigment, and this state was maintained unless cooled to 13°C or below. Thus, the skirt's color could be repeatedly changed by heating or cooling, and it could be maintained in either state at ambient temperatures (e.g., 25°C). Furthermore, when the skirt was placed on a doll, it could be deformed by external force when it reached a temperature of 28°C or higher due to human body temperature, etc., so it was possible to wrinkle the skirt by warming it with one's hand and deforming any desired part. Furthermore, because the laminate of Application Example 6 was provided with an anti-adhesion layer, even if the skirts (laminates) came into contact with each other after being wrinkled, they did not adhere to each other and could be easily peeled off. By warming it with one's hand again to 28°C or higher, the skirt could be restored to its original shape or wrinkled again. The above-mentioned clothing (skirt) had excellent marketability as a toy, as it could be repeatedly deformed.

[0216] Application example 8 Making doll clothes (doll accessories) The laminate of Application Example 6 was cut and sewn so that the adhesion-suppressing layer was on the inside (the color-changing layer was on the outside) to prepare doll clothing (cloak).

[0217] When the mantle of Application Example 8 was cooled to below 13°C, the microencapsulated pigment A completely developed its color, and it turned green, a mixture of the blue from the microencapsulated pigment A and the yellow from the regular pigment, and this state was maintained unless it was heated above 38°C. Furthermore, when heated above 38°C, the microencapsulated pigment A completely lost its color, turning it into the yellow from the regular pigment, and this state was maintained unless it was cooled below 13°C. Thus, the mantle could be repeatedly changed in color by heating or cooling, and could be maintained in either state at ambient temperatures (e.g., 25°C). Furthermore, when the cape is placed on a doll, it can be deformed by external force when it reaches a temperature of 28°C or higher due to human body temperature, etc., so by warming it with your hands and deforming any desired part, the cape can be wrinkled, recreating the appearance of the cape fluttering in the wind. Furthermore, because the laminate in Application Example 6 is provided with an anti-adhesion layer, even if the capes (laminates) come into contact with each other after being wrinkled, they do not adhere to each other and can be easily peeled off. By warming it with your hands again to 28°C or higher, the cape can be restored to its original shape or wrinkled again. The above clothing (cape) has excellent marketability as a toy because it can be repeatedly deformed.

[0218] Application example 9 Preparation of liquid composition A liquid composition (reversible thermochromic liquid composition) for use in spray coating was prepared by uniformly mixing 6.5 parts of microcapsule pigment B and 0.5 parts of a pink general pigment (non-discoloring colorant) in a vehicle consisting of 4.5 parts of a 4-methyl-1-pentene polymer (4-methyl-1-pentene·α-olefin copolymer) [manufactured by Mitsui Chemicals, Inc., product name: Absortomer EP-1001], 6.5 parts of a styrene oligomer (α-methylstyrene copolymer) [manufactured by Eastman Chemical Company, product name: Picolastic A-5], and 82.5 parts of a solvent (xylene).

[0219] Making a squeeze toy (see Figures 8 and 9) The same substrate as used in Application Example 1 was placed on a mold shaped like a cat's paw (i.e., a mold with five recesses, each with an opening at the top where the paw pad is located) and heated to 40°C, causing the substrate to partially conform to the mold under its own weight and deform into a recess. Next, the inner surfaces of the five recesses on the substrate were spray-painted with the above liquid composition, which was then dried and cured to form a discoloration layer. Next, an adhesive consisting of a urethane resin and ethyl acetate was applied to the flat surface of the substrate (the non-deformed area), and the ethyl acetate was evaporated to form an adhesive layer, resulting in Sheet 1. The liquid composition for forming an adhesion-suppressing layer of Application Example 6 was spray-coated on the surface of a substrate other than the above substrate, which was the same as the substrate used in Application Example 1, and dried and cured to provide an adhesion-suppressing layer, thereby forming Sheet 2. Sheet 2 was placed on the mold with the adhesion-suppressing layer facing downwards so as to cover the entire mold, and Sheets 1 and 2 were bonded together by pressing with a roll. Sheet 1 and Sheet 2 were cut along the shape of the mold and excess portions were removed to produce squeeze toys with air-filled spaces between the sheets.

[0220] When the squeeze toy of Application Example 9 was cooled to 28°C or below, or at ambient temperature (e.g., 25°C), the microencapsulated pigment B completely developed its color, and the paw area turned black. When heated to 30°C or above, the microencapsulated pigment B completely lost its color, and the paw area turned pink due to the general pigment. Therefore, the color of the paw area of ​​the squeeze toy could be repeatedly changed by heating or cooling. The squeeze toy also had a uniform consistency in the paw area, an excellent appearance, and flexibility. When the temperature reached 28°C or higher due to human body temperature or other factors, the flexibility of the paw area changed, becoming even more flexible. It felt excellent to the touch when the paw area was crushed with a finger, and returned to its original shape when the finger was removed from the paw area. The squeeze toy of Application Example 9 has a structure in which the color-changing layer of Sheet 1 and the adhesion-suppressing layer of Sheet 2 face each other in the space, and the color-changing layer also functions as an adhesion-suppressing layer. Therefore, even when the sheets come into contact with each other by crushing the paw area, they do not adhere to each other and can naturally return to their original shape. The above squeeze toy can be crushed with a finger and then returned to its original shape when the finger is removed, making it suitable for repeated play, and is a highly marketable toy. [Explanation of symbols]

[0221] t1 full color temperature t2 color development start temperature t3 decolorization start temperature t4 complete color erasure temperature T1 complete discoloration temperature T2 decolorization start temperature T3 color development start temperature T4 full color temperature ΔH Hysteresis width 1. Laminate 2 Base material 3 Discoloration layer 3′ Discoloration layer 4 Transparent resin layer 5 Non-discoloring layer 6 Adhesion suppression layer 7 Adhesive layer 8 Space section 11 Squeeze toys

Claims

1. A color-changing liquid composition for use with a substrate, comprising a 4-methyl-1-pentene polymer (A), wherein there is at least one temperature in the range of 10 to 100°C at which a maximum value of the loss tangent, determined by dynamic viscoelastic measurement under the conditions of a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, is observed, and the maximum value of the loss tangent is 0.5 to 3.

5. Discolorable materials, A vehicle containing at least a 4-methyl-1-pentene polymer (B) and a solvent, A color-changing liquid composition comprising the following.

2. The liquid composition according to claim 1, wherein the 4-methyl-1-pentene polymer (B) comprises a structural unit derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene.

3. The liquid composition according to claim 1, wherein the vehicle further comprises a styrene oligomer.

4. The liquid composition according to claim 1, wherein the color-changing material is a reversible thermochromic material or a reversible photochromic material.

5. The liquid composition according to claim 4, wherein the reversible thermochromic material is a reversible thermochromic microcapsule pigment containing a reversible thermochromic composition comprising at least (a) an electron-donating color-developing organic compound, (b) an electron-accepting compound, and (c) a reaction medium that controls the color-developing reactions of (a) and (b).

6. A liquid composition according to claim 1, selected from the group consisting of printing inks, paints, inkjet inks, and ultraviolet-curable inks.

7. A color-changing laminate comprising a substrate composed of a 4-methyl-1-pentene polymer (A), wherein there is at least one temperature in the range of 10 to 100°C at which a maximum value of the loss tangent, determined by dynamic viscoelastic measurement under the conditions of a heating rate of 4°C / min, a frequency of 1.59 Hz, and a strain of 0.1%, is observed, and the maximum value of the loss tangent is 0.5 to 3.5, on which a color-changing layer is provided, comprising the liquid composition described in any one of claims 1 to 6.

8. The laminate according to claim 7, wherein the substrate is provided with an adhesion-suppressing layer on the opposite side from where the discoloration layer is provided.

9. The laminate according to claim 8, wherein the adhesion-suppressing layer comprises a liquid composition containing at least an adhesion inhibitor, the 4-methyl-1-pentene polymer (B), and the solvent.

10. A discoloration- and deformable article made using the laminate described in claim 7.

11. A toy, a discoloration-changing and deformable article according to claim 10.

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