JP6510651B2 - Colored composition for heating device decoration, transfer material for heating device decoration, heating device and cooker - Google Patents

Description

  The present invention relates to a coloring composition for heating device decoration, a transfer material for heating device decoration, a heating device and a cooker.

Materials, such as glass and ceramics which are low thermal expansion, are used from a heat resistant viewpoint as heating appliances, such as a cooker top plate used for an electromagnetic heating cooker and an infrared heating cooker. Moreover, also in a gas cooker, glass, a ceramic material, etc. of low thermal expansion are used from the beauty | look and cleaning property being excellent. In a heating device using such glass etc., a metal film such as a Ti (titanium) film is formed on a substrate as a decorating material to visually conceal the cooker, temperature sensor etc. inside, and the metallic luster The aesthetics such as is given to the heating equipment.
However, in the case of using a Ti film as a decorating material (light shielding layer), it was not possible to color the color other than silver which is the color tone of the Ti film which is a protective layer. For this reason, it is possible to color a decorating material in various colors, and a heating implement excellent in heat resistance is required.

On the other hand, Patent Document 1 discloses a cooker top plate disposed above the cooker, which is a glass substrate and an interference layer formed on one surface of the glass substrate and made of silicon nitride or aluminum nitride. And at least one selected from silicon nitride, zirconium nitride, titanium nitride, tantalum nitride, tungsten nitride, and niobium nitride provided on the light shielding layer and provided on the light shielding layer, provided on the interference layer. And an interference layer and a protective layer which are thin films formed in a gas atmosphere having a content of N ₂ gas of 90 to 100% by volume by physical vapor deposition. Is described.

  Patent Document 2 describes a method of transferring a decorative material (pattern layer) formed of an ink containing a pigment for heat-resistant glass and an acrylic resin on a substrate sheet to a heating device which is a cooker top plate. .

  Patent Document 3 shows a cooker top plate used as a top plate of a cooker provided with an electromagnetic heating device, wherein a decorative material (decorative layer) is formed on the surface of a transparent crystallized glass plate, and a decorative layer is formed. A cooker in which 10 to 100 parts by mass of an inorganic pigment is mixed with 100 parts by mass of a silicone resin having a molar ratio of organic groups to Si atoms (organic group / Si) of 0.1 to 1.5. The top plate is described.

International Publication WO2009 / 081649A1 Japanese Patent Application Laid-Open No. 61-121280 JP, 2005-298266, A

When the present inventors examined the performance of the cooker top plate having the decorative material formed by the physical vapor deposition method (sputtering method) described in Patent Document 1, the color adjustment when it deviated from the target color Was impossible, and it was found that improvement in toning properties is required.
Moreover, when the present inventors examined the performance of a heating device which is a cooker top plate having a decorative material using an acrylic resin described in Patent Document 2, improvement in heat resistance from the viewpoint of coloring is required. I understood it.
As a result of examining the performance of the cooker top plate having the decorative material using the trifunctional silicone resin described in the example of Patent Document 3, the inventors of the present invention have been requested to improve the heat resistance from the viewpoint of cracking. I understand. Moreover, when the present inventors examined the performance of the cooker top plate which has the decorating material using the bifunctional silicone resin as described in the comparative example of patent document 3, the improvement in the scratch resistance when it touched with a finger is improved. It turned out that it was asked.

The problem to be solved by the present invention is to provide a coloring composition for heating appliance decoration which is excellent in scratch resistance, heat resistance in view of cracking, heat resistance in view of coloring and color matching property. .
The problem to be solved by the present invention is a heating appliance containing a coloring composition for heating appliance decoration, which is excellent in scratch resistance, heat resistance in view of cracking, heat resistance in view of coloring and color matching property It is an object of the present invention to provide a decorative transfer material and a heating device, and a cooker having the heating device.

  As a result of intensive investigations by the present inventors to solve the above problems, it has been found that the above problems can be solved by using a silicone resin or a silicone rubber-based decorative material having a specific structure.

The present invention, which is a specific means for solving the above problems, and preferred embodiments of the present invention are as follows.
[1] with colorants,
A silicone having a D-body structure represented by the following general formula D and a T-body structure represented by the following general formula T, and a D / T ratio represented by the following formula exceeding 0 and 2.5 or less A coloring composition for heating device decoration, comprising: a resin; and at least one of silicone rubber having a D-body structure;
D / T ratio = (molar amount of silicon atoms contained in D structure) / (molar amount of silicon atoms contained in T structure)
In the general formula D and the general formula T, R ^D1 , R ^D2 and R ^T1 each independently represent a methyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and the wave portion represents another It represents a binding site to the structure.
[2] It is preferable that the coloring composition for heating appliance decoration as described in [1] is used for a cooker top plate.
[3] The coloring composition for heating appliance decoration according to [1] or [2] has a D / T ratio of more than 0 and a silicone resin having a D / T ratio of 0.5 or less. It is preferable that it is a silicone resin which is more than 2.5.
[4] The coloring composition for heating appliance decoration according to any one of [1] to [3] is D / T of silicone resins contained in the coloring composition for heating appliance decoration of a coloring agent. Preferably, the content ratio to the total of silicone resins having a ratio of less than 1 exceeds 1.0.
[5] In the coloring composition for heating device decoration according to any one of [1] to [4], the colorant is preferably an inorganic pigment.
[6] The coloring composition for heating device decoration according to any one of [1] to [5] preferably further contains a graft type silicone polymer represented by the following general formula 1;
In General Formula 1, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, and R ¹¹ and R ¹² each independently represent an arylene group or 1 to 1 carbon atom. 3 represents an alkylene group, R ¹³ and R ¹⁴ each independently represent a single bond or a divalent organic linking group, A represents a group having a pigment adsorption site, and B is a structure represented by the following general formula 2 And l and n each independently represent an integer of 1 or more, and m represents an integer of 0 or more;
In the Formula 2, each of R ¹⁵ and R ¹⁶ independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, k represents an integer of 1 or more.
[7] It has a temporary support and a colored layer,
A transfer material for heating device decoration, the coloring layer comprising the coloring composition for heating device decoration according to any one of [1] to [6].
[8] Have a decorative material on the substrate,
The heating fixture containing the coloring composition for heating fixture decorating as described in any one of [1]-[6].
[9] Have a decorating material on the substrate,
A heating device, wherein the decorative material is a transfer product of the colored layer of the transfer material for heating device decoration according to [7].
[10] The heating device described in [8] or [9] preferably has a protective layer on the side of the decorative material opposite to the substrate.
[11] The heating device according to any one of [8] to [10] preferably has a touch panel.
[12] In the heating device according to [11], the touch panel is preferably a capacitive input device.
[13] In the heating device according to any one of [8] to [12], the heating device is preferably a cooker top plate.
[14] A cooker having the heating appliance according to any one of [8] to [13].

  According to the present invention, it is possible to provide a coloring composition for heating appliance decoration, which is excellent in scratch resistance, heat resistance in view of cracking, heat resistance in view of coloring and color matching properties.

It is a partial expanded sectional view which shows an example of a decorating material. It is a partial expanded sectional view which shows another example of a decorating material. It is a partial expanded sectional view which shows another example of a decorating material. It is a partial expanded sectional view showing the inclination angle which an inclination part and a board | substrate make. It is a cross-sectional schematic which shows the structure of an example of a touch panel. It is the cross-sectional schematic which shows the structure of the other example of a touch panel. It is explanatory drawing which shows an example of the 1st transparent electrode pattern in a touch panel, and a 2nd transparent electrode pattern. It is a cross-sectional schematic which shows the structure of an example of the cooking device of this invention.

Hereinafter, the present invention will be described. The description of the configuration requirements described below may be made based on representative embodiments and examples of the present invention, but the present invention is not limited to the embodiments and examples. In addition, the numerical range represented using "-" in this specification means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
In the notation of groups (atomic groups) in the present specification, notations not describing substitution and non-substitution include those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acrylic” represents acrylic and methacrylic, and “(meth) acryloyl” represents acryloyl and methacryloyl.
Moreover, in the present invention, "mass part" and "part" are synonymous.
Moreover, in the present invention, a combination of preferred embodiments is a more preferred embodiment.
In the present invention, the molecular weight of the polymer component is a weight average molecular weight in terms of polystyrene as measured by gel permeation chromatography (GPC) when tetrahydrofuran is used as a solvent. Specifically, it can be measured under the following conditions.
Column: GPC column TSKgelSuper HZM-H (manufactured by Tosoh Corporation)
-Solvent: Tetrahydrofuran-Standard substance: Monodispersed polystyrene In the present specification, "transparent" means that the average transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more. Therefore, a transparent layer refers to a layer whose average transmittance of visible light with a wavelength of 400 nm to 700 nm is 80% or more. It is preferable that the average transmittance | permeability of visible light with a wavelength of 400 nm-700 nm of a transparent layer is 90% or more.
The average transmittance of visible light of wavelengths 400 nm to 700 nm of the transfer film of the present invention or the transparent layer of the transfer film is measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

[Coloring composition for heating device decoration]
The coloring composition for heating appliance decoration of the present invention comprises a coloring agent,
A silicone having a D-body structure represented by the following general formula D and a T-body structure represented by the following general formula T, and a D / T ratio represented by the following formula exceeding 0 and 2.5 or less A coloring composition for heating device decoration, comprising: a resin; and at least one of silicone rubber having a D-body structure;
D / T ratio = (molar amount of silicon atoms contained in D structure) / (molar amount of silicon atoms contained in T structure)
In the general formula D and the general formula T, R ^D1 , R ^D2 and R ^T1 each independently represent a methyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and the wave portion represents another It represents a binding site to the structure.
By this configuration, the coloring composition for heating appliance decoration of the present invention is excellent in scratch resistance, heat resistance in the viewpoint of cracking, and heat resistance and color matching in the viewpoint of coloring. Although the detailed mechanism of action is not clear, by using a silicone resin, heat resistance and color matching property in terms of coloring can be modified with a decorative material using acrylic resin or a decorative material formed by sputtering. It can be improved by comparison. When the D / T ratio of the silicone resin exceeds 0, the bifunctional D-body structure part imparts flexibility to the cured film, and relaxation stress caused by curing is heat resistance in view of cracking. Is presumed to be a factor that can be improved. When the D / T ratio of the silicone resin is 2.5 or less, it is presumed that controlling the viscosity within an appropriate range is one factor that can improve the scratch resistance.
Generally, by thickening the decorative material, it is possible to improve the whiteness of the decorative material, but in the case of a thick decorative material, cracking tends to occur. The coloring composition for heating appliance decoration of this invention which can suppress generation | occurrence | production of a crack is suitable also when this decorating material is thickened.
The coloring composition for heating appliance decoration of the present invention is preferably used for a cooker top plate, that is, preferably a coloring composition for decorating a cooker top plate.
Hereinafter, the preferable aspect of the coloring composition for heating implement decoration of this invention is demonstrated.

<Colorant>
The coloring composition for heating appliance decoration of the present invention has a coloring agent.
The colorant may be used alone or in combination of two or more.
There is no restriction | limiting in particular as a coloring agent, A well-known pigment and well-known dye can be used. The colorant is preferably a pigment, more preferably an inorganic pigment.
Among the colorants, it is preferable to use a white pigment or a black pigment from the viewpoint of forming a white decorative material or a black decorative material.
The coloring composition for heating appliance decoration of the present invention has a coloring agent content ratio of 0 to the total of silicone resins having a D / T ratio of less than 1 among silicone resins contained in the heating appliance decorating coloring composition. More than 5 is preferable, more than 1.0 is more preferable, and 1.2 to 2.0 is particularly preferable.

(White pigment)
The white pigment is not particularly limited, but the white pigments described in paragraph 0015 and paragraph 0114 of JP-A-2005-7765 can be used.
Specifically, as the white pigment, titanium dioxide, zinc oxide, lithopone, light calcium carbonate, white carbon, aluminum oxide, aluminum hydroxide, barium sulfate are preferable, titanium dioxide and zinc oxide are more preferable, and the white pigment is titanium dioxide More preferred is rutile type or anatase type titanium dioxide, and rutile type titanium dioxide is most preferable.

The surface of titanium dioxide can be treated with silica treatment, alumina treatment, titania treatment, zirconia treatment, organic matter treatment and the like in combination.
Thereby, the catalytic activity of titanium dioxide can be suppressed, and the heat resistance, the fluorescence and the like can be improved.
From the viewpoint of suppressing the b value after the coating film of the coloring composition for heating appliance decoration of the present invention is subjected to high temperature treatment, the surface treatment to the surface of titanium dioxide is preferably alumina treatment, zirconia treatment, silica treatment, alumina / Combined treatment with zirconia or combined treatment with alumina / silica is particularly preferred.
As a commercially available white pigment, titanium dioxide described in JP-A-2014-137617 can be used, and in particular, CR-97, CR-63, CR-60, CR-90 (all manufactured by Ishihara Sangyo Co., Ltd.), etc. Can be preferably used.

The white pigment preferably has an average particle size of 0.10 μm to 0.3 μm, more preferably 0.15 μm to 0.27 μm, and more preferably 0.15 μm, from the viewpoint of dispersion stability and hiding power. More preferably, it is -0.25 μm. When the average particle diameter of the primary particles is 0.10 μm or more, the hiding power is high, the substrate is difficult to see, and the viscosity is hardly increased. On the other hand, if the thickness is 0.3 μm or less, the whiteness is sufficiently high, the hiding power is high, and the surface condition when coated is good.
The term "average particle size of primary particles" as used herein refers to the diameter when the electron micrograph image of the particles is a circle of the same area, and "number average particle size" refers to the above-mentioned particles for a large number of particles. Determine the diameter, say the average value of 100.
On the other hand, when measuring the average particle diameter in a dispersion liquid and a coating liquid, laser scattering HORIBAH (made by Horiba Advanced Techno) can be used.

The content of the white pigment is preferably 5 to 80% by mass, more preferably 15 to 75% by mass, based on the total solid content of the coloring composition for heating appliance decoration of the present invention, and 25 to 25%. More preferably, it is 75% by mass.
In addition, "total solid content" means the component which remove | eliminated volatile components, such as a solvent, from the coloring composition for heating implement decoration.

  In addition, the white pigment may be added to the coloring composition for heating appliance decoration as a white pigment dispersion described later, and the content of the white pigment in the white pigment dispersion is the entire coloring composition for heating appliance decoration It is preferable that it is 20-90 mass% with respect to, and it is more preferable that it is 30-80 mass%.

(Black pigment)
Examples of the black pigment include carbon black, titanium black, titanium carbon, iron oxide, titanium oxide, graphite and the like, and it is preferable that at least one of titanium oxide and carbon black be contained, and carbon black be contained. More preferable.
The content of the black pigment is preferably 3 to 60% by mass, more preferably 5 to 45% by mass, with respect to the total solid content of the coloring composition for heating appliance decoration, and more preferably 10 to 40%. More preferably, it is%.

  From the viewpoint of dispersion stability and hiding power, the black pigment preferably has an average primary particle diameter of 5 to 100 nm, and more preferably 10 to 50 nm. When the average particle size of the primary particles is 5 nm or more, the hiding power is high, the base of the black layer (also referred to as "light shielding layer") becomes difficult to see, and the viscosity increase of the coloring composition for heating appliance decoration hardly occurs . On the other hand, if it is 100 nm or less, the chromaticity is sufficiently high, the hiding power is high, and the surface condition when coated is good.

(Pigments of other colors)
As pigments of other colors, various known inorganic pigments and organic pigments can be used.
Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, etc. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides of the above, and composite oxides of the above metals.
As an organic pigment,
C. I. (Short for Color Index International) Pigment Red 177, 224, 242, 254, 255
C. I. Pigment Yellow 138, 139, 150, 180, 185
C. I. Pigment Green 7, 36, 58
C. I. Pigment Blue 15: 1, 15: 3, 15: 4, 15: 6,
C. I. Pigment Violet 23
Can be mentioned.
Moreover, it can adjust to a pastel color by adding the pigment of said other color to a white pigment.
The pigment other than the black pigment and the white pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments. In particular, C.I. I. Pigment red 177 (anthraquinone pigment), C.I. I. Pigment red 254 (diketopyrrolopyrrole pigment), C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment blue 15: 6 (phthalocyanine pigment), C.I. I. Pigment yellow 138 (quinophthalone pigment), C.I. I. Pigment yellow 139, 185 (isoindoline pigment), C.I. I. Pigment yellow 150 (azomethine pigment), C.I. I. Pigment Violet 23 (dioxazine pigment) is preferably exemplified. Moreover, FD-5060 and CP-525 (all are Asahi Kasei Metals Co., Ltd. product) which are the mineral spirit solution of aluminum paste as a silver-colored pigment are also preferable.
The content of the pigment of the other color is preferably 50 to 95% by mass, and more preferably 60 to 90% by mass, with respect to the total solid content of the heating appliance decorating coloring composition.
In addition, the content of the pigment other than the black pigment and the white pigment is preferably 3 to 99% by mass, and more preferably 5 to 90% by mass, based on the coloring composition for heating appliance decoration.

(dye)
The dye is not particularly limited and known dyes can be used.
For example, the dyes described in [0010] to [0188] of JP-A-2014-177502 can be preferably used, and the contents of this publication are incorporated herein.
As a specific example of the dye, for example, the following dyes can be preferably used.

<Specific silicone resin>
The coloring composition for heating appliance decoration has a D-body structure represented by the following general formula D and a T-body structure represented by the following general formula T, and a D / T ratio represented by the following formula is It contains silicone resin which is more than 0 and not more than 2.5.
D / T ratio = (molar amount of silicon atoms contained in D structure) / (molar amount of silicon atoms contained in T structure)
In the general formula D and the general formula T, R ^D1 , R ^D2 and R ^T1 each independently represent a methyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and the wave portion represents another It represents a binding site to the structure.
Hereinafter, a silicone resin having a D-body structure represented by the general formula D and a T-body structure represented by the general formula T and having a D / T ratio of more than 0 and 2.5 or less is specified. It is also called silicone resin.
The specific silicone resin is more preferable than the silicone rubber having the D-body structure from the viewpoint of scratch resistance.

In the general formula T and the general formula D, R ^D1 , R ^D2 and R ^T1 each independently represent a methyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, a methyl group or a substituted or unsubstituted group It is preferably an unsubstituted phenyl group, more preferably a methyl group or an unsubstituted phenyl group, and the wavy line portion indicates a binding site to another structure.

The D / T ratio of the specific silicone resin is more than 0 and 2.5 or less, preferably 0.2 to 2.5, and more preferably more than 0.5 and 2.5 or less, 0 It is particularly preferable that it is from 7 to 1.5, and it is even more preferable that it is from 0.7 to 1.0.
The coloring composition for heating device decoration preferably contains two or more types of specified silicone resins from the viewpoint of freely controlling the film quality so as to obtain desired performance such as cracking. In particular, the coloring composition for heating appliance decoration is a specific silicone resin having a D / T ratio of more than 0.5 and 2.5 or less and a specific silicone resin having a D / T ratio of more than 0 and 0.5 or less It is preferable to use in combination from the viewpoint that a decorative material capable of achieving both cracking and scratch resistance can be obtained.
The specific silicone resin whose D / T ratio in the coloring composition for heating device decoration is more than 0 and 0.5 or less, and the specific silicone resin whose D / T ratio is more than 0.5 and 2.5 or less The content ratio of is preferably 1: 1 to 100: 1, more preferably 3: 1 to 50: 1, particularly preferably 5: 1 to 40: 1, and 5: 1 to 5: 1. More particularly preferably 20: 1.

The specific silicone resin may contain a structure represented by the general formula T and other structures other than the structure represented by the general formula D, but the structure represented by the general formula T and the general formula D It is preferable that it is 80 mass% with respect to the mass of the whole silicone resin, and, as for the total amount of the structure represented, it is more preferable that it is 90 mass% or more.
As said other structure, the structure represented by the following formula M and the structure represented by the following Q are mentioned.

In the formulas M and Q, R ^M1 , R ^M2 and R ^M3 each independently represent an alkyl group, an aryl group, an allyl group or a hydrogen atom, preferably an alkyl group or an aryl group, preferably carbon It is more preferable that it is an alkyl group of the number 1-4, a phenyl group, or a naphthyl group, It is still more preferable that it is a methyl group or a phenyl group, A wavy line part represents a coupling | bonding site | part with another structure.

The specific silicone resin can be produced, for example, by a method of hydrolyzing a silane compound having a hydrolyzable group to generate a silanol group and then condensing the same by heating.
As said hydrolysable group, an alkoxy group or a halogen atom is mentioned, A C1-C4 alkoxy group or a chlorine atom is preferable.
Since the specific silicone resin contains the structure represented by the above general formula T and the structure represented by the above general formula D, the hydrolyzable group which can form the structure represented by the above general formula T after condensation is 3 It is preferable to condense a silane compound having one or two hydrolyzable groups capable of forming a structure represented by the above general formula D after condensation.
Moreover, in order to make the specific silicone resin contain the structure represented by the above formula M and the structure represented by the above formula Q, it has a silane compound having one hydrolysable group and four hydrolyzable groups. You may further condense with a silane compound.
The amount of the silane compound having three hydrolyzable groups and the silane compound having two hydrolyzable groups needs to make the D / T ratio of the specific silicone resin more than 0 and not more than 2.5, It is more preferable that (molar amount of silane compound having two hydrolyzable groups) / (molar amount of silane compound having three hydrolyzable groups) be more than 0 and not more than 2.5.

  As a silane compound which has three hydrolysable groups, as a compound which is represented by following formula T1, and a compound which has two hydrolysable groups, the compound represented by following formula D1 is mentioned preferably, respectively.

In formulas T1 and D1, R ^T1 , R ^D1 , and R ^D2 each independently represent an alkyl group, an aryl group, an allyl group, or a hydrogen atom, and R ^{T2 to} R ^T4 represent an alkyl group.
R ^T1 , R ^D1 and R ^{D2 in} Formula T1 and Formula D1 are preferably each independently an alkyl group or an aryl group, and are an alkyl group having 1 to 4 carbon atoms, a phenyl group or a naphthyl group Is more preferable, and a methyl group or a phenyl group is more preferable, and a wavy line portion represents a binding site to another structure.
Each of R ^{T2 to} R ^{T4 in} the formulas T1 and D1 is preferably independently an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and a methyl group or an isopropyl group Groups are more preferred.

The specific silicone resin preferably has a glass transition temperature (Tg) of -10 ° C or higher.
The Tg of the specific silicone resin is preferably 0 ° C. or higher, and more preferably 10 ° C. to 120 ° C. When the Tg is in the above range, the cured product obtained is excellent in cracking resistance at the time of heating, and can be more suitably used as a transfer material and a decorating material.
As a measuring method of Tg of specific silicone resin, the method of measuring using a differential scanning calorimeter (DSC) is mentioned.

  As a specific silicone resin whose D / T ratio is more than 0 and 2.5 or less, for example, Shin-Etsu Chemical Co., Ltd. KR-251, KR-311, X-40-9246, KR-255, KR-2621 -1, X-40-2667A, KR-211, KR-216, X-40-2406M etc. can be mentioned. Among them, KR-251, KR-311 and X-40-9246 are preferable.

  The weight average molecular weight of the specific silicone resin is preferably 1,000 or more, more preferably 2,000 or more, and preferably 5,000,000 or less, 3,000,000. It is more preferable that

  The content of the specific silicone resin is preferably 1 to 100% by mass, more preferably 10 to 95% by mass, with respect to the total solid content of the coloring composition for heating appliance decoration, and more preferably 30 to 95%. More preferably, it is%.

<Silicone rubber>
The coloring composition for heating appliance decoration of the present invention may contain silicone rubber which has D structure.
The silicone rubber is not particularly limited, but is preferably silicone rubber having a D-body structure.
As a silicone rubber, the compound which has a structure represented by following formula 12 is preferable.

In Formula 12, R ^b is a halogen atom, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and 2 carbon atoms To 20 linear, branched or cyclic alkenyl groups, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms.

The compound having a structure represented by Formula 12 preferably has two or more structures represented by Formula 12.
When it has two or more structures represented by Formula 12, two or more ^Rb may be same or different, respectively.
R ^b in Formula 12 is a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms It is preferably a group or an aralkyl group having 7 to 20 carbon atoms, more preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and methyl More preferably, it is a group or a phenyl group.
As a halogen atom in R ^b , a fluorine atom, a chlorine atom and the like can be mentioned.
As a C1-C20 linear, branched or cyclic alkoxy group in R ^b , for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group Sec-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, cyclopentyloxy, cyclohexyloxy and the like.
As a C1-C20 linear, branched or cyclic alkyl group in R ^b , for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like. Among the linear, branched or cyclic alkyl group having 1 to 20 carbon atoms for R ^b , an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.

Moreover, as a C1-C20 linear, branched or cyclic substituted alkyl group in R ^b , for example, an arylalkyl group, a fluoroalkyl group, a chloroalkyl group, a hydroxyalkyl group, a (meth) acryloxyalkyl Groups and mercaptoalkyl groups can be mentioned. Specific examples thereof include, for example, phenylmethyl (benzyl) group, diphenylmethyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenyl-n-propyl group, 2-phenyl-2-propyl (cumyl ), 3-phenyl-n-propyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl, 4-phenylbutyl, 1-phenylpentyl, 2-phenylpentyl, 3-) Phenylpentyl, 4-phenylpentyl, 5-phenylpentyl, 1-phenylhexyl, 2-phenylhexyl, 3-phenylhexyl, 4-phenylhexyl, 5-phenylhexyl, 6-phenylhexyl Group, 1-phenylcyclohexyl group, 2-phenylcyclohexyl group, 3-phenylcyclohexyl group 1-phenylheptyl group, 2-phenylheptyl group, 3-phenylheptyl group, 4-phenylheptyl group, 5-phenylheptyl group, 6-phenylheptyl group, 1-phenyloctyl group, 2-phenyloctyl group, 3-phenylheptyl group Phenyloctyl group, 4-phenyloctyl group, 5-phenyloctyl group, 6-phenyloctyl group, 1-naphthylethyl group, 2-naphthylethyl group, 1-naphthyl-n-propyl group, 2-naphthyl-2-propyl group Group, 3-naphthyl-n-propyl group, 1-naphthylbutyl group, 2-naphthylbutyl group, 3-naphthylbutyl group, 4-naphthylbutyl group, 1-naphthylpentyl group, 2-naphthylpentyl group, 3-naphthyl group Pentyl group, 4-naphthylpentyl group, 5-naphthylpentyl group, 1-naphthylhexyl group, 2-naphthy Hexyl group, 3-naphthylhexyl group, 4-naphthylhexyl group, 5-naphthylhexyl group, 6-naphthylhexyl group, 1-naphthylcyclohexyl group, 2-naphthylcyclohexyl group, 3-naphthylcyclohexyl group, 1-naphthylheptyl group , 2-naphthylheptyl group, 3-naphthylheptyl group, 4-naphthylheptyl group, 5-naphthylheptyl group, 6-naphthylheptyl group, 1-naphthyloctyl group, 2-naphthyloctyl group, 3-naphthyloctyl group, 4 Arylalkyl groups such as -naphthyloctyl group, 5-naphthyloctyl group, 6-naphthyloctyl group, etc .; fluoromethyl group, trifluoromethyl group, 2-fluoroethyl group, (trifluoromethyl) methyl group, pentafluoroethyl group, 3-fluoro-n-propyl group, 2- ( Trifluoromethyl) ethyl group, (pentafluoroethyl) methyl group, heptafluoro-n-propyl group, 4-fluoro-n-butyl group, 3- (trifluoromethyl) -n-propyl group, 2- (pentafluoro) Ethyl) Ethyl group, (Heptafluoro-n-propyl) methyl group, nonafluoro-n-butyl group, 5-fluoro-n-pentyl group, 4- (trifluoromethyl) -n-butyl group, 3- (pentafluoro) Ethyl) -n-propyl group, 2- (heptafluoro-n-propyl) ethyl group, (nonafluoro-n-butyl) methyl group, perfluoro-n-pentyl group, 6-fluoro-n-hexyl group, 5- (Trifluoromethyl) -n-pentyl group, 4- (pentafluoroethyl) -n-butyl group, 3- (heptafluoro-n-propyl) -n- Ropyl group, 2- (nonafluoro-n-butyl) ethyl group, (perfluoro-n-pentyl) methyl group, perfluoro-n-hexyl group, 7- (trifluoromethyl) -n-heptyl group, 6- (6 Pentafluoroethyl) -n-hexyl group, 5- (heptafluoro-n-propyl) -n-pentyl group, 4- (nonafluoro-n-butyl) -n-butyl group, 3- (perfluoro-n-pentyl group) ) -N-propyl group, 2- (perfluoro-n-hexyl) ethyl group, (perfluoro-n-heptyl) methyl group, perfluoro-n-octyl group, 9- (trifluoromethyl) -n-nonyl Group, 8- (pentafluoroethyl) -n-octyl group, 7- (heptafluoro-n-propyl) -n-heptyl group, 6- (nonafluoro-n-butyl) -n-hexene group Group, 5- (perfluoro-n-pentyl) -n-pentyl group, 4- (perfluoro-n-hexyl) -n-butyl group, 3- (perfluoro-n-heptyl) -n-propyl group Fluoroalkyl groups such as 2- (perfluoro-n-octyl) ethyl group, (perfluoro-n-nonyl) methyl group, perfluoro-n-decyl group, 4-fluorocyclopentyl group, 4-fluorocyclohexyl group and the like; And chloromethyl group, 2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 3-chlorocyclopentyl group, 4-chlorocyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group, 3- (meth) acryloxypropyl group and 3- mercapto group The ropir group etc. can be mentioned. Among the linear, branched or cyclic substituted alkyl group having 1 to 20 carbon atoms for R ^b , an arylalkyl group is preferable, and a cumyl group is more preferable.

Moreover, as a C3-C20 linear, branched or cyclic alkenyl group in R ^b , for example, 1-methylvinyl group, 1-propenyl group, allyl group (2-propenyl group), 2-methyl -2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 3-cyclopentenyl group, 3-cyclohexenyl group and the like can be mentioned. Moreover, in addition to the specific example mentioned above, the alkenyl group in R ^b can preferably illustrate a vinyl group.
Moreover, as a C6-C20 aryl group in R ^b , for example, a phenyl group, an orthotolyl group, a metatolyl group, a paratolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group And 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 1-naphthyl group and the like. Among the aryl groups having 6 to 20 carbon atoms in R ^b, from the viewpoint of hardly generating benzene upon heating, other than unsubstituted phenyl group, that is, orthotolyl group, metatolyl group, paratolyl group, 2,3-xylyl group, 2 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 1-naphthyl group is preferable, and ortho-tolyl group, meta-tolyl group and para-tolyl group are preferable. More preferable. On the other hand, a phenyl group is preferred from the viewpoint of easy availability.

Moreover, as a C7-C20 aralkyl group in R ^b , for example, a benzyl group, a phenethyl group and the like can be mentioned.

  The compound having at least a structure represented by Formula 12 in the molecule preferably further has a structure represented by Formula 13 below.

In Formula 13, each R ^c independently represents a halogen atom, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, It represents a linear, branched or cyclic alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

R ^c in Formula 13 is each independently a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms Preferably an aryl group of 20 to 20 or an aralkyl group having 7 to 20 carbon atoms, and is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms It is more preferable that it is a methyl group or a phenyl group.
Specific examples of the halogen atom, alkoxy group, alkyl group, alkenyl group, aryl group and aralkyl group for R ^c and preferred embodiments thereof include alkoxy group, alkyl group, alkenyl group, aryl group and aralkyl for R ^b described above It is the same as the specific example of the group and its preferred embodiment.
The compound having a structure represented by Formula 12 is preferably a compound having a silicone chain, and the compound having a structure represented by Formula 12 and a silicone chain having a structure represented by Formula 13 bonded in any order. It is more preferable that
In addition, the compound having a structure represented by Formula 12 is preferably a linear silicone compound having a structure represented by Formula 12. Furthermore, the total number of silicone bonds (-O-Si-O-) in the compound having a structure represented by Formula 12 may be 1 or more, preferably 2 to 200, and 5 to 100. Is more preferable, and 10 to 50 is more preferable.
When the compound having the structure represented by Formula 12 further has the structure represented by Formula 13, the structure represented by Formula 12 and the structure represented by Formula 13 in the compound having the structure represented by Formula 12 There are no particular restrictions on the molar ratio with. The structure represented by Formula 12: The structure represented by Formula 13 is preferably 10: 1 to 1: 100, more preferably 5: 1 to 1:20, and 2: 1 to 1:10. It is further preferred that
The compound having a structure represented by Formula 12 is preferably a silicone rubber, and more preferably a vinyl methyl silicone rubber or a phenyl vinyl methyl silicone rubber. In addition, vinyl methyl silicone rubber does not need to have a vinyl group on all the silicon atoms, and at least one part of the methyl group on the silicon atom of methyl silicone rubber should just be substituted by the vinyl group. In addition, phenyl vinyl methyl silicone rubber does not have to have a vinyl group on all silicon atoms, and at least a part of methyl group and / or phenyl group on silicon atom of phenyl methyl silicone rubber is replaced with vinyl group If it is

  In addition, a compound having a raw rubber-like siloxane structure and having a structure represented by Formula 12 and particles (for example, silica) as a reinforcing material are blended with various types of additives as necessary. A silicone rubber compound (silicone rubber precursor) can also be used. If necessary, a vulcanizing agent such as an organic peroxide or a catalyst is added to the silicone rubber compound at the time of use and heat curing is performed to obtain silicone rubber in a narrow sense. Silicone rubber includes both silicone rubber compounds and silicone rubber in a narrow sense after heat curing.

  As silicone rubber, a linear polyorganosiloxane compound having a vinyl group only at both ends, a linear polyorganosiloxane compound having a vinyl group at both ends and a side chain, and a branched group having a vinyl group only at the end A silicone rubber formed by crosslinking at least one silicone selected from the group consisting of a polyorganosiloxane compound and a branched polyorganosiloxane compound having a vinyl group at an end and a side chain is also included.

The linear polyorganosiloxane compound having a vinyl group only at both ends is a compound represented by any one of the following formulas. Also, the linear polyorganosiloxane compound having a vinyl group at both ends and side chains, some of R ^s in the above formula is a compound which is a vinyl group.

In the above formulae, R ^s represents the following organic group, and ns represents an integer of 1 or more.

The branched polyorganosiloxane compound having a vinyl group only at the end is a compound represented by the following formula. The branched polyorganosiloxane compound having a vinyl group at an end and a side chain is a compound in which a part of R ^{s in} the following formula is a vinyl group.

In the above formula, R ^s represents the following organic group, ms represents an integer of 1 or more, and ns represents an integer of 1 or more.
The organic group (R ^s ) bonded to a silicon atom other than the vinyl group may be different or the same type, but specific examples thereof include alkyl groups such as methyl group, ethyl group and propyl group, phenyl group, tolyl group, etc. A monovalent group excluding aryl groups, or the same or different types of unsubstituted or substituted aliphatic unsaturated groups in which part or all of hydrogen atoms bonded to carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. It is preferably a hydrocarbon group. Further, the polyorganosiloxane compound, at least 50 mole% of the total R ^s is may preferably be mentioned those which are methyl groups. These polyorganosiloxane compounds may be a single type of compound or a mixture of two or more types.

The content of the vinyl group (Si—CH = CH ₂ ) bonded to the silicon atom in the compound having a structure represented by Formula 12 is preferably 0.1 to 11.5 mmol / g, It is more preferable that it is -10.0 mmol / g. Within the above range, it is possible to obtain a decorative material which is more excellent in crack resistance at the time of heating and less in heat coloring.

  Commercially available silicone rubbers are non-solvent type, solvent type and emulsion type, but any of them can be used. Among them, the non-solvent type is very advantageous in terms of safety, hygiene and air pollution because it does not use a solvent. When considering the economy, it is preferable to use a non-solvent type silicone rubber.

As silicone rubber, for example, Shin-Etsu Chemical Co., Ltd. KE-109, KE-106, KE-1031, KE-103, KE-108, KE-581U, KE-167U, KE-153U, KE-5634U KE-1820 and KE-1886, X-21-3043 can be mentioned. Among them, KE-581U, KE-167U, KE-153U, KE-5634U, and X-21-3043 are preferable, and KE-581U and X-21-3043 are more preferable.
The weight average molecular weight of the silicone rubber is preferably 1,000 to 500,000, more preferably 1,000 to 300,000, and still more preferably 1,000 to 200,000, 1 It is especially preferable that they are 1,000 to 100,000. Sufficient hardenability is acquired as it is the said range, and a cured film excellent in crack resistance can be obtained.
The silicone rubber may be used alone or in combination of two or more.

  The content of the silicone rubber is preferably 1 to 99% by mass, more preferably 10 to 95% by mass, and more preferably 30 to 92% by mass, with respect to the total solid content of the coloring composition for heating appliance decoration It is further preferred that

The coloring composition for heating appliance decoration of the present invention can contain a pigment dispersant, a solvent, another resin, a condensation catalyst, a coating aid, an antioxidant, and other additives.
Each component will be described below.

<Other resin>
In the present invention, the coloring composition for heating device decoration may contain other resins.
The other resin contained in the coloring composition for heating device decoration is not particularly limited, but is preferably a heat crosslinkable resin. Examples of the thermally crosslinkable resin include other silicone resins having a siloxane bond in the main chain, epoxy resins, melamine resins and the like. Among these, other silicone resins having a siloxane bond in the main chain are preferable. Other silicone resins are silicone resins other than the specific silicone resin, silicone rubber and graft silicone polymer.

As other silicone resins, known ones can be used, and methyl-based straight silicone resin (polydimethylsiloxane), methylphenyl-based straight silicone resin (polydimethylsiloxane in which a part of methyl group is substituted with phenyl group), acrylic resin Modified silicone resin, polyester resin modified silicone resin, epoxy resin modified silicone resin, alkyd resin modified silicone resin, silicone alkoxy oligomer, etc. can be preferably used. Among them, methyl-based straight silicone resin, methylphenyl-based straight silicone resin, acrylic resin-modified silicone resin and silicone alkoxy oligomer are more preferable, and methyl-based straight silicone resin, methylphenyl-based straight silicone resin and silicone alkoxy oligomer are particularly preferable.
The coloring composition for heating appliance decoration of the present invention preferably contains a silicone resin having a D / T ratio of less than 1 among silicone resins from the viewpoint of suppressing cracking after heating. And the aspect containing the silicone resin whose D / T ratio is 0 is also preferable from the viewpoint of scratch resistance from the coloring composition for heating tool decorating.
Among other silicone resins, preferred are silicone resins having a silanol group and having a Tg of 10 ° C. or more. It is excellent by the crack resistance at the time of the heating of the hardened | cured material obtained as it is the said aspect, coloration resulting from the heat of hardened | cured material is less, and it is excellent by the abrasion resistance of hardened | cured material.
Other silicone resins may be used alone or in combination of two or more. The physical properties of the film can also be controlled by mixing these in any ratio.
As the other silicone resin, one dissolved in an organic solvent or the like may be used, and for example, one dissolved in a xylene solution or a toluene solution can be used.

  As other silicone resin, you may use a commercially available silicone resin, For example, Shin-Etsu Chemical Co., Ltd. product KR242A, KR271, KR300 etc. are mentioned preferably.

  The weight average molecular weight of the other silicone resin is preferably 1,000 or more, preferably 5,000,000 or less, more preferably 3,000,000 or less, 2, More preferably, it is less than 000,000.

  The content of the other silicone resin is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, based on the total solid content of the coloring composition for heating appliance decoration, and 0 to 10 More preferably, it is mass%.

<Pigment dispersant>
The coloring composition for heating appliance decoration used in the present invention preferably contains a pigment dispersant from the viewpoint of suppressing color separation. When the coloring composition for heating device decoration contains a pigment dispersant, the dispersibility in the coloring composition for heating device decoration of a coloring agent can be improved. Moreover, it is preferable that a dispersing agent has silicone in frame | skeleton from the point of heat resistance (coloring).
The pigment dispersant can be appropriately selected from known pigment dispersants and used.
The pigment dispersant is a compound having a function of improving the dispersibility of the pigment alone, and in the present invention, a polymer dispersant is preferably exemplified. The polymer dispersant preferably has both a group having a pigment adsorption site and a steric repulsion chain.

Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamide amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer), “BYK-P 104, P 105 (high molecular weight unsaturated polycarboxylic acid)”, EFKA “EFKA 4047, 4050, 4010” (Polyurethane-based), 4165 (polyurethane-based), EFKA 4300 (acrylic block copolymer), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight poly) Carboxylates, 6220 (fatty acids) Polyester), 6745 (Phthalocyanine Derivative), 6750 (Azo Pigment Derivative) ", Ajinomoto Fine Techno Co., Ltd." Adispar PB 821, PB 822 ", Kyoeisha Chemical Co., Ltd." Flower TG-710 (urethane oligomer) " No. 50E, No. 300 (acrylic copolymer), manufactured by Kushimoto Kasei Co., Ltd. “Disparone KS-860, 873 SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725 ", Kao Corporation" Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensation " ), “Hogenol L-18 (polymeric polycarboxylic acid)”, “Emulgen 920, 30, 935, 985 (polyoxyethylene nonylphenyl ether) "," Acetamine 86 (stearylamine acetate) "," Sorspurse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester amine), manufactured by Lubrisol Corporation, 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft-type polymer) ", Nikko Chemicals Co., Ltd." NIKKOL T106 (polyoxyethylene sorbitan monooleate), MYS -IEX (polyoxyethylene monostearate), Shin-Etsu Silicone Co., Ltd. "KP-541, KP-578 (acrylic silicone)", etc. are mentioned.
Among these, silicone-based pigment dispersants are preferable, and specific examples thereof include “KP-541, KP-578 (acrylic silicone)” and the like manufactured by Shin-Etsu Silicone Co., Ltd.

  In the present invention, a graft type silicone polymer represented by the following general formula 1 is preferably exemplified as the pigment dispersant.

In General Formula 1, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, and R ¹¹ and R ¹² each independently represent an arylene group or 1 to 1 carbon atom. 3 represents an alkylene group, R ¹³ and R ¹⁴ each independently represent a single bond or a divalent organic linking group, A represents a group having a pigment adsorption site, and B is a structure represented by the following general formula 2 And l and n each independently represent an integer of 1 or more, and m represents an integer of 0 or more;
In the Formula 2, each of R ¹⁵ and R ¹⁶ independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, k represents an integer of 1 or more.

In General Formula 1, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, and may be an aryl group or an alkyl group having 1 to 3 carbon atoms Preferably, it is an alkyl group having 1 to 3 carbon atoms.
Examples of the aryl group in R ^{1 to} R ¹⁰ include a phenyl group and a substituted phenyl group.
The alkyl group having 1 to 3 carbon atoms in R ¹ to R ^10, there may be mentioned methyl group, ethyl group, n- propyl group, i- propyl group, a methyl group, an ethyl group are preferable, and more a methyl group preferable.
R ^{1 to} R ¹⁰ may further have a substituent. For example, when R ^{1 to} R ¹⁰ represent a hydroxy group, it may further have an optional alkyl group as a substituent to form an alkoxy group. However, it is preferable that R ^{1 to} R ¹⁰ further have no substituent.

When l is 2 or more, l R ⁴ and R ⁵ may be identical to or different from each other.
When m is 2 or more, m R ⁶ may be the same as or different from each other.
When n is 2 or more, n R ^{7 s} may be the same as or different from each other.

In the Formula ^{1, R 11} and ^{R 12} independently represent an arylene group or an alkylene group having 1 to 3 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms.
When m is 2 or more, m R ^{11 s} may be the same as or different from each other.
When n is 2 or more, n R ^{12 s} may be the same as or different from each other.

In general formula 1, R ¹³ represents a single bond or a divalent organic linking group.
When m is 2 or more, m R ¹³ may be the same as or different from each other.
In General Formula 1, R ¹⁴ represents a single bond or a divalent organic linking group.
When n is 2 or more, n R ^{13 s} may be the same as or different from each other.
Examples of the divalent organic linking group for R ¹³ or R ¹⁴ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 A group consisting of -20 sulfur atoms is included, and may be unsubstituted or may further have a substituent.
Specific examples of the divalent organic linking group in R ¹³ or R ¹⁴ include structural units selected from the following structural unit group G, or a group formed by combining these structural units. it can.

R ¹³ or R ¹⁴ is a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms and 0 to 10 A divalent organic linking group consisting of sulfur atoms is preferred, and a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 oxygen atoms, 1 to 50 hydrogen atoms, and A divalent organic linking group consisting of 0 to 7 sulfur atoms is more preferable, and a single bond or 1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 10 carbon atoms Particular preference is given to divalent organic linking groups which consist of 30 hydrogen atoms and 0 to 5 sulfur atoms.

R ¹³ or R ¹⁴ is a single bond, or a structural unit selected from the above structural unit group G or a combination of these structural units, “1 to 10 carbon atoms, 0 to 5 A divalent organic linking group consisting of a nitrogen atom, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms and 0 to 5 sulfur atoms (which may have a substituent; Is, for example, an alkyl group having 1 to 20 carbon atoms such as methyl or ethyl, an aryl group having 6 to 16 carbon atoms such as phenyl or naphthyl, a hydroxyl group, an amino group, a carboxy group, a sulfonamide group, N-sulfonylamido group, C1-C6 acyloxy group such as acetoxy group, C1-C6 alkoxy group such as methoxy group and ethoxy group, halogen atom such as chlorine and bromine, methoxycarbonyl group, ethoxy Carbonyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, or a t- like carbonate group such as butyl carbonate.).
R ¹³ is preferably a divalent organic linking group represented by — (CH ₂ ) —CH (R ^13A ) —. R ^13A represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is preferably a hydrogen atom or a methyl group. R ^13A may further have a substituent, and when it has a substituent, a carboxy group is preferable.
R ¹⁴ is preferably a divalent organic linking group represented by — (CH ₂ ) —CH (R ^14A ) —C (= O) —O— (C _q H _2q ) —. R ^14A represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and is preferably a hydrogen atom or a methyl group. R ^14A may further have a substituent. q represents an integer of 0 or more, preferably 1 or more.

In general formula 1, A represents a group having a pigment adsorption site.
When m is 2 or more, m pieces of A may be the same as or different from each other.
A may have one pigment adsorption site or may have a plurality of pigment adsorption sites. When A has a plurality of pigment adsorption sites, they may be identical to or different from one another.
A represents, for example, a pigment adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, 1 to 400 hydrogen atoms and 0 to 40 sulfur atoms. It is preferable that it is a monovalent organic group formed by bonding with a constituent organic linking group. In the case where the pigment adsorption site itself constitutes a monovalent organic group, the pigment adsorption site itself may of course be the organic group represented by A.

  The pigment adsorption site is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, a heterocyclic group, an amide group, alkoxysilyl group It is preferable to include at least one site selected from the group consisting of an epoxy group, an isocyanate group, a hydroxy group and a thiol group, an acidic group, a group having a basic nitrogen atom, a urea group, a coordinating oxygen atom It is more preferable to include at least one kind of site selected from the group consisting of: a group having a heterocyclic group, an amido group, an alkoxysilyl group, a hydroxy group and a thiol group, and selected from the group consisting of an acidic group and an alkoxysilyl group It is further preferable to include at least one type of moiety, with a carboxylic acid group, a phosphoric acid group or a trimethoxysilyl group being particularly preferable.

  As an acidic group in a pigment adsorption site, a carboxylic acid group, a sulfonic acid group, a mono-sulfuric acid ester group, a phosphoric acid group (such as a phosphono group), a phosphonooxy group, a monophosphoric acid ester group and a boric acid group are preferably mentioned. An acid group, a sulfonic acid group, a monosulfuric acid ester group, a phosphoric acid group, a phosphonooxy group, and a monophosphoric acid ester group are more preferable, and a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are particularly preferable.

As a group having a basic nitrogen atom at a pigment adsorption site, an amino group (-NH ₂ ), a substituted imino group (-NHR ^C1 , -NR ^C2 R ^C3 , wherein R ^C1 , R ^C2 and R ^C3 are each independently And an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms or an aralkyl group having 7 or more carbon atoms), a guanidyl group or an amidinyl group, and the like.

As a urea group at a pigment adsorption site, -NR ^C4 CONR ^C5 R ^C6 (wherein R ^{C4 to} R ^C6 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or And N represents an aralkyl group having a carbon number of 7 or more), and -NR ^C4 CONHR ^C6 (wherein R ^C4 and R ^C6 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 or more carbon atoms Is more preferably an aryl group of 7 or more and an aralkyl group of 7 or more carbon atoms, and -NHCONHR ^C6 (wherein, R ^C6 is a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an aryl group of 6 or more carbon atoms or carbon And particularly preferably represents an aralkyl group of 7 or more.

As a urethane group at a pigment adsorption site, -NHCOOR ^C7 , -NR ^C8 COOR ^C9 , -OCONHR ^C10 , -OCON R ^C11 R ^C12 (wherein R ^{C7 to} R ^C12 are each independently an alkyl group having 1 to 20 carbon atoms) And an aryl group having 6 or more carbon atoms or an aralkyl group having 7 or more carbon atoms), and the like, and -NHCOOR ^C7 , -OCONHR ^C10 (wherein R ^C7 and R ^C10 are each independently a ^C 1 to ^C 1 carbon atom). 20 alkyl groups, aryl groups having 6 or more carbon atoms or aralkyl groups having 7 or more carbon atoms are more preferable, and -NHCOOR ^C7 , -OCONHR ^C10 (wherein R ^C7 and R ^C10 are each independently carbon) An alkyl group having a number of 1 to 10, an aryl group having a carbon number of 6 or more, or an aralkyl group having a carbon number of 7 or more Be.) Is particularly preferred.

  As a group which has a coordinating oxygen atom in a pigment adsorption site, acetylacetonato group, crown ether, etc. are mentioned.

  Examples of the hydrocarbon group having 4 or more carbon atoms in the pigment adsorption site include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, etc. And an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms is more preferable, and an alkyl group having 4 to 15 carbon atoms (eg, octyl group, dodecyl group, etc.), an aryl group having 6 to 15 carbon atoms (eg, , A phenyl group, a naphthyl group and the like) or an aralkyl group having a carbon number of 7 to 15 (eg, a benzyl group and the like) is particularly preferable.

  As a heterocyclic group at a pigment adsorption site, thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, Dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimido, phthalimido, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, and anthraquinone And groups having a heterocyclic ring selected from the group consisting of

As an amide group in a pigment adsorption site, -CONHR ^C13 (here, R ^C13 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms or an aralkyl group having 7 or more carbon atoms), etc. It can be mentioned.

  Examples of the alkoxysilyl group at the pigment adsorption site include a trimethoxysilyl group and a triethoxysilyl group.

  Examples of other possible modes of the organic group having a pigment adsorption site include the modes described in paragraphs 0016 to 0046 of JP 2013-43962 A, and paragraphs 0016 to 0046 of JP 2013-43962 A. The contents of are incorporated herein by reference.

  In General Formula 1, B represents a group having a structure represented by the following General Formula 2.

In the Formula 2, each of R ¹⁵ and R ¹⁶ independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, k represents an integer of 1 or more.

Each of R ¹⁵ and R ¹⁶ independently is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
k represents an integer of 1 or more, preferably an integer of 2 to 300, and more preferably an integer of 10 to 200.

B represents a group having a structure represented by General Formula 2.
The structure represented by the general formula 2 is preferably a structure derived from a silicone-based monomer. B alone may be a structure derived from a silicone-based monomer, and a combination of B and R ¹⁴ may be a structure derived from a silicone-based monomer. The silicone based monomer may be a silicone based macromer. In the present specification, “macromer (also referred to as macromonomer)” is a generic term for oligomers having a polymerizable functional group (polymerization degree: about 2 or more and about 300 or less) or polymers; (Monomers) and both properties. The structure represented by the above formula 2 has a weight average molecular weight of 1,000 to 50,000 (more preferably 1,000 to 10,000, still more preferably 1,000 to 5,000). It is preferred that the structure is derived from a macromer.

  Furthermore, the graft type silicone polymer represented by the general formula 1 is preferably soluble in an organic solvent. When the affinity to the organic solvent is high, for example, when it is used as a dispersant, the affinity to the dispersion medium becomes strong, and it is easy to secure an adsorption layer sufficient for dispersion stabilization.

  Examples of the group having a structure represented by the general formula 2 include X-22-174 ASX, X-22-174 BX, KF-2012, X-22-173 BX, X-22- X manufactured by Shin-Etsu Chemical Co., Ltd. 3710-derived groups can be mentioned.

In the general formula 1, l represents an integer of 1 or more and is preferably an integer of 1 to 100, more preferably an integer of 1 to 60, and particularly preferably an integer of 1 to 30.
In the general formula 1, m represents an integer of 0 or more, preferably 1 or more, from the viewpoint of enhancing the dispersibility of the pigment, more preferably an integer of 1 to 60, and an integer of 1 to 30 Being particularly preferred.
In the general formula 1, n represents an integer of 1 or more and is preferably an integer of 1 to 100, more preferably an integer of 1 to 60, and particularly preferably an integer of 1 to 30.

The ratio of the content of each partial structure in the graft type silicone polymer represented by the general formula 1 is not particularly limited. That is, in the general formula 1, the ratio of l to m to n is not particularly limited.
In addition, partial structures in the graft type silicone polymer represented by the general formula 1 (structures in the parentheses with subscripts of 1 to n at the lower right, and a repeating unit represented by There is no particular limitation on the order, and they may be combined in any order, and for example, they may be combined by forming a block or randomly.
In the general formula 1, m preferably represents an integer of 1 or more.

The graft type silicone polymer represented by the general formula 1 may have other repeating units other than l, m, n and k repeating units, but it is preferable not to have any other repeating unit.
As other repeating units, other repeating units having a pigment adsorption site other than A can be mentioned. For example, the graft type silicone polymer represented by the general formula 1 may have a repeating unit having a (unreacted) thiol group represented by the following formula 4.

In the formula ^4, respectively ^{R 17} and ^{R 18} are independently a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, s represents an integer of 0 or more.

Preferred embodiments of R ¹⁷ and R ¹⁸ in Formula 4 are the same as the preferred embodiments of R ⁶ and R ¹¹ in General Formula 1.
s is preferably 0.
As an example of the polymer containing the repeating unit which has a thiol group represented by Formula 4, Shin-Etsu Chemical Co., Ltd. KF-2001 and KF-2004 etc. can be mentioned.

  The graft type silicone polymer represented by the general formula 1 is more preferably a compound represented by the following formula 3.

In Formula 3, R ¹¹ and R ¹² each independently represent an arylene group or an alkylene group having 1 to 3 carbon atoms, and R ¹³ and R ¹⁴ each independently represent a single bond or a divalent organic linking group, A ¹ represents an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, a heterocyclic group, an amide group, an alkoxysilyl group, A group having a pigment adsorption site having at least one group selected from the group consisting of an epoxy group, an isocyanato group, a hydroxy group, and a thiol group, B represents a group having a structure represented by the following general formula 2 And each of l, m1 and n independently represents an integer of 1 or more.

In the Formula 2, each of R ¹⁵ and R ¹⁶ independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, k represents an integer of 1 or more.

^R 11 in Formula ^{3, R 12, R 13,} R 14, B, definition of l and n, and the preferred range, ^R 11 in the general formula ^{1, R 12, R 13,} R 14, B, l and n And their preferred ranges are the same as the above.
The preferred ranges of A ¹ and m ¹ in Formula 3 are the same as the preferred ranges of A and m in General Formula 1, respectively.

(Method for producing graft type silicone polymer)
There is no restriction in particular as a manufacturing method of a graft type silicone polymer denoted by the above-mentioned general formula 1.
For example, it can be synthesized by combining the following compound A which is a mercapto-modified silicone, compound B which is a silicone macromonomer, and compound C which is a macromonomer having a pigment adsorption site, for example, can be synthesized according to the following scheme 1 . Although Scheme 1 below shows an example using Compound B and Compound C, which are macromonomers (specifically, radically polymerizable monomers, more specifically, (meth) acrylic monomers), the above general formula 1 is used. The method for producing the graft type silicone polymer represented by is not limited to this production method.
Compound A, B, in C and ^{Scheme 1, R 1 ~R 11,} l, m and,, n is, ^R 1 ^{to R} 11 in the general formula 1, l, m and,, n and have the same meanings, p is an integer of 0 or more, k is an integer of 1 or more, R ^B is an arbitrary substituent, R and X each represent the following substituents, and PGMEA is propylene, which is an example of an ester solvent It is glycol monomethyl ether acetate, and V-601 is dimethyl-2,2'-azobis (2-methyl propionate) which is an example of a polymerization initiator.

  The method for producing the pigment dispersant may refer to the description of [0110] to [0134] of JP 2013-43962 A, and the contents of [0110] to [0134] of JP 2013-43962 A. Is incorporated herein. However, the present invention is not limited to these.

  The weight average molecular weight of the graft type silicone polymer is preferably 1,000 to 100,000, more preferably 2,000 to 70,000, and still more preferably 3,000 to 50,000. . When the weight average molecular weight is 1,000 or more, the pigment dispersibility is good.

The pigment dispersant may be used alone or in combination of two or more.
The content of the pigment dispersant is preferably 1 to 40 parts by mass, more preferably 2 to 30 parts by mass, and still more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the white pigment. .

(Pigment dispersion)
The pigment may be added as a pigment dispersion to the coloring composition for heating appliance decoration.
The pigment dispersion may contain the white pigment, the pigment dispersant, and at least one solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, and alcohol solvents. preferable.
As said pigment dispersant, the said graft-type silicone polymer is preferable.
The method of preparing the pigment dispersion is not particularly limited, but it is preferable to use only the pigment, the graft type silicone polymer, the solvent, and optionally a small amount of the dispersion binder when dispersing the pigment. In addition, at the time of pigment dispersion, additives such as the above-mentioned specific silicone resin which functions as a dispersion aid and a condensation catalyst described later may be added as a material of the pigment dispersion.

As the solvent used for the pigment dispersion, it is preferable to use at least one solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents and alcohol solvents.
Preferred hydrocarbon solvents are xylene, toluene, benzene, ethylbenzene, hexane and the like.
Preferred ketone solvents are methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetone, diethyl ketone and the like.
As an ester solvent, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate and the like are preferable.
As an alcohol solvent, propylene glycol monomethyl ether, ethyl cellosolve, butyl cellosolve, normal propyl alcohol, butanol and the like are preferable.
Among them, at least one solvent selected from the group consisting of hydrocarbon solvents, ester solvents and ketone solvents is preferable, and is selected from the group consisting of xylene, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate. Particularly preferred are at least one solvent.
As content of the solvent with respect to a pigment dispersion liquid (total of a total solid and a solvent), 5-98 mass% is preferable, and 10-95 mass% is more preferable.

  The dispersing machine used to disperse the pigment is not particularly limited, and, for example, the kneader and roll mill described in Asakura Koji, "Pigment Encyclopedia", First Edition, Asakura Shoten, 2000, p. 438. Known dispersers such as attritors, super mills, dissolvers, homomixers, sand mills and bead mills. Furthermore, the pigment may be pulverized by using the frictional force by mechanical grinding described on page 310 of the aforementioned document.

A binder may be added to the pigment dispersion to suppress sedimentation and aggregation of the pigment particles. As a binder, a modified silicone compound is mentioned from the point of heat coloring. As the modified silicone compound, a compound having a siloxane bond in the main chain and having a hydroxy group or a carboxy group at the main chain terminal and / or the side chain terminal is suitably used. In particular, the black pigment dispersion preferably contains a modified silicone compound.
As content of the binder with respect to the total solid in a pigment dispersion liquid, 0.1-30 mass% is preferable, 0.2-20 mass% is more preferable, 0.5-10 mass% is especially preferable.
The content of the graft type silicone polymer in the pigment dispersion is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, with respect to 100 parts by mass of the white pigment or the black pigment. It is further more preferable that it is -20 mass parts.

<Solvent>
The coloring composition for heating implement decoration of this invention may contain the solvent.
The solvent is not particularly limited, and known solvents can be used. Among them, at least one solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents and alcohol solvents as described above is preferable, and is selected from the group consisting of hydrocarbon solvents and ketone solvents. At least one solvent is more preferable, and at least one solvent selected from the group consisting of aromatic hydrocarbon solvents and ketone solvents is particularly preferable.
The solvents may be used alone or in combination of two or more.

  Although the content of the solvent in the coloring composition for heating appliance decoration is not particularly limited, it is preferably 10 to 90 mass% and 20 to 85 mass% with respect to the total mass of the white resin composition. Is more preferred.

<Condensation catalyst>
When the coloring composition for heating appliance decoration contains a silicone resin, a condensation catalyst (sometimes referred to as a condensation reaction curing catalyst or polymerization catalyst) is used to accelerate the crosslinking reaction and form a cured film. May be The condensation catalyst is preferably a metal salt, and more preferably a condensation catalyst containing an organic acid metal salt.

  As condensation catalysts comprising metal salts (except for alkali metal salts and alkaline earth metal salts), more preferably organic acid metal salts (except for alkali metal salts and alkaline earth metal salts), known condensation catalysts are preferably used. Used. That is, the curing catalyst may include aluminum salts, tin salts, lead salts or transition metal salts of organic acids, and organic acids and the aforementioned metal ions may form a complex salt represented by a chelate structure. . The curing catalyst is particularly preferably a condensation catalyst containing one or more metals selected from aluminum, titanium, iron, cobalt, nickel, zinc, zirconium, cobalt, palladium, tin, mercury or lead, and organic Acid zirconium salts, organic acid tin salts and organic acid aluminum salts are most preferably used.

  Specific examples of condensation catalysts include organic acid tin salts such as dibutyltin diacetate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylate, etc .; tetra (i-propyl) 2.) Organic acid titanium salts such as titanate, tetra (n-butyl) titanate, dibutoxy bis (acetylacetonate) titanium, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, etc. Tetrabutyl zirconate, tetrakis (acetylacetonato) zirconium, tetraisobutyl zirconate, butoxy tris (acetylacetonato) zirconi Organic acid zirconium salts such as zirconium naphthenate and zirconium octylate; aluminum salts of organic acids such as aluminum tris (ethylacetoacetate) and aluminum tris (acetylacetonate); zinc naphthenate, zinc formate, zinc acetylacetonate, Examples thereof include metal salts of organic acids such as iron acetylacetonate, cobalt naphthenate and cobalt octylate. Moreover, you may use CAT-AC, D-15, D-20, D-25 (above, Shin-Etsu Chemical Co., Ltd. product), ZC-200 (Matsumoto Fine Chemical Co., Ltd. product) as a commercial item.

  The amount of the condensation catalyst used may be a catalytic amount, but it is preferably used in an amount of 0.1 to 20% by mass as a metal component based on the pigment dispersant, the dispersion binder and the additional binder resin, and can be arbitrarily selected according to the curing conditions .

<Other additives>
The coloring composition for heating device decoration may contain other additives other than those described above.

  There is no restriction | limiting in particular as another additive, A well-known additive can be used, For example, Paragraph [0017] of patent No. 4502784, and paragraph [0060]-[0071] of Unexamined-Japanese-Patent No. 2009-237362. The surfactant described in claim 4, the thermal polymerization inhibitor described in paragraph [0018] of Japanese Patent No. 4502784, and further, the other additions described in paragraphs [0058] to [0071] of JP-A 2000-310706. Agents.

[Transfer material for heating equipment decoration]
The transfer material for heating device decoration of the present invention has a temporary support and a colored layer, and the colored layer contains the coloring composition for heating device decoration of the present invention.

<Temporary support>
The transfer material for heating tool decoration has a temporary support.
The temporary support is preferably flexible and does not cause significant deformation, contraction or elongation under pressure or under pressure and heat. Examples of temporary supports satisfying this property include polyethylene terephthalate films, cellulose triacetate films, polystyrene films, polycarbonate films and the like. Among them, biaxially stretched polyethylene terephthalate films are particularly preferable.
Although the film thickness of a temporary support body is not specifically limited, 5-300 micrometers is preferable and 20-200 micrometers is more preferable.
The temporary support may be transparent, or may contain dyed silicon, alumina sol, chromium salt, zirconium salt and the like.
Further, conductivity can be imparted to the temporary support by the method described in JP-A-2005-221726, or the like.

<Colored layer>
The transfer material for heating device decoration of the present invention has a colored layer, and the colored layer contains the coloring composition for heating device decoration of the present invention.
It is preferable that the colored layer contains at least one of a white layer and a black layer. When the colored layer includes a white layer and a black layer, it is preferable to have a black layer as a light shielding layer between the temporary support and the white layer.
As the white layer or the black layer, an uncured white layer (hereinafter, also referred to as "uncured white layer") or an uncured black layer (hereinafter, also referred to as "uncured black layer") is preferable.
The transfer material for heating tool decoration of the present invention more preferably has a black layer and a white layer in this order on the temporary support. In the following description, a transfer material for heating device decoration having a black layer and a white layer in this order on a temporary support will be mainly described, but the transfer material for heating device decoration of the present invention is limited thereto. It is not necessary to have a white layer, may not have a black layer, and may have a layer having another hue instead of the white layer or the black layer. Well, it is not particularly limited.

The transfer material for heating tool decoration preferably has a layer formed of a white resin composition or a layer obtained by drying a white resin composition (an uncured white layer) on a temporary support, and the above-mentioned temporary support It is preferable to have a layer made of the composition for forming a black layer or a layer obtained by drying the composition for forming a black layer (uncured black layer) between the above and the white layer. That is, the transfer material for heating tool decoration preferably has a temporary support, an uncured black layer, and an uncured white layer.
When an uncured white layer (decorative material 2a before heating) or an uncured black layer (decorative material 2b before heating) or the like described in FIG. There is no leakage and / or protrusion of the resist component from the opening portion even in the substrate (front plate) having a portion, particularly the decorative material 2a or the decorative material 2b which needs to form a light shielding pattern just above the boundary of the edge of the substrate. There is no leakage and / or protrusion of the resist component from the edge of the substrate. Therefore, it is possible to manufacture a thin-layer and lightweight touch panel in a simple process without contaminating the non-contact surface side of the substrate.

<Thermoplastic resin layer>
The transfer material for heating tool decoration may have at least one thermoplastic resin layer.
It is preferable that the thermoplastic resin layer be provided between the temporary support and the uncured white layer. That is, the transfer material for heating tool decoration preferably includes a temporary support, a thermoplastic resin layer, an uncured black layer and an uncured white layer in this order.
As a component to be used for the thermoplastic resin layer, an organic polymer substance described in JP-A-5-72724 is preferable, and a Vicater Vicat method (specifically, a polymer based on the American Society for Testing and Materials A.Esd.M.D. ASTM D 1235) It is particularly preferable that the softening point determined by the softening point measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less.

  Specific examples of the thermoplastic resin used for the thermoplastic resin layer include polyolefins such as polyethylene and polypropylene, copolymers of ethylene and vinyl acetate or their saponified products, and copolymers of ethylene and acrylic esters or their saponified products. Vinyl chloride copolymers such as ethylene copolymer, polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate and its saponified product, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene ) Styrene copolymers such as acrylic acid ester or copolymer with saponified product thereof, polyvinyl toluene, vinyl toluene copolymer such as vinyl toluene and copolymer of vinyl toluene and (meth) acrylic acid ester or saponified product thereof, poly (Meth) acrylic acid ester, butyl (meth) acrylate and vinyl acetate Organic polymers such as (meth) acrylic acid ester copolymer such as polymer, vinyl acetate copolymer nylon, copolymer nylon, N-alkoxymethylated nylon, and polyamide resin such as N-dimethylaminated nylon .

6-100 micrometers is preferable and, as for the film thickness of a thermoplastic resin layer, 6-50 micrometers is more preferable.
Even if it is a case where it is on a board | substrate that it is the said range, an unevenness | corrugation can fully be absorbed and it is excellent in smoothness.

<Middle class>
The transfer material for heating tool decoration may have at least one intermediate layer for the purpose of preventing mixing of components at the time of application of a plurality of application layers and at the time of storage after application.
The intermediate layer is preferably provided between the temporary support and the uncured white layer, and in the case of having a thermoplastic resin layer, between the thermoplastic resin layer and the uncured black layer. That is, the transfer material preferably includes a temporary support, a thermoplastic resin layer, an intermediate layer, an uncured black layer and an uncured white layer in this order.
As the intermediate layer, it is preferable to use an oxygen blocking film having an oxygen blocking function, which is described as "separation layer" in JP-A-5-72724. In this case, the sensitivity at the time of exposure is improved Time load is reduced and productivity is improved.
The oxygen blocking film is preferably one which exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkaline solution, and can be appropriately selected from known ones. Among them, a layer containing polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

  0.1-5.0 micrometers is preferable and, as for the film thickness of an intermediate | middle layer, 0.5-2.0 micrometers is more preferable. Within the above range, the oxygen blocking function does not decrease, and it does not take too much time during development or removal of the intermediate layer.

<Protective exfoliation layer>
The transfer material for heating device decoration may be provided with a protective release layer (preferably a protective film or a cover film) so as to cover the uncured white layer to protect from contamination and damage during storage. preferable. The protective release layer may consist of the same or similar material as the temporary support but must be easily separated from the uncured white layer. Suitable materials for the protective release layer are, for example, silicone paper, polyolefin or polytetrafluoroethylene sheet.
The film thickness of the protective release layer is preferably 1 to 100 μm, more preferably 5 to 50 μm, and particularly preferably 10 to 30 μm. If this film thickness is 1 μm or more, the strength of the protective release layer is sufficient and it is difficult to break, and if it is 100 μm or less, the price of the protective release layer does not increase, and when laminating the protective release layer. Less prone to wrinkles.

  As the protective release layer, commercially available ones are, for example, Alfan MA-410, E-200C, E-501 manufactured by Oji Paper Co., Ltd., polypropylene films such as Shin-Etsu Film Co., Ltd., etc., PS- manufactured by Teijin Ltd. No. 25 or the like, PS series, Tama Poly Co., Ltd. product, GF-1, GF-3, GF-8, GF series, etc., but not limited thereto. Moreover, it is possible to manufacture easily by sandblasting a commercially available film.

  As the protective release layer, a polyolefin film such as a polyethylene film can be used. In addition, the polyolefin film used as the protective release layer is suitably produced by heat melting the raw materials, kneading, extruding, biaxial stretching, casting or inflation method.

<Method of producing transfer material for heating device decoration>
Although it does not specifically limit as a method to manufacture the transfer material for heating implement decoration, For example, it can manufacture by the process as described in stage 0064-0066 of Unexamined-Japanese-Patent No. 2005-3861. Moreover, the transfer material for heating implement decoration can also be produced by the method of Unexamined-Japanese-Patent No. 2009-116078, for example.
As an example of a method for producing a transfer material for heating device decoration, the coloring composition for heating device decoration of the present invention (a composition for forming a black layer, a white resin composition, etc.) is coated on a temporary support and dried. And forming a layer, and covering the formed layer with a protective release layer.

Here, the transfer material for heating appliance decoration of the present invention may form at least two layers of an uncured white layer and an uncured black layer, while a heating appliance having a temporary support and an uncured white layer is provided. When the transfer material for decoration is transferred onto the substrate, the temporary support is removed, and the transfer material for heating equipment decoration including at least the temporary support and the uncured black layer is further transferred onto the uncured white layer. A layer and at least one layer of an uncured black layer may be used. In the former case, the transfer material for heating appliance decoration of the present invention may be a temporary support, on which an uncured white layer and an uncured black layer are laminated in this order, and in this case a substrate Preferably, a white layer and a black layer can be provided at one time on glass, which is preferable in terms of process.
In the transfer material for heating tool decoration of the present invention, other layers may be further formed as long as the gist of the present invention is not violated. In addition, the thermoplastic resin layer and / or the intermediate layer may be applied and formed before the formation of the uncured white layer.
On a temporary support, a coloring composition for heating appliance decoration (a composition for forming a black layer, a white resin composition, etc.) of the present invention, a coating solution for forming a thermoplastic resin layer, a coating solution for forming an intermediate layer, etc. A well-known application method can be used as a method of apply | coating. For example, it can be formed by applying and drying those coating liquids using a coating machine such as a spinner, a whirler, a roller coater, a curtain coater, a knife coater, a wire bar coater, or an extruder.

(solvent)
Each layer of the transfer material for heating tool decoration can be suitably prepared using a solvent together with each component.
As the solvent, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, lactic acid Ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-alkyloxypropionate and 3-alkyloxypropionic acid 3-alkyloxypropionic acid alkyl esters such as ethyl (eg methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), and 2-alkyloxypropionic acid alkyl esters such as methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate and propyl 2-alkyloxypropionate (eg methyl 2-methoxypropionate, ethyl 2-methoxypropionate) , Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), and methyl pyruvate Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;
Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol propyl ether acetate etc.
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone etc;
Aromatic hydrocarbons such as toluene, xylene and the like can be mentioned.
Among these, methyl ethyl ketone, methyl isobutyl ketone, xylene, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and the like are preferable.
The solvents may be used alone or in combination of two or more.

The method for covering the colored layer (preferably a white layer or an uncured white layer) with a protective release layer is not particularly limited. .
For pressure bonding, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator capable of further improving productivity can be used.
As pressure bonding conditions, an ambient temperature of 20 to 45 ° C. and a linear pressure of 1,000 to 10,000 N / m are preferable.

[Heating equipment]
The first aspect of the heating device of the present invention has a decorative material on a substrate, and the decorative material contains the coloring composition for heating device decoration of the present invention.
A second aspect of the heating device of the present invention has a decorating material on a substrate, and the decorating material is a transfer product of the colored layer of the transfer material for heating device decorating of the present invention.
The heating device of the present invention is preferably a cooking device, a laboratory device, a manufacturing facility, a clothes iron, a heating device, and more preferably a cooking device. Preferred embodiments of the cooker will be described later in the description of the cooker.
The heating device of the present invention may have a decorative material containing the coloring composition for heating device decoration of the present invention in any member of the heating device, but the heating device of the present invention is the top plate of the heating device It is preferable that there is, and it is more preferable that it is a cooker top plate. In addition, you may use the heating instrument of this invention for the cooker which does not have a top plate.
The heating device of the present invention preferably has a substrate and a decorating material in this order.
In the present invention, the colored layer contained in the heating device is also referred to as a "decorative material". However, the "decorative material" is preferably formed by heating the colored layer.
In heating appliances, it has been a problem that the decorative material is discolored (colored) by heat treatment or the like.
Furthermore, it is preferable that a white layer and / or a black layer contain the said graft-type silicone polymer.
The detailed action mechanism by which the color change of the white layer is suppressed by the white layer and / or the black layer including the above-mentioned grafted silicone polymer is not clear but is presumed as follows. That is, when the conventional dispersant is used as the dispersant in the white layer, it is considered that when the heat treatment is performed on the heating device, the conventional dispersant is colored and as a result, the color of the white layer is caused. Be When the conventional dispersant is used as the dispersant in the black layer, it is considered that part of the dispersant present in the black layer is transferred to the white layer, and when the heat treatment is performed on the heating device, the conventional It is believed that the dispersant becomes colored, which results in the color change of the white layer. The white layer and / or the black layer may contain the graft type silicone polymer represented by the general formula 1 described above as the dispersing agent, thereby suppressing the coloring, and as a result, it is considered that the color change of the white layer is suppressed. .

Moreover, it is preferable that the heating tool of this invention further has an electroconductive layer on the opposite side to a board | substrate of a decorating material (for example, black layer).
The heating device of the present invention preferably has a substrate, a white layer, a black layer and a conductive layer in this order.

The heating device of the present invention preferably has a substrate, a white layer, and a black layer in this order.
The heating device preferably has a light transmitting region which transmits light in the film thickness direction.
The decorative material (for example, the white layer and the black layer) is laminated on the substrate so as to surround the light transmitting region, and the film thickness of the decorative material decreases toward the inside of the light transmitting region at the inner edge of the decorative material. It is preferred to have the ramp formed as such.
Preferably, the inclination angle between the inclined surface and the substrate surface is 10 to 60 degrees. Between the decorative material and the portion of the substrate on which the decorative material is not formed, the decorative material has the inclined portion and the inclination angle between the surface of the inclined portion and the substrate surface is 10 to 60 degrees. Thus, the conductive layer on the decorative material is less likely to cause problems such as disconnection.
Hereafter, the preferable aspect of the heating instrument of this invention is demonstrated.

  In the heating device of the present invention, the optical density of the substrate is preferably 3.5 to 6.0, more preferably 4.0 to 5.5, and 4.5 to 5.0. Is particularly preferred.

A preferred embodiment of the decorative material is a frame-like pattern around a light transmitting area (display area) formed on the non-contact surface side of the touch panel front plate in a mode in which a heating device described later has a touch panel. It is formed for the purpose of making it invisible, etc., and the purpose of decoration. As an example is shown in FIGS. 1 to 3, the inner edge of the laminate of the decorative material 2 a and the decorative material 2 b provided on the substrate 1 faces the inward of the light transmission region, It is preferable to have the inclined part 2c formed so that a film thickness may become thin. It is preferable that the conductive layer 4 is formed on the decorating material, and extends on the substrate 1 along the slope 2c of the decorating material.
By providing the inclined portion, the film thickness difference between the decorative material and the portion of the substrate where the decorative material is not formed becomes gentle, and it becomes difficult to cause problems such as disconnection of the conductive layer.
It does not specifically limit about the formation method of an inclination part, The method of forming by shrinking the decorating material 2b by heating, the layer which consists of a coloring composition for heating implement decoration of this invention, or the heating implement decoration of this invention For example, a method of forming the layer obtained by drying the coloring composition for drying (uncured decorative material 2a) by melting by heating, and the like may be mentioned, and a method of forming the decorative material 2b by shrinkage by heating is preferable. When the decorative material 2b is shrunk by heating, the uncured decorative material 2a on the decorative material 2b side also shrinks following the decorative material 2b, while the uncured decorative material 2a on the substrate side is decorated Since it does not follow the material 2b, the inclined portion 2c can be formed.
About forming an inclination part by shrinking the decorating material 2b by heating, it mentions later.

  The shape of the inclined portion 2c in the decorative material is not particularly limited. For example, as shown in FIGS. 1 and 3 as an example, even if it has a raised projection, as shown in FIG. It may have a shape connected by a gentle curve. Further, as shown in FIGS. 1 to 3, it is sufficient that the film thickness of the decorating material 2 a is thinner toward the inside of the light transmitting region in the inclined portion 2 c, and the decorating material 2 b is also together with the decorating material 2 a The film thickness may be thinner toward the inside of the light transmitting region. As an example is shown in FIG. 3, the aspect by which two or more layers are laminated | stacked may be sufficient as the decorating material 2a.

As shown by the dotted lines in FIGS. 1 to 4, the inclination angle θ approximates the surface of the inclined portion to a plane, and is the inclination angle between this plane and the substrate surface. The inclination angle θ can be determined by cutting the substrate and measuring the angle between the substrate and the substrate from the cross-sectional direction using an optical microscope.
The inclination angle θ shown in FIG. 4 is 10 to 60 degrees, and more preferably 15 to 55 degrees. If the inclination angle θ is 10 degrees or more, the area where the decorative material 2b does not exist on the decorative material 2a decreases, and the appearance abnormality, that is, the area with low optical density decreases, and light leakage and display It is less likely to see the routing circuit of the device. On the other hand, when the inclination angle θ is 60 degrees or less, problems such as disconnection of the conductive layer are less likely to occur.
When forming the inclined portion by shrinking the decorative material 2b by heating, the desired inclination angle can be obtained by changing the kind and / or the composition of the resin constituting the decorative material 2a and / or the decorative material 2b. It is possible to form the inclined portion having.

Preferably, the inclination angle θ is provided such that the difference between the width of the decorative material 2 a on the substrate side and the width of the decorative material 2 b is 200 μm or less. With this configuration, problems such as appearance abnormality and disconnection of the conductive layer can be eliminated.
The difference between the width of the decorative material 2a on the substrate side and the width of the decorative material 2b (difference in edge) is preferably 200 μm or less, more preferably 5 to 100 μm, and still more preferably 10 to 90 μm.
The width | variety of the board | substrate side of the decorating material 2a means the width | variety of the decorating material 2a of the side which is in contact with the board | substrate among the decorating materials 2a.

<Board>
Although various substrates can be used as the substrate used for the heating apparatus of the present invention, a film substrate is preferable, and one having no optical distortion and one having high transparency are more preferable. It is preferable that the board | substrate in the heating instrument of this invention is 80% or more in the average transmittance | permeability of visible light with a wavelength of 400 nm-700 nm.

Specific materials when the substrate is a film substrate include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate (PC), triacetyl cellulose (TAC), cycloolefin polymer (COP) and cyclo olefin polymers).
The substrate may be glass or the like.
The substrate may be glass, TAC, PET, PC, COP, or silicone resin (however, silicone resin or polyorganosiloxane in the present specification is limited to the narrow meaning represented by the structural unit of R ₂ SiO). It is preferred that the resin be selected from silsesquioxane compounds represented by structural units of RSiO _1.5 ), and it is preferably made of glass, cycloolefin polymer or silicone resin.
The silicone resin preferably has a cage-type polyorganosiloxane as a main component, and more preferably a cage-type silsesquioxane as a main component. In addition, the main component of a composition or a layer means the component which occupies 50 mass% or more of the composition or that layer.
As a substrate containing a silicone resin, Japanese Patent No. 4142385, Japanese Patent No. 4409 397, Japanese Patent No. 5078269, Japanese Patent No. 4920513, Japanese Patent No. 4964748, Japanese Patent No. 5036060, Japanese Patent No. 2010-96848, Japanese No. 2011-194647 No. 2012-183818, 2012-184371, and 2012-218322 may be used, and the contents described in these publications are incorporated in the present specification.

In addition, various functions may be added to the substrate surface. Specifically, an antireflective layer, an antiglare layer, a retardation layer, a viewing angle improving layer, a protective layer, a self-repairing layer, an antistatic layer, an antifouling layer, an anti-electromagnetic wave layer, and a conductive layer can be mentioned.
The heating device preferably has a conductive layer on the surface of the heating device.
Preferred examples of the conductive layer include those described in JP-A-2009-505358.
Preferably, the substrate further comprises at least one of a scratch resistant layer and an antiglare layer.

  The thickness of the substrate is preferably 35 to 200 μm, more preferably 40 to 150 μm, and particularly preferably 40 to 100 μm.

  Moreover, in order to improve the adhesiveness of a decorating material, it can surface-treat to the surface by the side of the decorating material of a board | substrate beforehand. As surface treatment, it is preferable to carry out surface treatment (silane coupling treatment) using a silane compound. As a surface treatment using a silane compound, for example, a silane coupling solution (N-β (aminoethyl) γ-aminopropyltrimethoxysilane 0.3% by mass aqueous solution, trade name: KBM 603, Shin-Etsu Chemical Co., Ltd. product) Spray with a shower for 20 seconds, and wash with pure water. After this, the reaction is carried out by heating. A heating tank may be used, and the reaction can be promoted by preheating the substrate of the laminator.

<Decorative material>
(White decorative material)
It is preferable that the heating tool of this invention contains a white decorating material as a decorating material. The white decorative material is preferably provided adjacent to the substrate.
It is preferable that a white decorating material contains a white pigment and the condensate which the at least specific silicone resin condensed.
Similarly to the method of measuring the D / T ratio described in the specific silicone resin, the D / T ratio of the resin contained in the white decorative material is measured, and if the D / T ratio is more than 0 and 2.5 or less, It is possible to assume that the specific silicone resin in the present invention was used.
The D / T ratio can be measured in the same manner as the D / T ratio in the specific silicone resin.
Moreover, it is preferable that a white decorating material further contains each component other than the white pigment and specific silicone resin demonstrated in the coloring composition for heating implement decoration of this invention mentioned above.

(Black decoration material)
The heating device of the present invention preferably includes a black decorative material, and more preferably includes the black decorative material on the side opposite to the substrate with respect to the white decorative material. The black decorative material is preferably provided adjacent to the white decorative material, but an adhesive layer or the like may be provided between the white decorative material and the black decorative material.
It is preferable to produce a black decorating material by the above-mentioned composition for black layer formation.
Moreover, it is preferable that a black decorating material contains each component demonstrated in the composition for black layer formation of this invention mentioned above.
The film thickness of the black decorative material in the heating device of the present invention is preferably 1.0 to 5.0 μm, preferably 1.0 to 4.0 μm from the viewpoint of enhancing the hiding power of the black decorative material. It is more preferable that
The optical density (OD; Optical Density) of the black decorative material is preferably 3.5 or more, particularly preferably 4.0 or more, from the viewpoint of enhancing the hiding power of the black decorative material.
The surface resistance of the black decorative material is preferably 1.0 × 10 ¹⁰ Ω / □ or more, more preferably 1.0 × 10 ¹¹ Ω / □ or more, and 1.0 × 10 ¹² Ω / □. More preferably, it is □ or more, and particularly preferably 1.0 × 10 ¹³ Ω / □ or more. Note that Ω / □ is Ω per square.

<Protective layer>
The heating device of the present invention preferably has a protective layer on the side of the decorative material opposite to the substrate.
When a silicone resin or silicone rubber excellent in heat resistance is applied to a heating device, the scratch resistance can be further improved by providing a protective layer on the opposite side of the decorative material to the substrate.
There is no restriction | limiting in particular as a material of a protective layer. As materials for the protective layer, materials known as materials for hard coat layers such as acrylic resin, and compounds having a siloxane bond such as silicone resin and silicone rubber can be used. Among them, the material of the protective layer is preferably a silicone resin or a silicone rubber from the viewpoint of enhancing the scratch resistance while improving the heat resistance (cracking and coloring). The silicone resin or silicone rubber can improve the scratch resistance without adversely affecting the heat resistance (cracking and coloring) as compared to a material known as a material for a hard coat layer such as an acrylic resin. The D / T ratio of the specific silicone resin used in the protective layer is preferably more than 0 and 2.5 or less, and more preferably 0.2 to 1.0. Other preferred embodiments of the silicone resin and silicone rubber used in the protective layer are the same as the preferred embodiments of the silicone resin or silicone rubber used in the coloring composition for heating appliance decoration of the present invention.
The thickness of the protective layer is preferably 30 to 500 μm from the viewpoint of enhancing the scratch resistance, and particularly preferably 50 to 300 μm.
Compared with materials known as materials for hard coat layers such as acrylic resins, compounds having siloxane bonds such as silicone resins and silicone rubbers generally have a brittle film quality when a film is formed, and it is difficult to increase the surface hardness. Therefore, when using silicone resin or silicone rubber as the material of the protective layer, increase the film thickness of the protective layer to enhance the scratch resistance and make it easier to handle the heater when it is used or when it is manufactured. Is preferred.

<Conductive layer>
The heating device of the present invention preferably further comprises a conductive layer on the decorative material, and more preferably further comprises a conductive layer on the black decorative material.
As the conductive layer, those described in JP-A-2009-505358 can be preferably used. In addition, the configuration and shape of the conductive layer will be described in the description of the first transparent electrode pattern, the second electrode pattern, and another conductive element in the description of the touch panel described later.
The conductive layer preferably contains indium (including indium-containing compounds such as indium tin oxide (ITO) and indium alloys).
In the present invention, since the cracking resistance of the decorative material is high, the film physical properties of the decorative material can be improved even when the conductive layer is deposited by sputtering.

<Touch panel>
The heating device of the present invention preferably has a touch panel.
In recent years, electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, bank terminals, etc. have been equipped with a liquid crystal display device having a touch panel type input device, and an image displayed on the liquid crystal display device etc. There is an electronic device which can input a desired instruction by making contact etc.
The input device (touch panel) includes a resistive film type, a capacitance type, and the like. The capacitance-type input device has an advantage that it is sufficient to form a transparent conductive film on only one substrate. The capacitive touch panel of the cover glass integrated type (OGS: One Glass Solution) touch panel can be thinned and / or reduced in weight because the front plate is integrated with the capacitive input device.
In a capacitive input device, an information display unit (an image display unit, a transparent display, or the like) that is touched with a finger or a touch pen or the like in order to prevent the user from visually recognizing the routing circuit or the like of the display device. A decorative material is formed in a frame shape surrounding the light region, and decoration is performed. As a decorating material for decorating, a white decorating material is calculated | required from a viewpoint of a design and appearance. In addition, a black decorative material (sometimes called a light shielding layer) or other material may be used so that the wiring circuit or the like of the display device can not be seen through by the white decorative material (white layer) alone. It may be required to use decorative materials colored in colors.
When manufacturing decorating materials, such as a white decorating material, a coloring layer (for example, white resin composition) is arrange | positioned on a board | substrate, and another coloring layer (for example, composition for light-shielding layer formation) as needed. Preferably, the uncured colored layer is cured by post-baking (heating) after disposing to make a decorative material.
The touch panel is preferably a capacitive input device.

(Capacitive input device)
The capacitive input device has a front plate (also referred to as a substrate), at least the following elements (1) to (4) on the non-contact surface side of the front plate, and 1) It is preferable to include the heating instrument of this invention as a laminated body of a decorating material.
(1) Decorative material (2) A plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through connection portions (3) A first transparent electrode pattern and electricity And a plurality of second electrode patterns (4) consisting of a plurality of pad portions formed to extend in a direction intersecting the first direction, and the first transparent electrode pattern and the second electrode pattern In addition, in the capacitive input device, the second electrode pattern may be a transparent electrode pattern.
Furthermore, the capacitive input device may further have the following (5).
(5) A conductive element electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern, and different from the first transparent electrode pattern and the second transparent electrode pattern The capacitive input device is a laminate having a front plate (substrate), (1) a decorating material, and at least one electrode pattern of (2), (3) and (5) described above as a conductive layer, More preferably, the heating device of the present invention is included.
(1) It is preferable that a decorating material further has a light shielding layer.

(Configuration of capacitive input device)
First, the configuration of the capacitive input device will be described.
FIG. 5 and FIG. 6 are cross-sectional views showing preferable configurations among the capacitance type input device.
In FIG. 5, the capacitance-type input device includes glass 1G (cover glass), a decorating material 2a, a decorating material 2b, a first transparent electrode pattern 3, a second transparent electrode pattern 4, and insulation It comprises a layer 5, another conductive element 6 and a transparent protective layer 7. The inclined portion 2c is provided in the decorative material 2a, and the decorative material 2a is formed so as to be thinner toward the inner side of the capacitive input device.

The substrate is preferably made of a transparent substrate.
The front plate provided with the decorative material is a mode in which the decorative material is provided on the front plate made of glass 1G (cover glass) or added to the front plate including glass 1G (cover glass) and substrate 1 (film substrate) Any of the embodiments provided with a decorative material can be used.
The aspect which provided the decorating material in the front plate which consists of cover glass is preferable from a viewpoint of touch-panel thickness reduction.
The embodiment in which the decorative material is provided on the front plate including the cover glass and the film substrate can be manufactured by providing the decorative material on the film substrate and laminating the film substrate on the cover glass, which is preferable from the viewpoint of touch panel productivity .
Moreover, a cover glass can be further provided on the opposite side of the electrode of the film substrate.
As glass, tempered glass etc. which are represented by the gorilla glass of Corning Inc. can be used.
Moreover, in FIG.5 and FIG.6, the side in which each element of a board | substrate is provided is called the non-contact surface 1a. In the capacitive input device, it is preferable that the input be performed by bringing a finger or the like into contact with the contact surface of the substrate (the surface opposite to the non-contact surface 1a).

Moreover, the decorating material 2a and the decorating material 2b are provided on the non-contacting surface of a board | substrate. The preferable aspect of the decorating material containing the decorating material 2a and the decorating material 2b is a frame-like pattern of the translucent area | region (display area) periphery formed in the non-contact surface side of a touch-panel front plate, It is formed for the purpose of making it invisible, etc. and the purpose of decoration.
The capacitive input device can be provided with a wiring outlet (not shown).
When forming a substrate with a decoration material of a capacitance type input device having a wiring extraction portion, the decoration material 2a may be formed using a liquid resist for formation of a decoration material or screen printing ink, but the back side of the substrate In order to easily prevent the contamination of the substrate, it is preferable to use a substrate with a decorating material having a wiring extraction portion.

On the non-contact surface of the substrate, a plurality of first transparent electrode patterns 3 formed by extending a plurality of pad portions in the first direction through the connection portions, a first transparent electrode pattern 3 and an electric And a plurality of second transparent electrode patterns 4 composed of a plurality of pad portions formed extending in a direction intersecting the first direction, the first transparent electrode patterns 3 and the second transparent An insulating layer 5 electrically insulating the electrode pattern 4 is formed. Examples of materials of the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 described later include metal films, and transparent and conductive materials such as ITO and IZO (Indium Zinc Oxide). Metal oxide film. Examples of the metal film and the metal oxide film include metal films of Al, Zn, Cu, Fe, Ni, Cr, Mo and the like; metal oxide films of ITO, SiO _{2 and the} like, and the like. At this time, the film thickness of each element can be 10 to 200 nm.
When the amorphous ITO film is converted to a polycrystalline ITO film by firing, the electrical resistance can also be reduced.
In addition, the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 described later may be manufactured using a transfer film having a decorative material using conductive fibers. it can. In addition, when forming a 1st transparent electrode pattern etc. by ITO etc., Paragraph 0014-0016 etc. of patent 4506785 can be referred to.

  In addition, at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 is disposed across both the non-contact surface of the substrate and the surface of the decorative material 2b opposite to the substrate. Can. In FIG. 5 and FIG. 6, the second transparent electrode pattern 4 is disposed across both regions of the non-contact surface of the substrate and the surface of the decorative member 2b opposite to the substrate. One aspect in which the second transparent electrode pattern 4 covers the side surface is shown. However, the width of the decorating material 2a can also be made narrower than the width of the decorating material 2b, in which case at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 The contact surface, the decorative material 2a and the decorative material 2b can be installed across the area of the surface opposite to the substrate. As described above, even when laminating a transfer film across the decorative material 2a and the decorative material 2b requiring a certain film thickness and the front plate back surface, a transfer material for heating tool decoration (especially, By using a transfer material for heating equipment decoration having a thermoplastic resin layer, even without using expensive equipment such as a vacuum laminator, there is a laminate in which no bubbles are generated at partial boundaries of the decoration material 2a in a simple process. It will be possible.

The first transparent electrode pattern 3 and the second transparent electrode pattern 4 will be described using FIG. 7.
FIG. 7 is an explanatory view showing an example of the first transparent electrode pattern and the second transparent electrode pattern.
As shown in FIG. 7, the first transparent electrode pattern 3 is formed by extending the pad portion 3a in the first direction via the connection portion 3b. Further, the second transparent electrode pattern 4 is electrically insulated from the first transparent electrode pattern 3 disposed via the insulating layer 5, and the second transparent electrode pattern 4 extends in a direction intersecting the first direction (a second direction in FIG. 7). And the plurality of pad portions formed extending in the Here, when the first transparent electrode pattern 3 is formed, the pad portion 3a and the connection portion 3b may be manufactured integrally, or only the connection portion 3b is manufactured to form the pad portion 3a and the second transparent. The electrode pattern 4 may be integrally manufactured (patterned). When the pad portion 3a and the second transparent electrode pattern 4 are integrally manufactured (patterned), as shown in FIG. 7, a portion of the connection portion 3b and a portion of the pad portion 3a are connected, and an insulating layer Each layer is formed such that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated by the reference numeral 5.

  In FIG.5 and FIG.6, another electroconductive element 6 is installed in the surface side on the opposite side to the board | substrate of the decorating material 2b. Another conductive element 6 is electrically connected to at least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4, and the first transparent electrode pattern 3 and the second transparent electrode pattern 4 Is another element. FIGS. 5 and 6 show an aspect in which another conductive element 6 is connected to the second transparent electrode pattern 4.

  Moreover, in FIG.5 and FIG.6, the transparent protective layer 7 is installed so that all of each component may be covered. The transparent protective layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the transparent protective layer 7 may be the same material or different materials. As a material which comprises the insulating layer 5 and the transparent protective layer 7, a thing with high surface hardness and heat resistance is preferable, and a well-known photosensitive siloxane resin material, an acrylic resin material, etc. are used.

  These show examples that embody the above description, and the scope of the present invention is not limitedly interpreted by these drawings.

  Capacitive type input devices and image display devices provided with the capacitive type input devices as components are the "latest touch panel technology" (issued July 6, 2009, Techno Times Inc.), Mitani The configuration disclosed in Yuji ed., "Touch panel technology and development", CMC Publishing (2004.12), FPD International 2009 Forum T-11 lecture text book, Cypress Semiconductor Corporation application note AN2292 etc. can be applied. .

<Method of manufacturing heating appliance>
The method of manufacturing the heating device preferably includes a layer forming step of forming a colored layer on a substrate, and a post-baking step of heating the colored layer to form a decorative material, and preferably further include other steps.

(Colored layer formation process)
The colored layer forming step is not particularly limited, but a layer consisting of a white resin composition and a layer consisting of a composition for forming a black layer, or a layer obtained by drying the white resin composition (uncured white layer) and black It is preferable to prepare a colored layer such as a layer obtained by drying the composition for forming a layer (uncured black layer) by a method selected from the group consisting of transfer, thermal transfer printing, screen printing and inkjet printing. It is more preferable to produce by film transfer (lamination method) using the transfer material for heating instrument decoration. As the above-mentioned transfer material, the transfer material for heating tool decoration of the present invention is preferably used.
The heating device of the present invention uses a silicone resin or silicone rubber of a specific structure, while the heating material manufactured by the sputtering method can not produce wiring or the like because the decorative material has conductivity. A touch panel can be provided to use the decorative material.
Specifically, the colored layer forming step preferably includes the step of laminating an uncured white layer and an uncured black layer in this order on the substrate. In the colored layer forming step, an uncured white layer and an uncured black layer are at least an uncured white layer from a heating material decorating transfer material including at least one of an uncured white layer and an uncured black layer on a temporary support. And a method of removing the temporary support after transferring one of the uncured black layers; the temporary support of the thermal transfer material side of the thermal transfer material including at least one of the uncured white layer and the uncured black layer on the temporary support; Thermal transfer printing for transferring at least one of an uncured white layer and an uncured black layer from a body; screen printing of a composition for forming a white layer or a composition for forming a black layer; and a composition for forming a white layer or a black layer It is preferred to make by a method selected from the group consisting of inkjet printing of the composition.
In addition, the decorating material has a frame-like shape surrounding the light transmitting region on the substrate, and an inner edge of the decoration material is an inclined portion in which the film thickness of the decoration material decreases toward the inside of the light transmitting region. It is preferable to include the step of forming

In the method of manufacturing the heating device, the colored layer of the heating device is formed by printing the coloring composition for heating device decoration of the present invention, or the coloring layer of the heating device is the transfer material for heating device decoration of the present invention It is preferable to be formed by transferring the colored layer of
Colored layers such as an uncured white layer and an uncured black layer may be formed by combining a plurality of film transfer, thermal transfer printing, screen printing, and inkjet printing.
Furthermore, in the method of manufacturing the heating device,
A method of removing the temporary support after transferring the uncured black layer and the uncured white layer onto the substrate from the transfer material for heating device decoration, comprising at least the temporary support, the uncured black layer and the uncured white layer in this order; ,
After transferring the uncured white layer onto the substrate from the transfer material for heating device decoration having the temporary support and the uncured white layer, the temporary support is removed, and further heating device containing at least the temporary support and the uncured black layer. It is preferable to form an uncured white layer and an uncured black layer using a method of transferring the uncured black layer from the decorative transfer material onto the uncured white layer and then removing the temporary support.
Hereinafter, the film transfer in the colored layer forming process, thermal transfer printing, screen printing, inkjet printing, post-baking process, and details of other processes will be described for the method of manufacturing the heating device.

-Transcription-
In the present invention, transfer (lamination method) is a method using the transfer material for heating tool decoration of the present invention, and a white layer and a black layer, or a layer obtained by drying the composition for forming a white layer (uncured white The method preferably includes a transfer step of transferring a colored layer such as a layer) and a layer obtained by drying the composition for forming a black layer (uncured black layer) to at least a substrate.
Transfer (bonding) of the colored layer such as the uncured white layer and the uncured black layer to the substrate surface is performed by overlapping the uncured white layer on the substrate surface, and applying pressure and heating. For lamination, the above-described known laminator can be used.
The lamination method is preferable from the viewpoint of high accuracy because it is a single-leaf type, since the desired punched colored layers such as the uncured white layer and the uncured black layer are transferred to the substrate. The laminating method is preferably a method in which air bubbles do not enter between the substrate and the colored layer such as the uncured white layer from the viewpoint of increasing the yield. Specifically, it is preferable to use a vacuum laminator.
As an apparatus used for a laminate (continuous type / sheet-fed type), V-SE340aaH etc. made by Crime Products Co., Ltd. can be mentioned, for example.
Examples of the vacuum laminator device include those manufactured by Takano Seiki Co., Ltd., FVJ-540R, FV700 manufactured by Taisei Laminator Co., Ltd., and the like.

  By including a step of laminating a further support on the opposite side of the temporary support to the colored layer before affixing the transfer material for heating tool decoration to the substrate, it is possible to obtain a preferable effect that air bubbles are not inserted at the time of lamination. May be There is no particular limitation on the additional support used at this time. Examples of the material of the further support include polyethylene terephthalate, polycarbonate, triacetyl cellulose and cycloolefin polymer. Furthermore, the film thickness of the further support is preferably in the range of 50 to 200 μm.

  In the method of manufacturing the heating device, when the colored layer forming step is performed by film transfer, the method of manufacturing the heating device preferably further includes the step of removing the temporary support from the transfer material attached to the substrate.

In the method of manufacturing the heating device, the colored layer forming step is performed by film transfer, and when the transfer material for heating device decoration includes a thermoplastic resin layer or an intermediate layer, the method of manufacturing the heating device includes the thermoplastic resin layer and Alternatively, it is preferable to further include the step of removing the intermediate layer.
The step of removing the thermoplastic resin layer and / or the intermediate layer can be carried out using an alkaline developer generally used in the photolithography method.
There is no restriction | limiting in particular as an alkali developing solution, Well-known developing solutions, such as a thing of Unexamined-Japanese-Patent No. 5-72724, can be used. The developing solution is preferably one in which the decorating material has a dissolution type developing behavior, for example, a compound of pKa (power of Ka; Ka represents an acid dissociation constant) = 7 to 13 in an amount of 0.05 to 5 mol / L. Although it is preferable to include it in the concentration of (1), a small amount of an organic solvent miscible with water may be further added.
As an organic solvent miscible with water, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol And acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1 to 30% by mass.
In addition, known surfactants can be added to the alkali developer. The concentration of the surfactant is preferably 0.01 to 10% by mass.

  As a system of the process of removing a thermoplastic resin layer and / or an intermediate | middle layer, any, such as a paddle, a shower, shower & spin, a dip, etc. may be sufficient. Here, to describe the shower, the thermoplastic resin layer and / or the intermediate layer can be sprayed with a developing solution by a shower to remove the thermoplastic resin layer and / or the intermediate layer. In addition, after development, it is preferable to spray a cleaning agent or the like on the thermoplastic resin layer and / or the intermediate layer with a shower and remove the residue while rubbing with a brush or the like. The temperature of the developer is preferably 20 ° C to 40 ° C, and the pH (power of hydrogen) is preferably 8 to 13.

-Thermal transfer printing-
When using thermal transfer printing, heat the temporary support side of the thermal transfer material including at least one of the uncured white layer and the uncured black layer on the temporary support and the colored layer such as the uncured white layer and the uncured black layer. It is preferable to prepare by thermal transfer printing in which at least one of the uncured white layer and the uncured black layer is transferred onto the substrate from the temporary support. In thermal transfer printing, it is preferable to carry out at a heating temperature and heating time that do not completely cure colored layers such as the uncured white layer and the uncured black layer.
As a method of thermal transfer printing, ink ribbon printing is preferable. As a method of ink ribbon printing used in a method of manufacturing a heating device, mention may be made of the method described in "Non-impact printing-technology and materials-(CMC publication, December 1, 1986)" and the like. it can.

-Screen printing-
When screen printing is used, a colored layer such as an uncured white layer and / or an uncured black layer is coated on a substrate with a colored composition for heating tool decoration such as a white resin composition and / or a composition for forming a light shielding layer. It is preferable to make by screen printing method.
The screen printing method is not particularly limited, and any known method can be used. For example, the method described in Japanese Patent No. 4021925 can be used. In addition, by performing screen printing a plurality of times, the film thickness can be increased even by screen printing.

-Ink jet printing-
When ink jet printing is used, a colored layer such as an uncured white layer and / or an uncured black layer is coated on a substrate with a colored composition for heating tool decoration such as a white resin composition and / or a composition for forming a black layer. It is preferable to produce by the method of inkjet printing. As a method of inkjet printing used for the manufacturing method of a heating instrument, the method as described in "Electronics application of inkjet technology (Realize Riko Center Co., Ltd., Inc., September 29, 2006)" can be mentioned.

(Post-bake process)
When forming a heating tool, it is preferable to include a post-baking step after the colored layer forming step, and when performing a colored layer forming step by film transfer, post-baking is performed after the step of removing the thermoplastic resin layer and / or the intermediate layer. More preferably, the steps are carried out. It is preferable to harden a colored layer such as an uncured white layer and / or an uncured black layer by post-baking to form a decorative material.
In the method of manufacturing the heating device, the coloring composition for heating device decoration of the present invention is cured to form a decorative material or a colored layer of the transfer material for heating device decoration of the present invention is transferred by a post-baking step. It is preferable to cure the formed transfer material to form a decorating material.
In the post-baking process, colored layers such as the uncured white layer and the uncured black layer of the transfer material for heating tool formation are formed by heating to 50 ° C. to 300 ° C. under an environment of 0.08 to 1.2 atmospheres. Is preferable from the viewpoint of achieving both strength and productivity. In addition, it is 1 atmospheric pressure = 0.101325 Mpa.
In addition, it is preferable that the inner edge of the decorative material has an inclined portion formed in such a manner that the film thickness of the decorative material decreases toward the inward of the light transmission region. The layer is preferably formed by shrinking by heating. For example, in the post-baking step, the colored layer can be shrunk by heating the decorative material at 50 ° C. to 300 ° C., thereby forming the sloped portion.

The post-baking heating is more preferably performed under an environment of 0.5 atm or more. On the other hand, it is more preferable to carry out under an environment of 1.1 atm or less, and it is particularly preferable to carry out under an environment of 1.0 atm or less. Furthermore, it is more preferable to carry out under about 1 atm (atmospheric pressure) environment from the viewpoint of reducing the manufacturing cost without using a special pressure reducing device. Here, conventionally, when forming a colored layer such as an uncured white layer and an uncured black layer by curing by heating, the strength after baking is performed under a reduced pressure environment at a very low pressure to lower the oxygen concentration. However, by using the transfer material for heating tool decoration, the color tone of the colored layer such as the white layer and the black layer is improved even after baking in the above pressure range (b * value is reduced). ), Whiteness can be increased.
50 degreeC-300 degreeC is preferable, as for the temperature of post-baking, 100 degreeC-300 degreeC is more preferable, and 120 degreeC-300 degreeC is more preferable.
Also, post-baking may be performed at two or more different temperatures for a predetermined time. For example, it can be heated first at preferably 50 ° C. to 200 ° C., more preferably 100 ° C. to 200 ° C., and then preferably heated at 200 ° C. to 280 ° C., more preferably 220 ° C. to 260 ° C.
The post-baking time is more preferably 20 to 150 minutes, and particularly preferably 30 to 100 minutes. When post-baking is performed at two or more temperatures, it is preferable that the total of the post-baking time in each stage be 20 to 150 minutes.
Post-baking may be performed in an air environment or in a nitrogen-substituted environment, but it is particularly preferable to perform in an air environment from the viewpoint of reducing the manufacturing cost without using a special pressure reducing device.

<Other process>
The method of manufacturing the heating device may have other steps other than those described above.
In addition, as an example of the process of removing a thermoplastic resin layer and / or an intermediate | middle layer, and another process, the method as described in stage 0035-0051 of Unexamined-Japanese-Patent No. 2006-23696 is suitably used also in this invention. be able to.

[Cooking device]
The cooker of the present invention comprises the heating device of the present invention.
Hereinafter, the preferable aspect of the cooker of this invention is demonstrated.

<Structure of cooker>
The structure of an example of the cooker of this invention is shown in FIG. The cooker 31 of the present invention shown in FIG. 8 has the induction heating unit 21 on the heating device which is the cooker top plate 23, and the cooker top plate 23 is formed with the decorating material 2a and the decorating material 2a. The touch panel 22 is provided in the part which is not.
The cooker top plate 23 may be formed on a substrate (not shown).
The cooker of the present invention is not particularly limited, but is preferably a cooker having an image display unit and a touch panel. For example, the cooker of the present invention is preferably an induction heating (IH) cooker, an infrared cooker, a gas cooker, a microwave oven, an oven, a rice cooker, a heater, a pan, an electric pot, etc. What provided an image display part and a touch panel in these cookers is more preferable. In addition, the cooker according to the present invention is preferably influenced by recent changes in IoT (Internet of Things) and can be operated from the outside via the Internet, and is preferably a cooker having an image display unit. . Among these, the cooker of the present invention is more preferably an electromagnetic cooker, an infrared cooker, or a gas cooker which is a cooker having a cooker top plate, and particularly preferably an electromagnetic cooker. .

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. In addition, unless there is particular notice, "part" and "%" are mass references.

[Examples 1 to 22, Comparative Examples 1 to 6]
<Preparation of coloring composition (white coloring composition) for heating appliance decoration>
The coloring composition for heating implement decorating of Examples 1-22 and Comparative Examples 1-6 which are white coloring compositions described in the following Table 1 or Table 2 was prepared using the following materials. The numerical values in Tables 1 and 2 below indicate the content (parts by mass) of each component with respect to the total mass of the coloring composition for heating appliance decoration, and "-" indicates that each component is not contained. ing.

The details of the compounds described in the above Table 1 or Table 2 are as follows.
White pigment dispersion 1: FP White AD 4035, Sanyo Dye Co., Ltd. (70% titanium oxide concentration, 73% solid content concentration)

White pigment dispersion liquid 2: Zirconia beads (particle size 0.5 mm) are added to a mixture obtained by mixing the following materials, and 2000 rpm (revolutions per minute) is obtained using a bead mill (BSG-01 manufactured by Imex Co., Ltd.) Dispersion treatment was carried out for 1 hour to obtain a white pigment dispersion liquid 2.
Titanium oxide (CR-97, manufactured by Ishihara Sangyo Co., Ltd.): 60.0 parts Dispersant A (described below for the synthesis method): 6.0 parts Xylene: 34.0 parts

-Synthesis of Dispersant A-
45.8 parts of KF-2001 (Shin-Etsu Chemical Co., Ltd. product), 53.3 parts of KF-2012 (Shin-Etsu Chemical Co., Ltd. product), 0.9 parts of methacrylic acid are dissolved in 100 parts of xylene, and polymerization is carried out 0.3 mol% of an initiator (dimethyl-2,2'-azobis (2-methyl propionate), V-601, manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in a ratio to all the polymerization components, under a nitrogen atmosphere The polymerization was carried out at 80 ° C. On the way, after 2 hours from the start of polymerization, a polymerization initiator (V-601) was additionally added by 0.3 mol% in a ratio to all the polymerization components, and polymerization was performed for a total of 4 hours. After polymerization, purification treatment and drying were performed to obtain Dispersant A (weight average molecular weight 40,000).
KF-2001 is a structure represented by the following formula ( ^RA represents an arbitrary linking group and a1 and a2 represent natural numbers), and has a functional group equivalent weight of 1,900 (g / mol) .
KF-2012 is a structure represented by the following formula (R represents an arbitrary substituent or a linking group, n represents a natural number), and has a functional group equivalent of 4,600 (g / mol) .

· Silicone resin 1 (KR-251, Shin-Etsu Silicone Co., Ltd.): Toluene solution of silicone resin (solid content: 20% by mass)

· Silicone resin 2 (X-40-9246, manufactured by Shin-Etsu Silicone Co., Ltd.): alkoxysilicone oligomer (solid content: 100% by mass)

・ Silicone resin 3: Synthetic (For synthesis, see below)
-Synthesis method of silicone resin 3-
In a reaction vessel equipped with a stirrer, a condenser, a thermometer and a heating and cooling jacket, 477 parts of toluene, 420.7 parts of triethoxymethylsilane (made by Tokyo Kasei Co., Ltd.) and 77.4 parts of dichlorodimethylsilane (Manufactured by Tokyo Kasei Kogyo Co., Ltd.) was charged and stirred to be uniform.
Subsequently, 200 parts of pure water was dropped to the reaction vessel to carry out hydrolysis. Then, the temperature of the reaction solution was raised to 50 ° C. with stirring, and stirring was continued for another 80 minutes while maintaining the temperature constant under reflux. Then, the reaction solution was allowed to stand to separate the organic layer and the aqueous layer. 200 parts of pure water was added to the separated organic layer and washed with water. The mixture was allowed to stand and separated again, and 500 parts of a pale yellow transparent silicone resin in toluene solution was obtained in the separated organic layer. Furthermore, toluene was added to the organic layer to obtain a solution (silicone resin 3) having a silicone resin content of 30% by mass.
The weight average molecular weight of the silicone resin 3 is 3,000,000, and the D / T ratio of the silicone resin 3 is 0.25.

・ Silicone resin 4: Composite (For the synthesis, see below)
In the synthesis of the silicone resin 3, the silicone resin 4 was obtained by synthesizing 394.4 parts of triethoxymethylsilane and 96.8 parts of dichlorodimethylsilane.
The weight average molecular weight of the silicone resin 4 is 2,500,000, and the D / T ratio of the silicone resin 4 is 0.33.

・ Silicone resin 5: Synthetic (For synthesis, see below)
In the synthesis of the silicone resin 3, a silicone resin 5 was obtained by synthesizing 260.0 parts of triethoxymethylsilane and 185.0 parts of dichlorodimethylsilane.
The weight average molecular weight of the silicone resin 5 is 2,500,000, and the D / T ratio of the silicone resin 5 is 1.03.

· Silicone resin 6 (KR300, manufactured by Shin-Etsu Silicone Co., Ltd.): Xylene solution of silicone resin (solid content: 50% by mass)

· Silicone resin 7 (KR 311, manufactured by Shin-Etsu Silicone Co., Ltd.): Xylene solution of silicone resin (solid content: 60% by mass)

· Silicone resin 8 (KR 271, manufactured by Shin-Etsu Silicone Co., Ltd.): Xylene solution of silicone resin (solid content: 50% by mass)

· Silicone resin 9 (KR 242A, manufactured by Shin-Etsu Silicone Co., Ltd.): solution of silicone resin in toluene / isopropyl alcohol (solid content: 50% by mass)

・ Silicone resin 10: Synthetic (For synthesis, see below)
-Synthesis method of silicone resin 10-
In a reaction vessel equipped with a stirrer, a condenser, a thermometer and a heating and cooling jacket, 1600 parts of toluene, 534.5 parts of triethoxymethylsilane (made by Tokyo Kasei Co., Ltd.) and 447.6 parts of dichlorodimethylsilane (Tokyo Chemical Industry Co., Ltd.) and 882.0 parts of dichlorodiphenylsilane (Tokyo Chemical Industry Co., Ltd.) were charged and stirred uniformly.
Subsequently, 200 parts of pure water was dropped to the reaction vessel to carry out hydrolysis. Then, the temperature of the reaction solution was raised to 50 ° C. with stirring, and stirring was continued for another 80 minutes while maintaining the temperature constant under reflux. Then, the reaction solution was allowed to stand to separate the organic layer and the aqueous layer. 200 parts of pure water was added to the separated organic layer and washed with water. The mixture was allowed to stand and separated again, and a toluene solution of pale yellow transparent silicone resin was obtained in the separated organic layer. Furthermore, toluene was added to the organic layer to prepare a solution (silicone resin 10) having a silicone resin content of 50% by mass.
The weight average molecular weight of the silicone resin 10 is 5,000, and the D / T ratio of the silicone resin 10 is 2.30.

・ Silicone resin 11: compound (for synthesis see below)
In the synthesis of the silicone resin 10, the silicone resin 11 is synthesized by synthesizing 712.4 parts of triethoxymethylsilane, 383.9 parts of dichlorodimethylsilane, and 755.8 parts of dichlorodiphenylsilane. Obtained.
The weight average molecular weight of the silicone resin 11 is 6,000, and the D / T ratio of the silicone resin 11 is 1.50.

・ Silicone resin 12: Synthetic (See below for the synthesis)
In the synthesis of the silicone resin 10, the silicone resin 12 is synthesized by synthesizing 511.8 parts of triethoxymethylsilane, 882.0 parts of dichlorodimethylsilane, and 755.8 parts of dichlorodiphenylsilane. Obtained.
The weight average molecular weight of the silicone resin 12 is 5,000, and the D / T ratio of the silicone resin 12 is 3.00.

-Silicone rubber 1 (KR-581U, manufactured by Shin-Etsu Silicone Co., Ltd.): silicone rubber (solid content: 100% by mass)
・ Silicone rubber 2 (X-21-3043, Shin-Etsu Silicone Co., Ltd. product): Silicone rubber (solid content: 100% by mass)

-Acrylic resin 1: Compound of the following structure
In the acrylic resin 1, x / l / y / z = 51.5 / 2 / 26.5 / 20, and the weight average molecular weight of the acrylic resin 1 is 30,000 (solid content 100%).

Condensation catalyst 1 (ZC-200, manufactured by Matsumoto Fine Chemical Co., Ltd.): Zirconium octylate compound (solid content: 80% by mass)
・ Antioxidant 1 (IRGAFOS 168, manufactured by BASF, the following compounds)

Surfactant 1 (Megafuck F-780F, manufactured by DIC Corporation): methyl ethyl ketone solution of surfactant (solid content: 30% by mass)

(D / T ratio measurement method)
The D / T ratio is measured by the following method with reference to the method described in Chapter 20 of "Silicone Handbook (Kunio Ito, Nikkan Kogyo Shimbun Co., Ltd.)".
The D / T ratio of the silicone resin is determined from the peak area ratio of ²⁹ Si-NMR using ²⁹ Si-NMR (ECP 400 manufactured by Nippon Denshi Co., Ltd.). The measurement conditions of ²⁹ Si-NMR are as follows: using a PTFE 10 mm diameter sample tube, probe: T10, resonance frequency 79.42 MHz, pulse width 10 μsec (sec is abbreviation of second), waiting time 20 sec, integration time 1,500 times Relaxation reagent: Chromium (III) acetylacetonate Cr (acac) ₃ 0.1% by mass, external standard sample: tetramethylsilane. Moreover, the chemical shift of < ²⁹ > Si-NMR derived from each structure is as follows.
D structure: -20 to -25 ppm
T body structure: -60 to -70 ppm
The D / T ratio of the silicone resin or the D / T ratio of the silicone rubber in the composition containing two or more types of silicone resins or silicone rubbers can be measured by the above measurement method.

[Examples 23 to 28 and Comparative Example 7]
<Preparation of coloring composition (black coloring composition) for heating appliance decoration>
The coloring composition for heating implement decoration of Examples 23-28 and Comparative Example 7 which are black coloring compositions described in the following Table 3 was prepared using the following materials. Numerical values in Table 3 below indicate the content (parts by mass) of each component with respect to the total mass of the coloring composition for heating appliance decoration, and "-" indicates that each component is not contained.

The details of the compounds described in Table 3 above are as follows.
-Black pigment dispersion 1: GC4151, Sanyo Dye Co., Ltd. product (carbon black concentration 15%, solid content concentration 20.7%)

-Black pigment dispersion liquid 2: With respect to the mixture which mixed the following materials, it disperse | distributed for 3 hours with a bead mill using zirconia beads 0.5 mm in diameter, and the black pigment dispersion liquid 2 was obtained.
Carbon black (Mitsubishi Chemical Co., Ltd. product): 15.0 parts Dispersant A (the synthetic method mentioned above): 4.8 parts Silicone oil (X-22-4039, Shin-Etsu Chemical Co., Ltd. product): 3.0 parts Xylene : 77.2 parts

Condensation catalyst 2 (D-15, manufactured by Shin-Etsu Chemical Co., Ltd., a xylene solution of a zinc-containing catalyst (solid content 25% by mass))

[Examples 29 to 41]
<Preparation of coloring composition (coloring composition) for heating appliance decoration>
The coloring composition (coloring composition) for heating implement decoration of Examples 29-41 of following Table 4 was prepared using the following materials. Numerical values in the following Table 4 indicate the content (parts by mass) of each component with respect to the total mass of the coloring composition for heating appliance decoration, and "-" indicates that each component is not contained.

The details of the compounds described in Table 4 above are as follows.
Silver pigment dispersion 1 (FD-5060, manufactured by Asahi Kasei Metals Co., Ltd.): Mineral spirit solution of aluminum paste (solid content: 72% by mass)
Silver pigment dispersion 2 (CP-525, manufactured by Asahi Kasei Metals Co., Ltd.): Mineral spirit solution of aluminum paste (solid content: 79% by mass)
-Yellow dye: What melt | dissolved 12.5 mass parts of following yellow dye compounds in 87.5 mass parts of tetrahydrofuran (made by Wako Pure Chemical Industries, Ltd.) (dye as described in Unexamined-Japanese-Patent No. 2014-177502).

-Cyan pigment: Cyan pigment dispersion prepared by the following method (preparation of cyan pigment dispersion)
The components of the following composition were mixed and stirred at a rotational speed of 3000 rpm for 3 hours using a homogenizer to mix, and a mixed solution containing a pigment was prepared.
-Composition of mixed solution containing pigment-
-Pigment Yellow 185 125 parts-Phthalocyanine derivative 5 parts (Sol Sparse 3000, manufactured by Nippon Lubrizol Co., Ltd.)
Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (weight average molecular weight: 5,000) (50% solid content) 15 parts Dispersant (Disperbyk-161) Bic Chemie Japan Co., Ltd. 60 parts, propylene glycol monomethyl ether acetate 795 parts

Subsequently, the mixed solution containing the pigment obtained above is further subjected to dispersion treatment for 12 hours with a bead disperser Dispermat (manufactured by GETZMANN Co., Ltd.) using 0.3 mm diameter zirconia beads, and then a pressure reduction mechanism is further provided. Dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.). This dispersion process was repeated 10 times to obtain a cyan pigment dispersion.

Blue pigment: Blue pigment dispersion prepared by the following method (preparation of blue pigment dispersion)
After kneading each component of the following composition A with a kneader for 30 minutes, high viscosity dispersion treatment was further performed by two rolls.
-Composition A-
30 parts of pigment (C.I. (C.I. is abbreviation of Color Index International) Pigment Blue 15: 6) 3 parts of dispersant (Disper 163, BYK Co.) Resin (benzyl (meth) acrylate / methacrylic acid 20 parts of a propylene glycol monomethyl ether acetate solution (solid content: 50%) of copolymer

Each component of the following composition B is added to the dispersion obtained as described above, and the resulting mixture is stirred for 3 hours using a homogenizer, and then further stirred with a 0.3 mm zirconia bead disperser (trade name: Dispermat, manufactured by GETZMANN) 4 As a result of performing time fine dispersion treatment, a blue pigment dispersion was obtained.
-Composition B-
・ Propylene glycol monomethyl ether acetate solution of resin (benzyl (meth) acrylate / methacrylic acid copolymer) (solid content 50%) 20 parts ・ Propylene glycol monomethyl ether acetate 170 parts

[Examples 101 to 130 and Comparative Examples 101 to 107]
<Preparation of transfer material for heating device decoration>
(Preparation of release film)
The following release films were prepared as a temporary support with a release layer of a transfer material for heating tool decoration.
Unipeel TR6 (product of Unitika Co., Ltd., has an olefin-based release layer having a matting agent raised by 200 nm from the release layer on a PET film with a thickness of 75 μm)

(Preparation of protective film)
Next, the following protective films were prepared.
GF-8 (manufactured by Tamapoly Co., Ltd., a polyethylene film with a film thickness of 35 μm)

(Preparation of a colored layer (white colored layer or black colored layer) on a temporary support)
The coloring composition for heating tool decoration of Examples 1 to 20 and Comparative Examples 1 to 6 described in Table 1 or Table 2 above on the release layer of the temporary support with release layer using an extrusion type coating machine. The product (white colored composition) was applied to a dry film thickness of 40.0 μm and dried. The above protective film was crimped onto the white colored layer.
Thus, transfer materials for heating implement decoration of Examples 101 to 120 and Comparative Examples 101 to 106 shown in the following Table 5 in which the temporary support and the white colored layer were integrated were produced.
Further, instead of the white coloring composition, the coloring composition (black coloring composition) for decorative heating appliances of Examples 23 to 28 and Comparative Example 7 described in Table 3 above has a dry film thickness of 4.0 μm. By apply | coating to this, the transfer material for heating implement decoration of Example 121-126 of the following Table 5 and the comparative example 107 was produced.

(Preparation of a colored layer (a laminate of a black colored layer and a white colored layer) on a temporary support)
A coloring composition for heating tool decoration according to the above-mentioned Table 3 for forming a black colored layer on a release layer of a temporary support having a release layer using an extrusion type coating machine (black coloring composition) Among them, the coloring composition for decorating heating appliances described in Table 5 below (black coloring composition) was applied to a dry film thickness of 3.0 μm and dried.
Among the coloring compositions for decorating a heating device (white coloring composition) described in the above Table 1 or 2 for forming a white coloring layer on a black coloring layer, the heating devices described in the following Table 5 The decorative coloring composition (white coloring composition) was applied to a dry film thickness of 40.0 μm and dried.
The above protective film was crimped onto the white colored layer.
In this way, a transfer material for heating implement decoration of Examples 127 to 130 described in Table 5 below having a temporary support, a laminate of a black colored layer and a white colored layer, and a protective film was produced.

[Examples 201 to 230 and Comparative Examples 201 to 207]
<Fabrication of heating equipment (transfer method)>
Glass cleaning agent in which crystallized glass (“Neoceram N-0” manufactured by Nippon Electric Glass: average linear thermal expansion coefficient at 30 ° C. to 500 ° C .: 1 × 10 ⁻⁷ / ° C., film thickness 4 mm) was adjusted to 25 ° C. The solution was washed with a rotating brush having nylon hair while being sprayed by a shower for 20 seconds. This was used as a glass substrate. The glass substrate was preheated at 90 ° C. for 2 minutes in a substrate preheating apparatus.
In order to form the transfer material for heating tool decoration of Example 101 into a frame shape corresponding to the four sides of the glass substrate on the above glass substrate and form a touch panel described later, a portion corresponding to a panel operation portion It punched and removed by the die-cut method. After peeling off the protective film from the transfer material for heating tool decoration after punching, the white colored layer and the temporary support were transferred onto a glass substrate. Thereafter, the temporary support of the transfer material for heating implement decoration of Example 101 was peeled off. In order to cure the white colored layer, the obtained film is heated at 150 ° C. for 30 minutes for each glass substrate (substrate), and further heat treated (baked) three times in the order of 240 ° C. for 30 minutes and 300 ° C. for 30 minutes. The heating implement (cooker top plate) of Example 201 which has a white decorating material formed by heating a white colored layer was obtained.
A white coloring layer and / or a black coloring on a glass substrate as in Example 201 except that the transfer material for heating tool decoration used in Example 201 is changed as described in Table 7 or Table 8 below. The heating apparatus of Examples 202-230 and Comparative Examples 201-207 in which the layer was formed was obtained.

[Examples 231 to 253 and Comparative Examples 208 to 210]
<Fabrication of heating equipment (printing method)>
The coloring composition for heating tool decoration of Example 1 was screen-printed with a screen printer (made by Mishima Corporation; UDF-5L, mesh size 250 micrometers) on the said glass substrate. A portion corresponding to a panel operation portion for forming a touch panel to be described later was subjected to printing so as not to receive ink, and then dried at 150 ° C. for 10 minutes. Furthermore, screen printing was performed as described above, and drying was performed at 100 ° C. for 10 minutes. The printing and drying steps were repeated a total of three times. The thickness of the colored layer after ink drying was 40 μm. After drying at 150 ° C. for 30 minutes, the heating device of Example 231 was produced.
By using the coloring composition for heating equipment decoration listed in the following Table 8 instead of the coloring composition for heating equipment decoration of Example 1, the heating equipment of Examples 232 to 253 and Comparative Examples 208 to 210 Was produced.

[Examples 254 and 255]
<Preparation of a heating device and a protective layer>
In Example 254, the protective layer coating solution A described in Table 6 below is coated on the decorative material of the heating apparatus of Example 241 with a screen printing machine (Misima Co., Ltd .; UDF-5L, mesh size 250 μm) Screen-printed and dried at 150 ° C. for 10 minutes. Furthermore, screen printing was performed as described above, and drying was performed at 100 ° C for 10 minutes. The steps from printing to drying were repeated, and coating and drying were repeated so that the thickness of the protective layer after drying was 100 μm. Finally, drying was carried out at 240 ° C. for 30 minutes to produce the cookware of Example 254, which is a cookware having a protective layer on the decorating material.
A cooking device of Example 255 was produced in the same manner as in Example 254 except that, in Example 254, the protective layer coating liquid B described in Table 6 below was used instead of the protective layer coating liquid A.
Silicone resin 13: Synthetic product In the synthesis of the silicone resin 3, the silicone resin 13 was obtained by synthesizing 368.1 parts of triethoxymethylsilane and 116.2 parts of dichlorodimethylsilane.
The weight average molecular weight of the silicone resin 13 is 2,500,000, and the D / T ratio of the silicone resin 13 is 0.43.

[Comparative Examples 211 and 212]
<Fabrication of cooker top plate (sputtering method)>
An interference layer, a light shielding layer, and a protective layer are sputtered in this order on the glass substrate using the film materials shown in Table 7 below so as to obtain the film thicknesses shown in Table 7 below (abbreviation of sputtering method) It formed by the method. A portion corresponding to a panel operation portion for forming a touch panel described later was protected from being sputtered. In addition, the film-forming atmosphere at the time of forming each layer by sputtering method was made into the gas atmosphere shown in following Table 7. In addition,% of gas atmosphere conditions shown to following Table 7 is volume%.
The resulting laminate was used as a heating device of Comparative Examples 211 and 212.

[Evaluation]
The evaluation method of the characteristic of the heating instrument obtained above is shown below.

<Scratch resistance>
About the heating instrument of each Example and a comparative example, it evaluated about the scratch resistance at the time of touching with a finger.
The evaluation results were evaluated as follows by sensory evaluation.
A: Even if I touch it hard, I can not see traces of fingerprints.
B: If you touch it with your finger, you can see marks, but if you touch it lightly, you can not see the marks you touch.
C: Stickiness can be seen by touching with a finger, and fingerprints etc. can be confirmed just by touching lightly.
As a level of scratch resistance, it is practically necessary that it is A and B evaluation, and it is preferred that it is A.
The obtained results are shown in Table 8 or Table 9 below.

<Heat resistant (cracked)>
About the heating instrument of each Example and a comparative example, the presence or absence of the crack was observed visually.
The evaluation results were evaluated as follows by sensory evaluation.
A: Cracks can not be confirmed visually.
B: 1 to 2 very slight cracks at a level of less than 1 mm at the end (a level that can be corrected with ink etc.).
C: Several slight cracks at a level of less than 1 mm at the end are recognized (levels that can be corrected with ink etc.).
D: Cracks can be seen on the entire surface.
It is practically necessary that the heat resistance (crack) level is A, B, C evaluation, preferably A, B, and more preferably A.
The obtained results are shown in Table 8 or Table 9 below.

<Heat resistance (coloring)>
About the heating instrument of each Example and a comparative example, the presence or absence of coloring was observed visually.
The evaluation results were evaluated as follows by sensory evaluation.
A: There is no change in color before and after bake treatment.
B: Although there is a change in color before and after the baking treatment, it is within an acceptable range.
C: Although there is a change in color before and after bake treatment, it is a range in which the color can be adjusted.
D: There is a color change before and after bake treatment, which is a range in which the color can not be adjusted.
The heat resistance (coloring) level is practically required to be A, B, C evaluation, preferably A, B, and more preferably A.
The obtained results are shown in Table 8 or Table 9 below.

<Toning properties>
It is preferable that the heating apparatus of each Example and a comparative example can be easily adjusted in color tone by adding another coloring agent.
At least one of white pigment dispersion liquid 1 and black pigment dispersion liquid 1 is added to show a region where color tone can be adjusted when it deviates from the target color, and the heating appliance decorative material of each example and comparative example It indicates whether it is possible to change the tint when adjusting the tint. The evaluation results were evaluated as follows by sensory evaluation.
A: The color tone can be adjusted by the addition of the white pigment dispersion 1 and the black pigment dispersion 1.
B: Taste is possible by addition of the white pigment dispersion liquid 1 (black direction can not be adjusted).
C: not adjustable (the white pigment dispersion 1 and the black pigment dispersion 1 can not be added).
It is practically necessary that the toning property be A or B, and preferably A.
The obtained results are shown in Table 8 or Table 9 below.

From the above Table 8 or Table 9, the heating devices of Examples 201 to 255 prepared by the transfer method or the printing method are excellent in scratch resistance, heat resistance in terms of cracking, heat resistance in terms of coloring, and color matching property. It turned out to be good. In particular, the heating devices of Examples 254 and 255 having the protective layer were found to be all very good in all of the heat resistance in terms of scratch resistance, heat resistance in terms of cracking, and color matching, and toning properties. . The effect of providing the protective layer in this manner is expected to be the same regardless of whether the manufacturing method is a transfer method or a printing method.
In the heating devices of Comparative Examples 201 to 203 and 208 in which the decorating material is formed using the material not containing the D-body structure in the silicone resin or the silicone rubber, many cracks occur after the baking process, and The heat resistance was bad, and a problem was seen in the appearance. On the other hand, the heating devices of Comparative Examples 204, 205, 209, and 210 in which the decorative material is formed using a material using only a silicone resin having a D / T ratio of 2.5 or more as a silicone resin, even after baking It was found that the film surface was tacky, the scratch resistance was poor, and the handling at the time of production was difficult.
The heating devices of Comparative Examples 206 and 207 in which the decorative material was formed using an acrylic resin had a large change in color after baking, had poor heat resistance from the viewpoint of coloring, and had problems with the appearance.
On the other hand, in the sputtering method shown in Comparative Examples 211 and 212, since the transmission density of the sputtered film is high, color adjustment using a coloring agent can not be performed, and the color of the top plate is silver (metal). Limited to the taste.

[Examples 301 to 355 and Comparative Examples 301 to 312]
<Correction of the heating device where a crack was seen>
With respect to the heating apparatus of Example 101 in which several slight cracks were observed at the end, the white pigment dispersion liquid 1 was applied to the cracked portions with a brush, and the cracks were corrected so as not to be noticeable. The modified heating device was subjected to heat treatment in the order of heating at 150 ° C. for 30 minutes and further 240 ° C. for 30 minutes, and the resulting heating device was used for the subsequent evaluation.
Similarly, the heat resistance (cracking) evaluation performed correction work similarly also to the heating instrument of the Example of B, C, D, and a comparative example.

<Formation of first transparent electrode pattern>
(Formation of transparent electrode layer)
The heating apparatus of Example 201 is introduced into a vacuum chamber, and DC (Direct Current) magnetron sputtering is performed using an ITO target (indium: tin = 95: 5 (molar ratio)) having a SnO ₂ content of 10% by mass. (Condition: substrate temperature 250 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), an ITO thin film with a film thickness of 40 nm was formed, and a front plate on which a transparent electrode layer was formed was obtained. The surface resistance of the ITO thin film was 80 Ω / □ (Ω per square).

-Preparation of transfer film E1 for etching-
The thermoplastic resin layer and the intermediate layer were formed on the temporary base material by the following method.
On a polyethylene terephthalate film temporary support having a film thickness of 75 μm, using a slit nozzle, a coating solution for a thermoplastic resin layer consisting of the following formulation H1 was applied and dried. Next, an intermediate layer coating solution consisting of the following formulation P1 was applied and dried. Furthermore, the coating liquid for photo-curable resin layers for etchings which consists of the following prescription E1 was apply | coated and dried. Thus, from the thermoplastic resin layer with a dry film thickness of 15.1 μm, the intermediate layer with a dry film thickness of 1.6 μm, and the photocurable resin layer for etching thickness of 2.0 μm on the temporary base material Finally, a protective film (12 .mu.m thick polypropylene film) was pressure bonded. Thus, a photosensitive film for etching E1 was produced in which the temporary base material, the thermoplastic resin layer, the intermediate layer, and the photocurable resin layer for etching were integrated.

--- Coating liquid for photo-curable resin layer for etching: Formulation E1--
・ Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (% by mass): 31/40/29, weight average molecular weight 6000
0, acid value 163 mg KOH / g): 16 parts by mass Monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
5.6 parts by mass.-Tetraethylene oxide monomethacrylate 0.5 mole adduct of hexamethylene diisocyanate: 7 parts by mass.-Cyclohexane dimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts. 2-chloro-N-butylacridone: 0.42 parts by mass. 2, 2-bis (orthochlorophenyl) -4, 4 ', 5, 5'-tetraphenylbiimidazole: 2.17 parts by mass malachite Green oxalate: 0.02 parts by mass, leuco crystal violet: 0.26 parts by mass, phenothiazine: 0.013 parts by mass, surfactant (trade name: Megafac F-780F, manufactured by Dainippon Ink Co., Ltd.) 0.03 part by mass, methyl ethyl ketone: 40 parts by mass, 1-methoxy-2-propanol: 20 parts by mass , Viscosity of 100 ° C. After solvent removal in an etching photocurable resin layer coating solution E1 was 2500 Pa · s.

-Coating liquid for thermoplastic resin layer: prescription H1-
Methanol: 11.1 parts by mass Propylene glycol monomethyl ether acetate: 6.36 parts by mass Methyl ethyl ketone: 52.4 parts by mass Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition ratio (Mole ratio) = 55 / 11.7 / 4.5 / 28.8, Molecular weight = 100,000, Tg 70 70 ° C): 5.83 parts by mass · Styrene / acrylic acid copolymer (copolymer composition ratio (mol) Ratio) = 63/37, weight average molecular weight = 10,000, Tg 100 100 ° C): 13.6 parts by mass Monomer (trade name: BPE-500, Shin-Nakamura Chemical Co., Ltd. product): 9.1 parts by mass Coating aid (Megafac F-780F, manufactured by DIC Corporation): 0.54 parts by mass The viscosity at 120 ° C. after removal of the solvent of the coating liquid H1 for thermoplastic resin layer is 1 , 500 Pa · sec.

-Coating solution for interlayer: Formulation P1-
-Polyvinyl alcohol: 32.2 parts by mass (trade name: PVA 205, manufactured by Kuraray Co., Ltd., degree of saponification = 88%, degree of polymerization 550
)
· Polyvinyl pyrrolidone: 14.9 parts by mass (trade name: K-30, manufactured by ISP Japan Co., Ltd.)
Distilled water: 524 parts by mass Methanol: 429 parts by mass

(Formation of first transparent electrode pattern)
The heating equipment on which the white decorative material and the transparent electrode layer are formed is washed, and the transfer film for etching E1 from which the protective film has been removed is made such that the surface of the transparent electrode layer faces the surface of the photocurable resin layer for etching. Lamination was performed (substrate temperature: 130 ° C., rubber roller temperature 120 ° C., linear pressure 100 N / cm, conveying speed 2.2 m / min). After peeling off the temporary base material, the thermoplastic resin layer and the intermediate layer were transferred to the surface of the transparent electrode layer together with the photocurable resin layer for etching. The distance between the exposure mask (quartz exposure mask having a transparent electrode pattern) surface and the aforementioned photocurable resin layer for etching is set to 200 μm, and photocurable for etching through the thermoplastic resin layer and the intermediate layer. The resin layer was pattern-exposed at an exposure dose of 50 mJ / cm ² (i line).
Next, using a triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (manufactured by Fujifilm Corporation) diluted 10-fold with pure water) at 100C at 25 ° C. It is developed for a second, the thermoplastic resin layer and the intermediate layer are dissolved, and a surfactant-containing cleaning solution (trade name: T-SD3 (Fuji Film Co., Ltd.) diluted 10 times with pure water) is used. Washing was carried out at 33 ° C. for 20 seconds. Pure water is jetted from the extra-high pressure cleaning nozzle, the residue of the thermoplastic resin layer and the intermediate layer is removed by the rotating brush, and post-baking treatment is performed at 130 ° C. for 30 minutes to obtain a white decorative material, a transparent electrode layer and The heating instrument in which the photocurable resin layer pattern for etching was formed was obtained.

A heating tool having a white decorative material, a transparent electrode layer and a photocurable resin layer pattern for etching is immersed in an etching bath containing ITO etchant (hydrochloric acid, potassium chloride aqueous solution, liquid temperature 30 ° C.) for 100 seconds. Treatment (etching treatment), dissolving and removing the transparent electrode layer in the exposed area not covered with the photo-curable resin layer for etching, with a white layer and a transparent electrode layer with a photo-curable resin layer pattern for etching I got a heating device.
Next, the front plate with a transparent electrode layer to which a photocurable resin layer pattern for etching was attached was coated with a resist stripping solution (N-methyl-2-pyrrolidone, monoethanolamine, surfactant (trade name: Surfynol 465, The product is immersed in a resist stripping tank containing an air product (liquid temperature 45 ° C.), treated for 200 seconds (stripping treatment), the photocurable resin layer for etching is removed, and a white decorative material and the above-mentioned heating tool The heating tool which formed the 1st transparent electrode pattern installed like FIG. 5 in the non-contact surface was obtained.

(Formation of insulating layer)
-Preparation of transfer film W1 for forming insulating layer-
The preparation of the etching transfer film E1 is the same as the preparation of the etching transfer film E1 except that the coating solution for the photocurable resin layer for etching described above is replaced with a coating solution for forming an insulating layer consisting of the following prescription W1. A transfer film W1 for forming an insulating layer is obtained, in which the temporary base material, the thermoplastic resin layer, the intermediate layer, the photocurable resin layer for the insulating layer, and the protective film are integrated (the photocurable resin layer for the insulating layer Film thickness is 1.4 μm).

-Coating liquid for insulating layer formation: prescription W1-
· Binder 3 (glycidyl methacrylate adduct of cyclohexyl methacrylate (a) / methyl methacrylate (b) / methacrylic acid copolymer (c) (d) (composition (% by mass): a / b / c / d = 46/1 / 10/43, weight average molecular weight: 36,000, acid value 66 mg KOH / g) 1-methoxy-2-propanol, methyl ethyl ketone solution (solid content: 45%)): 12.5 parts by mass dipentaerythritol hexaacrylate Propylene glycol monomethyl ether acetate solution (76% by mass) (Nippon Kayaku Co., Ltd. product): 1.4 parts by mass Urethane-based monomer (trade name: NK oligo UA-32P, Shin-Nakamura Chemical Co., Ltd. product, non-volatile) 75%, propylene glycol monomethyl ether acetate 25%): 0.68 parts by mass tripentae Slithol octaacrylate (trade name: V # 802, manufactured by Osaka Organic Chemical Industry Co., Ltd.): 1.8 parts by mass, diethylthioxanthone: 0.17 parts by mass, 2- (dimethylamino) -2-[(4- Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Irgacure 379, manufactured by BASF): 0.17 parts by mass Dispersant (trade name: Solsparse 20000, Avicia Co., Ltd.) Made: 0.19 parts by mass Surfactant (trade name: Megafac F-780F, manufactured by DIC Corporation): 0.05 parts by mass Methyl ethyl ketone: 23.3 parts by mass Propylene glycol monomethyl ether acetate: 59 .8 parts by mass The viscosity at 100 ° C after removal of the solvent of the insulating layer forming coating solution W1 was 4,000 Pa · sec.

The white decorative material described above and the heating device with the first transparent electrode pattern were washed, and the transfer film W1 for forming an insulating layer from which the protective film was removed was laminated to obtain a laminate (substrate temperature: 100 ° C., rubber Roller temperature 120 ° C., linear pressure 100 N / cm, conveying speed 2.3 m / min).
After peeling off the temporary base material from the obtained laminate, the distance between the exposure mask (quartz exposure mask having a pattern for insulating layer) surface and the above-mentioned photocurable resin layer for etching is set to 100 μm, and exposure is performed. Pattern exposure was performed with an amount of 30 mJ / cm ² (i line).
Next, the laminate (film substrate) after pattern exposure was treated with triethanolamine-based developer (containing 30% by mass of triethanolamine, trade name: T-PD2 (Fuji Film Co., Ltd.) by 10 times with pure water. Solution diluted at 25 ° C for 60 seconds at 33 ° C, sodium carbonate / sodium bicarbonate based developer (trade name: T-CD1 (Fujifilm Co., Ltd. product) diluted 5 times with pure water) at 25 ° C And washing treatment was carried out at 33 ° C. for 20 seconds using a surfactant-containing washing solution (trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10-fold with pure water) for 50 seconds. Pure water is jetted from the extra-high pressure cleaning nozzle, the residue of the thermoplastic resin layer and the intermediate layer is removed by the rotating brush, and post-baking treatment is carried out for 60 minutes at 230 ° C. The heating tool in which the electrode pattern and the insulating layer pattern were formed was obtained.

(Formation of second transparent electrode pattern)
-Formation of transparent electrode layer-
In the same manner as the formation of the first transparent electrode pattern, the heating device having the white decorative material, the first transparent electrode pattern, and the insulating layer pattern formed thereon is subjected to DC magnetron sputtering treatment (conditions: substrate temperature 50 ° C., argon pressure) An ITO thin film having a thickness of 80 nm was formed at 0.13 Pa and an oxygen pressure of 0.01 Pa, and a heating tool having a white decorative material, a first transparent electrode pattern, an insulating layer pattern, and a transparent electrode layer was obtained. The surface resistance of the ITO thin film was 110 Ω / □.

Similarly to the formation of the first transparent electrode pattern, a white decorative material, a first transparent electrode pattern, an insulating layer pattern, a transparent electrode layer, and a photocurable resin layer pattern for etching, using the transfer film E1 for etching Was obtained (post-baking treatment; 130 ° C., 30 minutes).
Furthermore, in the same manner as the formation of the first transparent electrode pattern, the white decorative material is etched (30 ° C., 50 seconds) to remove the photocurable resin layer for etching (45 ° C., 200 seconds). As shown in FIG. 5 across both the first transparent electrode pattern, the insulating layer pattern, the non-contact surface of the heating device described above, and the surface of the white decorative material opposite to the front plate described above. The heating instrument in which the installed 2nd transparent electrode pattern was formed was obtained.

(Formation of a conductive element different from the first transparent electrode pattern and the second transparent electrode pattern)
Similar to the formation of the first transparent electrode pattern and the second transparent electrode pattern, the front plate on which the white decorative material, the first transparent electrode pattern, the insulating layer pattern, and the second transparent electrode pattern are formed is DC magnetron Sputtering treatment was performed to obtain a heating apparatus in which an aluminum (Al) thin film having a thickness of 200 nm was formed.

Similarly to the formation of the first transparent electrode pattern and the second transparent electrode pattern, a white decorative material, a first transparent electrode pattern, an insulating layer pattern, a second transparent electrode using the etching transfer film E1 The heating tool which formed the pattern, the aluminum thin film, and the photocurable resin layer pattern for an etching was obtained (post-baking processing; 130 degreeC, 30 minutes).
Furthermore, in the same manner as the formation of the first transparent electrode pattern, the white decorative material is etched (30 ° C., 50 seconds) to remove the photocurable resin layer for etching (45 ° C., 200 seconds). , A heating device in which a first transparent electrode pattern, an insulating layer pattern, a second transparent electrode pattern, and another conductive element were formed.

(Formation of transparent protective layer)
Transfer film W1 for insulating layer formation from which the protective film has been removed is laminated on the front plate on which other conductive elements have been formed in the same manner as in the formation of the insulating layer, and after peeling off the temporary base, the exposure mask is not used. The entire surface is exposed with an exposure dose of 50 mJ / cm ² (i-line), developed, post-exposed (1000 mJ / cm ² ), post-baked, white decorative material, first transparent electrode pattern, insulating layer pattern, The heating apparatus which laminated | stacked the insulating layer (transparent protective layer) which covers two transparent electrode patterns and all other electroconductive elements like FIG. 5 was obtained. The resulting heating device can be used as a capacitive input device.

<Fabrication of a heating device having a touch panel>
The front plate (capacitance type input device) manufactured earlier is bonded to the liquid crystal display device manufactured by the method described in paragraph 0097 to paragraph 0119 of JP2009-47936A, and electrostatic capacitance is known by a known method. A heating device of Example 301 including a capacitive input device as a component was produced.
By using the heating devices of Examples 202 to 255 and Comparative Examples 201 to 212, instead of the heating device of Example 201, to prepare heating devices, Examples 302 to 355 and Comparative Examples 301 to 250 can be obtained. A heating device having a touch panel of 312 was produced.

<Touch panel operability and overall evaluation of heating equipment>
In the heating devices of Examples 301 to 355, there is no problem in the conductivity of each of the first transparent electrode pattern, the second transparent electrode pattern, and another conductive element different from these; It had insulation between the one transparent electrode pattern and the second transparent electrode pattern.
Furthermore, a touch panel excellent in display characteristics and operability was obtained.
On the other hand, in the heating devices of Comparative Examples 301 to 305 and 307 to 312, since a problem was observed in the operability of the touch panel, the heating devices having the touch panel could not withstand use.
The evaluation results of the touch panel operability of the heating device are shown in Table 8 or Table 9 above.

[Examples 401 to 455]
<Preparation of a cooker with a touch panel>
Remove the cooker top plate from a commercially available electromagnetic heating cooker (model name: KZ-T773S, manufactured by Panasonic Corporation), and instead obtain a heating appliance (cooker top plate) having the touch panel of Examples 301 to 355 obtained, It installed in a cooker and obtained the cooker of Example 401-455 which is a cooker with a touch panel.
The cookers of Examples 401 to 455 confirmed that the cooker and the touch panel on the cooker top plate operate without any problem.

1: Substrate (film substrate. Only the film substrate may be the front plate.)
1G: Glass (cover glass. Only the cover glass may be a front plate, or a laminate of a substrate and a glass may be a front plate)
2a: decorative material 2b: decorative material 2c: inclined portion 3: conductive layer (first transparent electrode pattern)
3a: pad portion 3b: connection portion 4: conductive layer (second transparent electrode pattern)
5: Insulating layer 6: Conductive layer (another conductive element)
7: Transparent protective layer 21: Touch panel 22: Induction heating unit 23: Cooker top plate 31: Cooker C: First direction D: Second direction

Claims (14)

With colorants,
A silicone having a D-body structure represented by the following general formula D and a T-body structure represented by the following general formula T, and a D / T ratio represented by the following formula exceeding 0 and 2.5 or less resins, and, and at least one of silicone rubber having a D structure seen including,
Further grafted silicone polymer coloring composition for including heating appliance decorative represented by the following formula 1;
D / T ratio = (molar amount of silicon atoms contained in the D-form structure) / (molar amount of silicon atoms contained in the T-body structure)
In the general formula D and the general formula T, R ^D1 , R ^D2 and R ^T1 each independently represent a methyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and the wave line part is Represents a binding site to another structure ;
In Formula 1, R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, and R ¹¹ and R ¹² each independently represent an arylene group or 1 carbon atom R ¹³ and R ¹⁴ each independently represent a single bond or a divalent organic linking group, A represents a group having a pigment adsorption site, and B is represented by the following general formula 2 Represents a group having a structure, and l and n each independently represent an integer of 1 or more, and m represents an integer of 0 or more;
In Formula 2, each of R ¹⁵ and R ¹⁶ independently represent a hydrogen atom, a hydroxy group, an aryl group or an alkyl group having 1 to 3 carbon atoms, k represents an integer of 1 or more.   The coloring composition for heating implement decoration of Claim 1 used for a cooker top plate.   The heating apparatus according to claim 1 or 2, wherein the silicone resin having a D / T ratio of more than 0 and 2.5 or less is a silicone resin having a D / T ratio of more than 0.5 and 2.5 or less. Colored composition for decoration. The colorant, prior SL D / T ratio of heating appliances decorative coloring composition according to any one of claims 1 to 3 content exceeds 1.0 relative to the total of less than one silicone resin.   The coloring composition for heating appliance decoration according to any one of claims 1 to 4, wherein the coloring agent is an inorganic pigment.   Having a temporary support and a colored layer,
  The colored layer is
    With colorants,
    A silicone having a D-body structure represented by the following general formula D and a T-body structure represented by the following general formula T, and a D / T ratio represented by the following formula exceeding 0 and 2.5 or less A coloring composition for heating device decoration comprising a resin and at least one of silicone rubber having a D-body structure,
Transfer material for heating equipment decoration.
  D / T ratio = (molar amount of silicon atoms contained in the D-form structure) / (molar amount of silicon atoms contained in the T-body structure)
  In the general formula D and the general formula T, R ^D1 , R ^D2 And R ^T1 Each independently represents a methyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted benzyl group, and the wavy line portion represents a binding site to another structure. Having a temporary support and a colored layer,
A transfer material for heating device decoration, wherein the colored layer comprises the coloring composition for heating device decoration according to any one of claims 1 to 5 . Has a decorative material on the substrate,
A heating device comprising the coloring composition for heating device decoration according to any one of claims 1 to 5 , wherein the decorative material is. Has a decorative material on the substrate,
A heating device which is a transfer material of the colored layer of the transfer material for heating device decoration according to claim 6 or 7.   The heating instrument according to claim 8 or 9, further comprising a protective layer on the side of the decorative material opposite to the substrate.   The heating instrument according to any one of claims 8 to 10 which has a touch panel.   The heating device according to claim 11, wherein the touch panel is a capacitive input device.   The heating device according to any one of claims 8 to 12, wherein the heating device is a cooker top plate.   A cooker comprising the heating device according to any one of claims 8 to 13.