JP2614022B2 - Labels and how to print them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a label,
The present invention relates to a heat-resistant label that can be baked on a heat-resistant material in a high-temperature processing step of up to 700 ° C. and a method of baking the label.

[0002]

2. Description of the Related Art In a wide range of industrial fields, such as food, machinery, and chemistry, products, or their packaging, are provided with symbols, characters, and patterns.
A label printed with a pattern or the like, that is, a pattern forming label is attached and used for process control. A typical example is a management system using barcode labels. This bar code management system manages the manufacturing and sales processes by mechanically reading information such as the manufacturing status and price of a product from a bar code label.

However, a conventional bar code label in which a label film is made of a resin or paper having low heat resistance and an adhesive made of an acrylic resin or the like is adhered to the label film has a thickness of 300% for both the label body and the adhesive. Decomposes and evaporates under severe temperature conditions of over ℃, ceramic industry,
It cannot be used in an industrial field having a high-temperature treatment step such as the steel making industry and the glass industry, for example, a cathode ray tube manufacturing step for a television having an enclosing and annealing step at 400 to 600 ° C. Therefore, a label film and an adhesive capable of withstanding a high temperature of 300 ° C. or more are required.

On the other hand, conventionally, glass fiber,
Heat-resistant films made by impregnating a heat-resistant binder resin such as silicone resin or polyamide resin into a cloth-like material woven from long-fiber amorphous inorganic fibers such as Some of them can withstand temperatures exceeding 300 ° C. for a short time.

[0005] However, when such a heat-resistant film is processed into a label and used for the above-mentioned applications, the film is rigid and poor in flexibility, so that only a product having a smooth surface is produced. Can only be pasted. However, even if it is possible to attach it, if it is attached to the surface of a cathode ray tube or metal plate and exposed to high temperatures, it will cause discoloration, and the label will not be able to withstand the thermal expansion of the cathode ray tube or metal plate, causing cracks on the label and peeling off. At high temperatures exceeding 300 ° C, use is limited, and at high temperatures exceeding 400 ° C,
At present, it can hardly be used.

In order to solve this problem, for example,
Japanese Patent Publication No. 2-142083 discloses ceramics, hollows,
A heat-resistant bar code label for a cathode ray tube manufacturing process in which a bar code is printed on a label film made of metal or the like with an ink containing a glassy inorganic compound having a low melting point (glass frit), an inorganic pigment and a solvent has been proposed. ing. However, although this heat-resistant bar code label has sufficient heat resistance, it has a drawback that it is rigid and cannot be attached to a curved surface. If the adhesive is exposed to a high temperature exceeding the temperature, the heat resistance of the pressure-sensitive adhesive is much lower than the heat resistance of the label itself.

Therefore, for example, Japanese Patent Application Laid-Open No.
No. 2, JP-A-4-335083 and the like propose a silicone resin-based heat-resistant adhesive. However, since these heat-resistant adhesives can withstand a high temperature exceeding 400 ° C. for a short time, these heat-resistant adhesives are attached to the heat-resistant barcode label and exposed to a high temperature exceeding 400 ° C. If it is attached to a product, it will fall off in a short time. For this reason, the only method of sticking that makes full use of the heat resistance of the label itself is screwing or inserting it into a pocket.For application to the actual manufacturing process,
The restrictions were very large and time-consuming.

[0008] As an attempt to solve such a problem and to realize a heat-resistant label which can be automatically applied by giving flexibility to the label without deteriorating or falling off the label even at high temperatures, WO 88/07937 is disclosed. Discloses a label in which a bar code is printed with a heat-resistant ink on a film containing a large amount of glass frit in a resin, and an adhesive having a low thermal decomposition temperature is applied. The glass frit used in this label melts when exposed to high temperatures,
Even after the adhesive has been degraded or decomposed, the bar code pattern can be fused and left on the product surface.

[0009]

However, in the label containing the glass frit, since the glass frit used is a solvent-insoluble powder having a large particle size of several μm to several tens μm at room temperature, a large amount of glass frit is used. Films containing glass frit are very brittle. For this reason, even if it is possible to apply it with a labeling machine, it is often damaged at that time, and in the worst case, the production line is stopped.

[0010] In view of the above problems, the present invention provides a heat-resistant label which is excellent in flexibility and heat resistance, and which can be baked at high temperatures especially on heat-resistant materials, and is therefore not easily dropped off at high temperatures. It is intended to be.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, a film containing a specific resin component and a specific inorganic fiber has a specific resin component and metal powder or By using this and a label to which a pressure-sensitive adhesive containing a boric acid compound is adhered, both flexibility and heat resistance are satisfied, and a label which is excellent in appearance and abrasion resistance even after being treated at a high temperature and which does not fall off can be obtained. This led to the completion of the present invention.

That is, the first aspect of the present invention is as follows.
A resin containing B-component resin and B) a single crystalline inorganic fiber in a ratio of 20 to 95% by weight of A component and 80 to 5% by weight of B component in the total amount of both A and B components, ) Silicone resin and E) metal powder in the total amount of both D and E components,
The present invention relates to a label to which an adhesive which is contained in a proportion of 10 to 80% by weight of the D component and 90 to 20% by weight of the E component is adhered.

A second aspect of the present invention is that A) a silicone resin;
B) Single crystalline inorganic fiber, and C) Decomposition onset temperature is 350 ° C
The following resin is the component A to 20% by weight, the component B 60 to 5% by weight, the component C 20
D) A silicone resin and E) a metal powder are contained in a film contained in an amount of about 5% by weight to 10% by weight of the D component and 90% by weight of the E component in the total amount of both the D and E components. The present invention relates to a label to which an adhesive which is contained at a ratio of about 20% by weight is attached.

A third aspect of the present invention is that A) a silicone resin;
B) The monocrystalline inorganic fiber is included in the total amount of both A and B components,
A film containing 20 to 95% by weight of the component A and 80 to 5% by weight of the component B contains D) a silicone resin;
E) a metal powder and F) a boric acid compound in a total amount of the D to F three components, 10 to 75% by weight of the D component, and 80 to 2 of the E component.
The present invention relates to a label to which an adhesive which is contained at a ratio of 4.9% by weight and F component at 10 to 0.1% by weight is attached.

A fourth aspect of the present invention is that A) a silicone resin;
B) Single crystalline inorganic fiber, and C) Decomposition onset temperature is 350 ° C
The following resin is the component A to 20% by weight, the component B 60 to 5% by weight, the component C 20
D) A silicone resin, E) a metal powder, and F) a boric acid compound are contained in a film contained in an amount of from 5 to 5% by weight. 75% by weight, E component 80 to 24.9% by weight, F component 10 to 0.1
The present invention relates to a label to which a pressure-sensitive adhesive contained in a percentage by weight is attached.

According to a fifth aspect of the present invention, the first material is added to the heat-resistant material.
~ After applying the label according to the fourth invention, 200 ~
The present invention relates to a label printing method characterized in that a label is printed on a heat-resistant material by treating at a temperature of 700 ° C.

[0017]

The label of the present invention comprises a film constituting the label body and an adhesive to be adhered to the label, and the former film requires two components A and B or three components A to C, The latter adhesive is D or E two component or D ~
The three types of F are essential, and the following four types exist depending on the combination of the above essential components of both materials.

The first is a combination of a film having two essential components, A and B, and an adhesive having two essential components, D and E. The second is a combination of a film essentially including three components A to C and a pressure-sensitive adhesive essentially including two components D and E. Further, the third is a combination of a film having two essential components, A and B, and an adhesive having three essential components, DF. The fourth is a combination of a film essentially including three components A to C and a pressure-sensitive adhesive essentially including three components D to F.

In the film constituting the label body, the silicone resin of component A is a compound having an organopolysiloxane structure in the molecule, and includes a straight silicone resin and a modified silicone resin. One or more of them are used. These resins are 100
It is preferable to use a so-called room temperature curing type silicone resin which cures at a temperature lower than ℃. Further, these resins are used as they are or as a resin solution dissolved in a solvent. However, in order to facilitate film formation at the time of producing a label, it is desirable to use these resins as a resin solution dissolved in a solvent.

The weight average molecular weight of such a silicone resin is from 200 to 5,000,000, preferably from 500 to 2,000,000, and more preferably from 1,0 to 5,000,000.
It is preferably from 00 to 1,000,000. In order to further improve the flexibility of the label, it is preferable to use a mixture of two or more kinds having different weight average molecular weights. In particular, A-L) weight average molecular weight 200-500,000,
A low molecular weight silicone resin, preferably from 500 to 200,000, more preferably from 1,000 to 100,000, and AH) 10 to 1,000 times the weight average molecular weight of the AL component. It is preferably a mixture with a high molecular weight silicone resin having a weight average molecular weight of 50 to 500 times, the proportion of which is 5 to 50% by weight of the A-L component,
Those having an AH component of 95 to 50% by weight are preferably used.

The straight silicone resin is an organopolysiloxane having a hydrocarbon group as a main organic group, and may have a hydroxyl group. The hydrocarbon group includes an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and among them, an aliphatic hydrocarbon group having 1 to 5 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms are preferable. . One or two or more of these hydrocarbon groups may be used.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a vinyl group, an allyl group, a propenyl group, a butenyl group and a pentenyl group. is there. Carbon number 6 ~
Examples of the 12 aromatic hydrocarbon groups include, for example, phenyl, methylphenyl, ethylphenyl, butylphenyl, tert-butylphenyl, naphthyl,
Examples include a styryl group, an allylphenyl group, and a propenylphenyl group.

[0023] The straight silicone resin is, for example,
One or two or more silane compounds comprising the above-mentioned chlorosilane compound or alkoxysilane compound containing an aliphatic hydrocarbon group or an aromatic hydrocarbon group are hydrolyzed and condensed, or tetrachlorosilane or It is obtained by hydrolyzing and co-condensing a mixture to which tetraalkoxysilane is added.

Examples of the above-mentioned chlorosilane compounds include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, methylethyldichlorosilane, vinylmethyldichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, methylphenyl Examples include dichlorosilane and vinylphenyldichlorosilane.

Further, as the alkoxysilane compound,
Methyltrimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, vinylmethylmethoxysilane, vinyltributoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, methylphenyldipropoxysilane, vinylphenyldimethoxysilane, etc. Can be

The modified silicone resin is an organopolysiloxane containing an organic group other than a hydrocarbon group, for example, a methoxy group-containing silicone resin, an ethoxy group-containing silicone resin, and an epoxy group-containing silicone resin. Resins, modified silicone resins, modified silicone resins, modified silicone resins, modified silicone resins, modified silicone resins, modified silicone resins, and modified epoxy resins.

These modified silicone resins include, for example, hydroxyl groups contained in the straight silicone resin,
Carboxyl group, acid anhydride group, which can react with this hydroxyl group,
A method of reacting with an organic compound having a functional group such as a hydroxyl group, an aldehyde group, an epoxy group, or a chloride group, and a straight silicone having an unsaturated hydrocarbon group such as a vinyl group.
A modified silane compound obtained by reacting the silane compound with another organic compound by hydrolysis or condensation or co-condensation. Can be The organic compound to be reacted may be a low molecular compound or a high molecular compound such as a resin.

In the film constituting the label body, the monocrystalline inorganic fiber of the B component is a fiber made of an inorganic single crystal, and from the sharpness of a printed pattern,
The average fiber length is preferably 200 μm or less, more preferably 100 μm or less. From the viewpoint of film strength, the average fiber length is preferably at least three times the average fiber diameter, more preferably at least five times.

Examples of such single-crystalline inorganic fibers include silicon carbide whiskers, silicon nitride whiskers, alumina whiskers, titanate whiskers, zinc oxide whiskers, magnesia whiskers, and aluminum borate whiskers. And wollastonite.
These inorganic fibers all have an average fiber length of at least 5 times the average fiber diameter. Among these inorganic fibers, potassium titanate whiskers, which are one kind of titanate whiskers, are particularly preferably used.

In the film constituting the label body, the resin of component C is preferably a resin whose decomposition starting temperature by a thermobalance under air atmosphere is 350 ° C. or lower, preferably 32 ° C.
It is a resin whose temperature is 0 ° C. or lower. The resin whose decomposition start temperature exceeds 350 ° C. generates carbides when exposed to high temperatures,
The appearance of the label is impaired. Specifically, poly (meta)
Acrylic esters, polyvinyl esters, polyalphamethylstyrene, polyalkylene oxides and the like can be mentioned. The average molecular weight of such a resin is usually 3,000 or more, preferably 10,000 or more.
If the molecular weight is too small, the effect of improving the flexibility of the label will be small.

The (meth) acrylate constituting the poly (meth) acrylate is an ester of (meth) acrylic acid and an aliphatic alcohol having 1 to 6 carbon atoms,
For example, methyl acrylate, butyl acrylate, hexyl acrylate, ethylene glycol monoacrylate, glycerin monoacrylate, glycerin diacrylate, methyl methacrylate, butyl methacrylate, hexyl methacrylate, ethylene glycol monoacrylate Examples include methacrylate, ethylene glycol dimethacrylate, glycerin monomethacrylate, and glycerin dimethacrylate.

The poly (meth) acrylate is obtained by polymerizing one or more of the above (meth) acrylates by a usual method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. And its decomposition onset temperature is about 170-320 ° C. Particularly preferred are polymethyl methacrylate and polymethyl acrylate, the decomposition starting temperature of which is about 200 to 300 ° C.

The vinyl ester constituting the polyvinyl ester is a fatty acid vinyl ester having 1 to 6 carbon atoms,
For example, there are vinyl formate, vinyl acetate, vinyl propionate, vinyl hexanoate and the like. The polyvinyl ester is obtained by polymerizing one or more of these fatty acid vinyl esters by a general method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. ~ 320 ° C. Particularly preferred is polyvinyl acetate, whose decomposition onset temperature is about 250-310 ° C.

Polyalphamethylstyrene is obtained by polymerizing alphamethylstyrene by a conventional method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the decomposition initiation temperature of this resin is about 220 to 280. ° C.

The alkylene oxide constituting the polyalkylene oxide is an alkylene oxide having 1 to 4 carbon atoms, such as ethylene oxide, propylene oxide and butylene oxide. Polyalkylene oxide is obtained by subjecting one or more of these alkylene oxides to addition polymerization by a known method, and the resin has a decomposition initiation temperature of about 150 to 300 ° C. Particularly preferred are polymethylene oxide, polyethylene oxide, polypropylene oxide, and a block copolymer of ethylene oxide and propylene oxide, the decomposition starting temperature of which is about 180 to 280 ° C.

In the label of the present invention, one of the films constituting the label body essentially comprises two components, the above-mentioned silicone resin of component A and the monocrystalline inorganic fiber of component B. Is used in an amount of 20 to 95% by weight, preferably 30 to 9% by weight, based on the total amount of both A and B components.
0% by weight, and 80 to 5% by weight of the B component, preferably 70% by weight.
-10% by weight. Outside of these ranges, there is a problem that sufficient heat resistance cannot be obtained and that the flexibility of the label decreases.

Another one of the films constituting the label body is composed of the above-mentioned silicone resin of the component A, the monocrystalline inorganic fiber of the component B, and the resin whose decomposition start temperature of the component C is 350 ° C. or lower. Three components are essential, and the use of the above-mentioned component C further improves the flexibility of the label. The amount of each component used is such that the A component is 20 to 90% by weight, preferably 30 to 85% in the total amount of the three components A to C.
% By weight, B component is 60 to 5% by weight, preferably 55 to 8%.
20% to 5% by weight, preferably 15 to 7% by weight.
% By weight. Outside of these ranges, the same problems as described above may occur. When the amount of the C component is less than 5% by weight, the effect of improving flexibility is reduced. When the amount is more than 20% by weight, heat resistance is reduced.

As described above, in order to particularly improve the heat resistance of a film containing two components of A and B or three components of A to C, the silicone resin of the component A is partially or wholly contained. It is desirable to use the prepared straight silicone resin so that the content of the straight silicone resin is 50% by weight or more, preferably 60% by weight or more in the component A.

When the label using the film having the above structure is treated at 200 to 700 ° C., a pyrolysis gas containing an organosiloxane as a main component is generated from the silicone resin of the component A, and the CRT present in the furnace. This gas may adhere to the attachments of labels and other parts such as, for example, and become contaminated. In this case, the contact angle of water on the surface of the contaminated cathode ray tube or the like becomes large, and the washing water is repelled in the subsequent steps, and the washing is not performed sufficiently, and defects such as unevenness due to subsequent painting or the like are caused. Easy to cause.
In order to solve this, it is necessary to use a silicone resin 10 of component A.
0.1 parts by weight of silicone resin crosslinking agent
It is preferable to add 100 parts by weight, preferably 0.2 to 50 parts by weight. If the amount is less than this range, contamination from the silicone resin cannot be sufficiently reduced. If the amount is more than this range, crosslinking may become too dense and the label may become brittle.

As the crosslinking agent for the silicone resin,
There are boric acid compounds and organometallic compounds. this house,
The boric acid compound is a compound containing a boric acid residue in the molecule, and examples thereof include boric acid, borate, and borate. As boric acid, there are orthoboric acid, metaboric acid, boric anhydride and the like, and as borate salts, sodium borate, potassium borate, magnesium borate,
Examples thereof include calcium borate, zinc borate, and aluminum borate. Examples of borate esters include methyl borate, ethyl borate, butyl borate, octyl borate, and dodecyl borate. Of these boric acid compounds, orthoboric acid is particularly preferred.

The organic metal compound includes an organic tin compound, an organic lead compound, an organic zinc compound, an organic aluminum compound, an organic titanium compound, and the like. Among them, the organic titanium compound is particularly preferable. Examples of the organic titanium compound include alkoxy titanium having an alkoxy group having 1 to 32 carbon atoms, titanium acylate having an acyl group having 1 to 32 carbon atoms, and titanium chelate compound having a ligand having 1 to 32 carbon atoms. For example, there are tetraisopropoxytitanium, tetrabutoxytitanium, tetrakis-2-ethylhexoxytitanium, titanium tetraacetate, di-iso-propoxybis (acetylacetonato) titanium and the like. Titanium is preferred.

In the present invention, the above-mentioned two components A and B or three components A to C are essential, and the flexibility, printing characteristics, heat resistance, tensile strength, etc. of the film obtained by appropriately adding the above-mentioned crosslinking agent to the two components are included. An additive can be added for the purpose of further improving the physical properties of. Examples of the additive include a plasticizer, an inorganic pigment, and a heat resistance improver.

Examples of the plasticizer include an aliphatic ester, an aromatic ester, a phosphate ester and the like. Aliphatic esters include methyl laurate, butyl oleate, diethylene glycol dilaurate, diadipate (2
-Ethyl butoxyethyl), and the aromatic esters include dimethyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate, dilauryl phthalate, oleyl benzoate, phenyl oleate, and the like. Examples thereof include tricresyl phosphate and trioctyl phosphate.

By adding these plasticizers, the flexibility of the label can be further improved. The addition amount is 20 parts by weight or less based on 100 parts by weight of the two components A and B or the three components A to C,
Preferably, the content is 10 parts by weight or less. If the amount is too large, the flexibility of the label becomes too large, and the label is difficult to peel off from the release paper used as the backing paper.

As the inorganic pigment, a pigment which does not cause discoloration at a high temperature of 300 ° C. or more is used. For example, zinc oxide, aluminum oxide, aluminum hydroxide, lithopone, titanium oxide, chromium oxide, manganese oxide, nickel titanium yellow , Chromium titanium ero, red iron, raster pigment, and the like. In addition to these coloring pigments, micro silica and calcium carbonate may be used as extenders. By adding these pigments, the contrast of printing can be increased and the adhesion of printing ink can be improved. The addition amount is 200 parts by weight or less, preferably 100 parts by weight or less based on 100 parts by weight of the two components A and B or the three components A to C. If it is too large, the flexibility of the label decreases.

As the heat resistance improver, any of known inorganic powders for improving the heat resistance of the silicone resin can be used. For example, aluminum powder, zinc powder, aluminum oxide powder, zinc oxide powder, zinc sulfate powder and so on. By adding these heat resistance improvers, the heat resistance of the label can be improved. The addition amount is 100 parts by weight or less, preferably 50 parts by weight or less based on 100 parts by weight of the two components A and B or the three components A to C. If it is too large, the flexibility of the label decreases.

In the present invention, the silicone resin of the component A is often commercially available as a resin solution containing a solvent, but a solvent may be further added to facilitate the production of a film. This diluting and dispersing solvent has a boiling point of 0-3.
It is a solvent of 00 ° C, preferably 25 to 200 ° C. The addition amount is 500 parts by weight or less, preferably 200 parts by weight or less based on 100 parts by weight of the two components A and B or the three components A to C. If the amount is too large, it takes a long time to dry the film, and no further effect is recognized, which is economically disadvantageous.

Examples of such a solvent for dilution and dispersion include aliphatic hydrocarbons such as hexane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and naphthalene, acetone, methyl ethyl ketone, and the like. Ketones such as cyclohexanone, alcohols such as methanol, ethanol and 2-ethylhexanol, ethylene glycol monomethyl ether
Ethers such as ter and diethylene glycol dibutyl ether; esters such as methyl acetate, ethyl formate and ethyl acetoacetate; petroleum distillation components such as gasoline, kerosene and light oil; and water. Among these, aromatic hydrocarbons and alcohols having excellent compatibility with the silicone resin are particularly preferred.

In the production of the film constituting the label body in the present invention, first, the two components A and B or the three components A to C are used alone or, if necessary, as a crosslinking agent for the above component A. Mix with other additives and solvents at room temperature or under heating. At this time, mixing may be performed using a disperser such as a day spar, a ball mill, a sand mill, a roll mill, and a homogenizer. The mixture may be applied or printed on a mold coated with release paper or a release agent by a known coating method or printing method, and dried at normal temperature or under heating to form a film. The thickness of the film is not particularly limited, but is usually 1 to 1,000.
μm is preferred.

In the pressure-sensitive adhesive to be adhered on the film constituting the label body, the same silicone resin as the component A can be used as the silicone resin as the component D. The weight average molecular weight of this resin is 200
It may be in the range of ５，5,000,000. In order to improve the heat resistance of the pressure-sensitive adhesive, a straight silicone resin is used as part or all of the silicone resin, and the content of the straight silicone resin is D.
In the components, it is preferably at least 50% by weight, preferably at least 60% by weight. However, unlike the silicone resin of the component A, the silicone resin of the component D has a temperature of 100 ° C.
So-called heat-curable silicone that cures at the above temperatures
Resin is preferred.

The metal powder of the component E is obtained by pulverizing a metal, and may have any shape such as a fragment, a sphere, a block, a granule, a flake, a needle, and a scale.
The particle size is preferably from 0.01 to 1,0 in order to obtain good heat resistance.
It is good to be 00 μm, preferably 0.1 to 500 μm. The type of the metal is not particularly limited, but a metal that is relatively stable in the atmosphere is preferable. For example, zinc, nickel,
Aluminum, tin, iron, stainless steel, gold, silver, platinum,
There are lead, copper, metallic silicon, titanium and alloys thereof, among which zinc, aluminum and stainless steel are particularly preferred. When these are used, the heat resistance is further improved.

The boric acid compound as the component F is a compound containing a boric acid residue in the molecule, and includes, for example, boric acid, borate and borate. Examples of boric acid include orthoboric acid, metaboric acid, and boric anhydride.Examples of borate salts include sodium borate, potassium borate, magnesium borate, calcium borate, zinc borate, and aluminum borate. And borate esters
Examples include methyl borate, ethyl borate, butyl borate, octyl borate, dodecyl borate, and the like. Of these boric acid compounds, orthoboric acid is particularly preferred.

One of the pressure-sensitive adhesives in the present invention essentially comprises a silicone resin as the D component and a metal powder as the E component.
E In the total amount of both components, D component is 10 to 80% by weight, preferably 20 to 70% by weight, E component is 90 to 20% by weight,
Preferably it is 80 to 30% by weight. Outside these ranges, sufficient heat resistance cannot be obtained.

The other one of the pressure-sensitive adhesives essentially comprises a boric acid compound of the component F in addition to the above-mentioned components D and E. By adding the component F, the heat resistance of the pressure-sensitive adhesive is improved. It can be further improved. The amount of each component used is
In the total amount of the D to F three components, the D component is 10 to 75% by weight,
Preferably 20 to 70% by weight, E component is 80 to 24.9.
% By weight, preferably 75 to 29.5% by weight, and the F component is 1%.
It is 0 to 0.1% by weight, preferably 5 to 0.5% by weight. Outside these ranges, sufficient heat resistance cannot be obtained.
When the amount of the F component is less than 0.1% by weight, the effect of improving the heat resistance is reduced. When the amount is more than 10% by weight, the adhesive strength as an adhesive is reduced.

In the two pressure-sensitive adhesives essentially including the two components D and E or the three components D to F, an appropriate additive may be added, if necessary, for the purpose of further improving physical properties such as tackiness and handleability. Can be added. For example, a plasticizer for improving tackiness, an inorganic pigment for improving flow characteristics and handleability, and a solvent for improving handleability are also used.

Examples of the plasticizer include an aliphatic ester, an aromatic ester and a phosphate ester. Aliphatic esters include methyl laurate, butyl oleate, diethylene glycol dilaurate, diadipate (2
-Ethylbutoxyethyl), and the aromatic esters include dimethyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate, dilauryl phthalate, oleyl benzoate, and phenyl oleate. Examples of the phosphate ester include tricresyl phosphate and trioctyl phosphate.

As the inorganic pigment, a pigment which does not cause discoloration at a high temperature of 300 ° C. or more is used. For example, zinc oxide, aluminum oxide, aluminum hydroxide, lithopone, titanium oxide, chromium oxide, manganese oxide, nickel titanium yellow , Chromium titanium ero, red iron, raster pigment, and the like. In addition to these coloring pigments, micro silica, calcium carbonate, and the like may be used as the extender.

These plasticizers and inorganic pigments are used in an amount of not more than 20 parts by weight, preferably not more than 10 parts by weight of the plasticizer and not more than 10 parts by weight, based on 100 parts by weight of the two components D and E or the three components DF. 100 parts by weight or less, preferably 50 parts by weight or less. If the amount of the plasticizer is too large, the adhesiveness becomes too large, so that the label is hardly peeled off from the release paper. If the amount of the inorganic pigment is too large, the adhesiveness decreases.

The two pressure-sensitive adhesives are prepared by mixing the D and E two-components or the DF three-components alone or, if necessary, with the above additives at room temperature or under heating. At this time, mixing may be performed using a disperser such as a day spar, a ball mill, a sand mill, a roll mill, and a homogenizer.

In the present invention, the adhesive prepared as described above can be attached to the film constituting the label body by, for example, applying the above adhesive on the film produced by the above-described method. It may be dried. On the other hand, on a mold coated with release paper or a release agent,
The above-mentioned pressure-sensitive adhesive may be applied or printed by a known application method or printing method, dried at room temperature or under heating, and then a film for forming a label body prepared in advance may be crimped thereon. The adhesion amount of the pressure-sensitive adhesive is not particularly limited, but usually, the thickness of the pressure-sensitive adhesive layer is 0.5 to
What is necessary is just to make it about 500 micrometers. After adhering the adhesive in this manner, the label of the present invention is produced by cutting the adhesive into an appropriate size.

When the label of the present invention thus produced is used, it may be used as it is as a plain label with an adhesive, but usually, a letter or bar code is formed using a known heat-resistant ink. Such as symbols
The label is printed and used as a label with an adhesive such as a bar code label.

As the heat-resistant ink, an ink that can withstand a temperature at which a high-temperature treatment step is performed, that is, a temperature of 200 ° C. or more for 2 hours or more is used. Particularly preferred is a heat-resistant ink using a metal oxide as a coloring pigment. Ink. Metal oxides used in this heat-resistant ink include iron, cobalt, nickel, chromium, copper, manganese,
One or a mixture of two or more oxides of a metal such as titanium or aluminum. These metal oxides are supplied as a powder and have a particle size of 0.01 to 50 μm, preferably 0.1 to 10 μm. It is.

The heat-resistant ink using the metal oxide is, for example, 1 to 1,000 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the metal oxide.
By mixing by weight, adding a solvent if necessary, and dispersing or kneading with a disperser such as a disperser, ball mill, roll mill, sand mill, etc. to produce a liquid or paste-like product. be able to. In this case, examples of the binder used include resins, waxes, fats and oils, and low-melting glass.

Examples of the resin include a silicone resin, a hydrocarbon resin, a vinyl resin, an acetal resin, an imide resin, an amide resin, an acrylic resin, a polyester resin, a polyurethane resin, an alkyd resin, a protein resin, and a cellulose resin. Examples include, for example, organopolysiloxane,
Polystyrene, polyethylene, polypropylene, polyvinyl acetate, polyvinyl butyral, polyvinyl formal
Or a mixture or copolymer of one or more of such as polyester, polyimide, polyamide, poly (meth) acrylate, gelatin, cellulose derivative, polyvinyl alcohol, and polyvinylpyrrolidone.

As waxes, paraffin waxes,
Natural waxes, higher alcohol waxes, higher amide waxes, higher fatty acids, ester waxes and the like, for example, paraffin wax, polyethylene wax, beeswax, carnauba wax, stearyl alcohol
, Palmityl alcohol, oleyl alcohol, stearoamide, oleamide, palmityloamide, ethylenebisstearamide, stearic acid, oleic acid, palmitic acid, myristic acid, ethyl stearate, butyl palmitate, palmityl stearee And stearyl stearate.

Examples of fats and oils include castor oil, soybean oil, linseed oil, olive oil, beef tallow, lard, mineral oil and the like. The low melting point glass has a melting point of 70 ° C.
The following glass or glass soluble in a solvent is available. For example, a glass frit having a melting point of 700 ° C. or less has a particle size of 0.1 to
100 μm, preferably 0.2 to 50 μm, and water glass.

Solvents used for dispersion or kneading include, for example, aliphatic hydrocarbons such as hexane, octane, decane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and naphthalene, and acetone. Ketones such as methyl, ethyl ethyl ketone, cyclohexanone, alcohols such as methanol, ethanol and 2-ethylhexanol, ethers such as ethylene glycol monomethyl ether, diethylene glycol dibutyl ether, methyl acetate, ethyl formate And esters such as ethyl acetoacetate, petroleum distillation components such as gasoline, kerosene and light oil, and water. The solvent used for these dilutions is 100% in total of the metal oxide and the binder.
It is good to use at 500 parts by weight or less, preferably at 200 parts by weight or less with respect to parts by weight. If the amount is too large, the dispersion stability of the heat-resistant ink will deteriorate.

To print on the label of the present invention using a heat-resistant ink composed of such a constituent material, known printing methods such as gravure offset printing, flat plate offset printing, relief printing, intaglio printing, An arbitrary pattern including symbols such as characters and bar codes may be printed by various printing methods such as silk screen printing, ink jet printing, and ribbon printing.

The label of the present invention can be used as a pattern-forming label for controlling the production process of a product including a high-temperature treatment step as well as a normal-temperature treatment step. Useful for management. In this case, by applying the label of the present invention to the heat-resistant material and then treating the label at a temperature of 200 to 700 ° C., the label can be integrally baked on the heat-resistant material. As a result, no dropout occurs during the manufacturing process, and no inconveniences such as deterioration of the appearance and abrasion resistance at the above temperature are caused.

[0070]

As described above, the label of the present invention is excellent in both flexibility and heat resistance, and has excellent appearance and abrasion resistance when baked on a heat-resistant material at a high temperature, and causes the label to fall off. Since it has excellent heat-peeling resistance, it is useful as a pattern-forming label for controlling the production process of a product having a high-temperature treatment step as well as at normal temperature. In particular,
Manufacturing process control of various industries having a high temperature treatment process of 200 to 700 ° C, more specifically, firing → sealing → degassing →
It can be used in the production process of a cathode ray tube for television, which consists of each assembly process.

[0071]

Next, the present invention will be described more specifically with reference to examples and comparative examples. The film and the adhesive constituting the label body used in the examples were manufactured by the following manufacturing examples 1 to 27. The film constituting the label body used in the comparative example was manufactured by the following comparative manufacturing examples 1 to 8.

Production Example 1 A straight silicone resin A1 [trade name "KR-25" manufactured by Shin-Etsu Chemical Co., Ltd.]
5 ") and a straight silicone resin A2 (trade name" KR-271 "manufactured by Shin-Etsu Chemical Co., Ltd.), and potassium titanate whisker as a monocrystalline inorganic fiber of the B component. -[Otsuka Chemical Co., Ltd. product name "TISMO
TYPE D "] to prepare a silicone resin solution for film by the following method.

Straight silicone resin A1: 152 g
(76 g as silicone resin, balance xylene), straight silicone resin A2: 14 g (7 g as silicone resin, balance xylene), 17 g of potassium titanate whisker, di (2-ethylhexyl) phthalate 3
g and 17 g of xylene were placed in a 500 milliliter four-necked flask, and stirred and mixed at 20 ° C. for 2 hours at 400 rpm by a stirrer with a turbine blade. Then, an auto homomixer manufactured by Tokushu Kika Co., Ltd. was used. Mix at 3,000 rpm for 10 minutes. Thereafter, the mixture was filtered through a sieve of 100 mesh and defoamed under reduced pressure to prepare a silicone resin liquid for a film.

Next, the silicone resin solution thus prepared was applied to a release paper with a bar coater to a thickness of 80 μm, and dried by blowing air at 80 ° C. for 2 hours. Then, the film was cooled to form a label body.

Production Examples 2 to 21 In the same manner as in Production Example 1, 20 kinds of silicone resin liquids for films were prepared according to the composition shown in Tables 1 to 7 below. In the same manner as in Example 1, a film constituting the label body was produced. Table 1 to Table 7
In the above, the parts by weight of the silicone resin of the component A are parts by weight of the resin content excluding the solvent. If xylene, a solvent added in advance for the stabilization of silicone resin products, is included, enter the total amount of xylene used as a diluting solvent in the xylene of other components did. Table 1 shows Production Example 1 for reference.
The composition of the silicone resin liquid for film described above is also described.

Production Example 22 A straight silicone resin A2 [trade name "KR-27" manufactured by Shin-Etsu Chemical Co., Ltd.]
1 ") and a low molecular weight straight silicone resin A3 (trade name" KR-212 "manufactured by Shin-Etsu Chemical Co., Ltd.), and aluminum powder (flake-like) as a metal powder of the E component. Aluminum powder, 100 mesh pass 10
0%, average particle size 20 μm) by the following method:
A diluent of the adhesive was prepared.

Straight silicone resin A2: 90 g
(45 g of silicone resin, 48.
9% by weight, balance xylene), straight silicone resin A3: 10 g (7 g as silicone resin, 7.6% by weight in adhesive solids, balance xylene), aluminum powder 40 g (43 in adhesive solids) 0.5% by weight), xylene 1
7 g is placed in a 200 milliliter four-necked flask,
The mixture was stirred and mixed at 20 ° C. for 2 hours at 400 rpm by a stirrer with a turbine blade, and then mixed for 10 minutes at 3,000 rpm by an automatic homomixer manufactured by Tokushu Kika Co., Ltd.
Thereafter, the mixture was filtered through a 100-mesh sieve and defoamed under reduced pressure to prepare a diluent of an adhesive.

Next, the diluted solution of the pressure-sensitive adhesive prepared as described above was applied to a release paper with a bar coater to a thickness of 50 μm, and dried by blowing air at 80 ° C. for 2 hours. ,
After cooling, an adhesive layer was formed on the release paper.

Production Examples 23 to 27 In the same manner as in Production Example 22, diluents of five kinds of pressure-sensitive adhesives were prepared according to the composition shown in Tables 8 and 9 below. Similarly, an adhesive layer was formed on release paper. In Tables 8 and 9, the parts by weight of the silicone resin as the component D indicate parts by weight of the resin excluding the solvent. If xylene, a solvent added in advance for the stabilization of silicone resin products, is included, enter the total amount of xylene used as a diluting solvent in the xylene of other components did. Also,
Table 8 also shows the composition of the diluent of the pressure-sensitive adhesive of Production Example 22 for reference.

In Tables 1 to 9 below, the silicone resin of the A and D components, the single crystalline inorganic fiber of the B component, the resin having a decomposition initiation temperature of the C component of 300 ° C. or less, the metal powder of the E component, The boric acid compound of the F component is as follows.

<A and D Components> Straight Silicone Resin A1: Trade name “KR-255” (Shin-Etsu Chemical Co., Ltd.) (weight average molecular weight 3 × 10 ⁵ ) Straight Silicone Resin A2: Shin-Etsu “KR-271” (product name, manufactured by Chemical Industry Co., Ltd.) (weight average molecular weight: 6 × 10 ⁵ ) Straight silicone resin A3: Product name (low molecular weight product), “KR-212” manufactured by Shin-Etsu Chemical Co., Ltd. (Weight average molecular weight 1.5 × 10 ³ ) Modified silicone resin A4: trade name (acrylic resin modified silicone resin) manufactured by Shin-Etsu Chemical Co., Ltd. “KR-9706” (Weight average molecular weight 1 × 10 3) ⁴ ) Modified silicone resin A5: Trade name of Shin-Etsu Chemical Co., Ltd. (alkyd resin-modified silicone resin) "SA-4" (weight average molecular weight 3 × 10 ⁴ ) Modified silicone resin A6: Shin-Etsu Chemical industry ( ) Trade name (epoxy resin-modified silicone - down resin) "ES-1004" (weight average molecular weight 5 × 10 ⁴⁾ modified silicone - down Resin A7: Shin-Etsu Chemical Co., trade name (polyester resin-modified silicone Resin) “KR-5203” (weight average molecular weight 1 × 10 ⁴ )

<Component B> Potassium titanate whisker: trade name “TISMO TYPE D” manufactured by Otsuka Chemical Co., Ltd. (average fiber length 17 μm, average fiber diameter 0.5 μm) Silicon nitride whisker: average fiber length 50 μm, Average fiber diameter 1μm

<Component C> Polymethyl methacrylate: decomposition starting temperature 289 ° C., average molecular weight 90,000 polyvinyl acetate: decomposition starting temperature 270 ° C., average molecular weight 20,000

<E component> Aluminum powder: scaly powder, 100% mesh pass, 100%, average particle diameter 20 μm Stainless steel powder: Trade name “Stainless Flake SP Ace # FK05” manufactured by Tozai Chemical Co., Ltd. Zinc powder: Fragmented powder, 100 mesh pass 100%, average particle size 30 μm

<F component> Orthoboric acid: Sanei Kako Co., Ltd., purity 99.5% Methyl borate: Tokyo Chemical Industry Co., Ltd.

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

[0090]

[Table 5]

[0091]

[Table 6]

[0092]

[Table 7]

[0093]

[Table 8]

[0094]

[Table 9]

Comparative Production Examples 1 to 8 Eight kinds of film silicone resin liquids were prepared in the same manner as in Production Example 1 according to the composition shown in Tables 10 and 11 below. In the same manner as in Example 1, a film constituting the label body was produced. In both tables, parts by weight of resin indicate parts by weight of resin except for solvent. If solvents previously added for the stabilization of silicone resin or polyimide resin products are included, the sum of xylene or dimethylformamide used for dilution should be included in the solvent component of other components. It was described as an amount.

In Tables 10 and 11, "polymethyl methacrylate" and "straight silicone
Resin A1 "and straight silicone resin A
"2" and "potassium titanate whisker" as other components are the same as those described in Tables 1 to 7 above, respectively, and the others are as follows.

<Resin component> Polyimide resin: decomposition initiation temperature 405 ° C. <Other components> Glass frit: trade name “ASF-1” manufactured by Asahi Glass Co., Ltd.
307F ”Glass fiber: trade name“ G ”manufactured by Asahi Fiber Glass Co., Ltd.
FC-150A "(average fiber length 70 μm, average fiber diameter 11 μm)

[0098]

[Table 10]

[0099]

[Table 11]

Example 1 The film constituting the label body produced in Production Example 1 was superimposed on the release paper having the adhesive layer formed in Production Example 22, and the pressure was 20 kg / cm ² at room temperature for 60 minutes. Perform a cold press and press-fit sufficiently, then 10mm × 5
It was cut to a size of 0 mm to produce a plain label.

Examples 2 to 22 As a release paper having a film constituting a label body and a pressure-sensitive adhesive layer on which the film is superimposed, a release paper obtained in a production example shown in Table 12 below is used in combination. ,
In the same manner as in Example 1, 21 types of plain labels were produced. In this table, the above combination of Example 1 is also described for reference.

Comparative Examples 1 to 11 Comparative Production Example 1 was used as a film constituting the label body.
The release paper having a pressure-sensitive adhesive layer on which the adhesive layers were laminated was used in combination with those obtained in the production examples shown in Table 13 below.
In the same manner as described above, 11 types of plain labels were produced.

Comparative Examples 12 and 13 Production films 17 and
18, and as a release paper having an adhesive layer on which the adhesive is superimposed, a commercially available heat-resistant adhesive G1 [trade name of Toray Silicone Co., Ltd.] shown in Table 13 below. "SD4560"] and G2 (trade name "X-40-3111" manufactured by Shin-Etsu Chemical Co., Ltd.) were obtained by forming a pressure-sensitive adhesive layer on release paper by a standard method of use. Two kinds of plain labels were produced in the same manner as in Example 1, except that the combination was used.

[0104]

[Table 12]

[0105]

[Table 13]

Comparative Example 14 A commercially available Teflon sheet (thickness: 100 μm, decomposition start temperature: 460 ° C.) was superposed on a release paper having an adhesive layer formed in Production Example 22, and pressed well. After that, it was cut into a size of 10 mm × 50 mm to prepare a plain label.

The above Examples 1-22 and Comparative Examples 1-1
Using each of the plain labels of No. 4, a flexibility test, a heat resistance test, a scratch resistance test, a heat peel test and a gas contamination test were performed in the following manner. These test results are shown in Table 1 below.
4 and Table 15. Table 1
5 shows the result of using a commercially available heat-resistant ceramic label (trade name “Ceralabel-Green 450” manufactured by Sigmax Corporation) as a reference example.

<Flexibility Test> For each of the Examples and Comparative Examples, 23 plain labels were peeled from the release paper.
One piece was attached to each of the 23 glass tubes having a diameter of 1 cm such that the major axis direction of the glass tube and the long side of the label were parallel. A fragile label with poor flexibility cannot follow the curvature of the glass tube and cracks occur. The sticking performance was evaluated based on the number of occurrences of the cracks. The evaluation criteria are as follows. ◎: All 23 sheets could be pasted. ○: Cracks occurred on 1 to 4 of 23 sheets. △: Cracks occurred on 5 to 11 of 23 sheets. ×: Cracks on 12 or more of 23 sheets. Has occurred,
Or it was rigid and could not be pasted itself

<Heat Resistance Test> In the same manner as in the case of the flexibility test, three glass tubes to which one plain label was attached were placed at 250 ° C., 300 ° C., 350 ° C., 400 ° C., and 450 ° C.
After heating for 1 hour at each temperature of 500 ° C. and 500 ° C., the temperature was cooled to room temperature, and the appearance was observed. . In addition, about what was evaluated as x in the flexibility test, the heat resistance test was not performed.

<Scratch Resistance Test> The plain label after the heat resistance test was lightly rubbed with a black cotton cloth, and evaluated in the following three stages. ：: The cloth is not stained at all. ：: Pigment is observed on the cloth, but the label is retained. ×: The label is scraped off or completely peeled off.

<Heat Resistance Peeling Test> One plain label was placed on 45
After heating for 1 hour at a temperature of 0 ° C., the mixture was cooled to room temperature, and then an adhesive tape (trade name “Scotch ^R Clear Tape” manufactured by Sumitomo 3M Ltd.) was affixed to the label.
After being strongly pressed with a finger, it was peeled off. After exposure to high temperatures, labels with poor adhesion will adhere to the adhesive tape and peel off from the glass tube. The heat-resistant adhesive strength was evaluated in this peeled state. The evaluation criteria are as follows. ◎: No peeling was observed at all ○: Less than 10% of the entire label surface was peeled △: 10% or more and less than 50% of the entire label surface was peeled ×: 50% or more of the entire label surface was peeled

<Gas contamination test> One plain label was
Attached to the center of a 00 mm x 100 mm x 2 mm glass plate, and attached to the center of the ceiling with an air hole with a diameter of 2 cm 4.5 liters (internal size 150 mm x 150 mm x 200 mm)
mm), the temperature was raised from 30 ° C. to 450 ° C. over 30 minutes, and then maintained at 450 ° C. for 30 minutes, cooled to 30 ° C. over 1 hour, and taken out. Immediately after the removal, the contact angle to water at a point 1 cm away from the label on the glass plate was measured. This measurement is
Five points were performed for one sample, and the average value was obtained. When the glass surface is contaminated with the decomposition gas, the contact angle increases. The contact angle of the glass plate, which was not attached, under the same conditions was 8 degrees.

[0113]

[Table 14]

[0114]

[Table 15]

As is clear from the above results, the labels of Examples 1 to 22 of the present invention can greatly improve the flexibility of the commercially available heat-resistant ceramic label of the reference example, exhibit excellent heat resistance, and exhibit high heat resistance. It can be seen that the abrasion resistance and the heat peelability after the test are also excellent. In addition, in particular, the labels of Examples 20 to 22 in which a silicone resin cross-linking agent was added to the film constituting the label body had a small contact angle of the attached glass plate, and no gas contamination was observed.

On the other hand, the labels of Comparative Examples 1 to 3 and 9 using resins other than silicone resin as the film constituting the label body, and amorphous inorganic fibers were used instead of the monocrystalline inorganic fibers. The labels of Comparative Example 4 using glass fibers and the labels of Comparative Examples 5 to 7 and 10 using glass frit all have little improvement in flexibility and insufficient heat resistance. In addition, the labels of Comparative Examples 8 and 11 using titanium oxide powder instead of single crystalline inorganic fibers, although using a silicone resin, had flexibility, but had poor heat resistance and abrasion resistance. Poor in heat-resistant peeling properties.

Further, the labels of Comparative Examples 12 and 13 in which a commercially available heat-resistant adhesive is adhered to the film constituting the label body used in the present invention are remarkably inferior in heat-peelability. Furthermore, the label of Comparative Example 14 using a commercially available Teflon sheet can improve the flexibility, but is extremely poor in heat resistance.

Claims (13)

(57) [Claims] 1. A component (A) is present in an amount of 20 to 9 in the total amount of both components (A) and (B).
In a film containing 5% by weight and 80% by weight of the B component, D) a silicone resin and E) a metal powder were mixed with 10% of the D component in the total amount of both the D and E components. A label to which an adhesive comprising 80% by weight and E to 90% to 20% by weight is attached. 2. A component (A) comprising a silicone resin, (B) a single crystalline inorganic fiber, and (C) a resin having a decomposition initiation temperature of 350 ° C. or lower, comprises A component (A) and (C). D) a silicone resin in a film comprising the following components: -90% by weight, B-component 60-60% by weight, C-component 20-5% by weight;
E) metal powder and D component 1 in the total amount of both D and E components
A label to which an adhesive comprising 0 to 80% by weight and E to 90 to 20% by weight is attached. 3. The composition of claim 2, wherein A) a silicone resin and B) a single-crystalline inorganic fiber, wherein A component is 20 to 9 in the total amount of both A and B components.
D) a silicone resin, E) a metal powder, and 5% by weight of a film containing 80% to 5% by weight of a B component.
F) The boric acid compound is 10 to 75% by weight of the D component, 80 to 24.9% by weight of the E component, and F in the total amount of the D to F three components.
A label to which an adhesive comprising 10 to 0.1% by weight of a component is attached. 4. The method according to claim 1, wherein A) a silicone resin, B) a single crystalline inorganic fiber, and C) a resin having a decomposition start temperature of 350 ° C. or less, wherein A component 20 is included in the total amount of A to C three components. D) a silicone resin in a film comprising the following components: -90% by weight, B-component 60-60% by weight, C-component 20-5% by weight;
E) a metal powder and F) a boric acid compound in a total amount of the D to F three components, 10 to 75% by weight of the D component, and 80 to 2 of the E component.
A label to which an adhesive comprising 4.9% by weight and F component at 10 to 0.1% by weight is attached. 5. The label according to claim 1, wherein the silicone resin of the component A and the component D has a weight average molecular weight of 200 to 5,000,000. 6. The silicone resin of component A, wherein: A-L) a low molecular weight silicone resin having a weight average molecular weight of 200 to 500,000; and AH) a weight average molecular weight of the above AL component. Of a high molecular weight silicone resin having a weight average molecular weight of 10 to 1,000 times that of the A-L component and the A-H component of 95 to 50% by weight. The label according to any one of claims 1 to 5. 7. The label according to claim 1 , wherein the silicone resin of the component A is a silicone resin that cures at a temperature of less than 100 ° C. 8. The label according to claim 1 , wherein the silicone resin of component D is a silicone resin which cures at a temperature of 100 ° C. or higher. 9. The label according to claim 1, wherein the silicone resin of the component A and the component D contains 50% by weight or more of the straight silicone resin. 10. A silicone resin 1 whose film is an A component.
The label according to any one of claims 1 to 9, comprising 0.1 to 100 parts by weight of a crosslinking agent based on 00 parts by weight. 11. The label according to claim 10, wherein the crosslinking agent is at least one selected from a boric acid compound and an organometallic compound. 12. The label according to claim 1, wherein the metal powder of component E is at least one selected from aluminum powder, zinc powder, and stainless steel powder. 13. After attaching the label according to any one of claims 1 to 12 to a heat-resistant material, 200 to 700
A label baking method comprising baking a label on a heat-resistant material by treating at a temperature of ° C.