JPH1152861A - Label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a label which has excellent flexibility, is stickable to a surface having a small radius of curvature and may be baked to a heat resistant material without the occurrence of dusting and cracking in spite of a high- temp. treating stage particularly at >=600 deg.C. SOLUTION: This label is formed by adhering a heat resistant tacky adhesive to a label base material which contains (A) cured silicon resin powder, (B) uncured silicone resin and (C) single crystalline inorg. fibers and of which the ratios to the total amt. of the component (A), the component (B) and the component (C) are 5 to 50 wt.% component (A), 15 to 90 wt.% component (B) and 5 to 80 wt.% component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a label.
More specifically, the present invention is excellent in flexibility and heat resistance.
The present invention relates to a label that can be baked on a heat-resistant material in a high-temperature processing step of 00 to 700 ° C.

[0002]

2. Description of the Related Art In a wide range of industrial fields such as food, fiber, and chemistry, a label on which a symbol, a character, a pattern, or the like is printed, that is, a pattern forming label is attached to a product or its packaging, and is used for process control. I have. A typical example is a management system using a barcode label. In this barcode management system, information such as the manufacturing status and price of a product is mechanically read from a barcode label to manage the manufacturing process and the sales status. However, a normal bar code label in which a label film is made of a resin or paper with low heat resistance and an adhesive made of an acrylic resin or the like is adhered to the film is a severe one having a label body and an adhesive of 300 ° C. or more. Under temperature conditions, it decomposes and evaporates. Therefore, it cannot be used in an industrial field having a high-temperature treatment step such as the ceramics industry, the steelmaking industry, and the glass industry, for example, a television cathode ray tube manufacturing step having a 400-600 ° C. enclosing and annealing step. Therefore, a label film and an adhesive that can withstand a high temperature of 400 ° C. or more are required. On the other hand, conventionally, glass fibers, a heat-resistant film obtained by impregnating a heat-resistant binder resin such as a polyamide resin with a cloth material woven of long inorganic amorphous fibers such as rock wool, There is known a pressure-sensitive adhesive tape to which a heat-resistant pressure-sensitive adhesive mainly containing crosslinked silicone is attached. However, if these are used as labels, 300
At high temperatures exceeding ℃, discoloration occurs, the tube cannot withstand thermal expansion of cathode ray tubes and metal plates, cracks occur on labels, and peeling occurs, limiting its use. Is the current situation. In order to solve such problems, for example,
No. 42083 discloses a heat resistance for a cathode ray tube manufacturing process in which a bar code is printed on a label film made of ceramics, porcelain, enamel, etc. with an ink containing a glassy inorganic compound (glass frit) having a low melting point, an inorganic pigment and a solvent. Bar code labels have been proposed. However, although this heat-resistant barcode label has sufficient heat resistance, there is no adhesive having the same or higher heat resistance as that of the base material, and since the base material is rigid, it can be attached to a curved surface. Can not. For this reason, the only method of sticking that makes full use of the heat resistance of the label itself is to use screws or insert it into pockets, and it is not possible to use an automatic label sticking machine (labeler). Cannot be applied to the manufacturing process. As an attempt to solve such a problem and to realize a heat-resistant label which can be automatically applied without causing the label to be degraded or dropped even at a high temperature, International Publication WO88 / 07937 discloses a resin containing a large amount of glass frit. On top of the film
A label has been proposed in which a barcode is printed with a heat-resistant ink and an adhesive having a low thermal decomposition temperature is applied. The glass frit used for this label melts when exposed to a high temperature, and the bar code pattern can be fused and left on the product surface even after the adhesive is degraded and decomposed. However, in the label containing the glass frit, the glass frit used is several μm at room temperature.
Since the powder is a solvent-insoluble powder having a large particle size of about several tens of μm, a film containing a large amount of glass frit becomes very brittle. For this reason, although it is possible to paste by an automatic pasting machine, it is often damaged at that time, and in the worst case, the production line is stopped.
To solve such a problem, Japanese Patent Application Laid-Open No.
In Japanese Patent Application Laid-Open No. 5 (1993) -5, a label base material in which inorganic powder is formed into a sheet shape with a silicone resin is proposed.
Japanese Patent No. 01843 proposes a composite material in which a woven or nonwoven fabric is coated or impregnated with a heat-resistant paint comprising a polymetallocarbosilane, a silicone resin, a granular inorganic filler and a short-fiber inorganic filler. However, in any of the label base materials, if there is no reinforcing fiber layer, there is a problem that the label strength is small and easily broken, and after passing through a high-temperature process, the contained inorganic powder may peel off from the surface, or the label may be broken. The so-called "powder wiping" phenomenon, in which fine pieces or the like generated by the surface shrinking and breaking due to high heat and contaminating the bar code printing surface and the surroundings, easily occurs, and the heat resistance is not sufficient. The present inventors have disclosed in Japanese Patent No. 2614022 as a method for solving the problems relating to these heat resistant labels.
JP-A-2003-209, the use of a label substrate composed of a silicone resin and a monocrystalline inorganic fiber and a silicone resin-based pressure-sensitive adhesive containing a metal powder eliminates the need for a reinforcing fiber layer and is less likely to cause a dusting phenomenon. Suggested. However, although the heat-resistant label shows sufficient performance up to about 500 ° C., at a temperature of 600 ° C. or more, minute cracks are generated on the surface due to the shrinkage of the label surface due to the high temperature, and the crack portion is peeled off. The surroundings were sometimes contaminated by the fine fragments generated by this. In order to prevent this, there is a method of using an inorganic powder in combination for the purpose of reducing the shrinkage of the label at a high temperature. However, when the inorganic powder is used in combination, the inorganic powder is caused by the inorganic powder at a temperature exceeding 600 ° C. Since a dusting phenomenon occurs, there is a possibility that a problem may occur in an encapsulation process that dislikes fine dust.

[0003]

DISCLOSURE OF THE INVENTION The present invention is excellent in flexibility and can be attached to a surface having a small radius of curvature, and can prevent dusting or cracking even in a high-temperature treatment step of 200 ° C. or more, especially 600 ° C. or more. It is intended to provide a label which can be baked on a heat-resistant material without causing it.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, in a label made of a silicone resin and a monocrystalline inorganic fiber, the label was previously cured in the silicone resin. Even if the inorganic powder is not used or the amount used is greatly reduced by using the silicone resin powder, cracks due to shrinkage of the label hardly occur at a temperature exceeding 600 ° C., and a dusting phenomenon also occurs. No heat-resistant label was obtained, and the present invention was completed based on this finding.
That is, the present invention comprises (1) (A) a cured silicone resin powder, (B) an uncured silicone resin, and (C) a monocrystalline inorganic fiber, and the components (A), (B) and (C) The heat-resistant adhesive is applied to a label substrate in which the proportion of the component (A) to the total amount of the component (A) is 5 to 50% by weight, the component (B) is 15 to 90% by weight, and the component (C) is 5 to 80% by weight. A label characterized by being attached, and (2) the label according to (1), wherein the heat-resistant adhesive is a silicone-based adhesive containing metal powder. Further, as preferred embodiments of the present invention, (3) the label according to (1), wherein the average particle diameter of the cured silicone resin powder is 0.01 to 500 μm, and (4) the weight average molecular weight of the uncured silicone resin is ,
(5) The label according to (1), wherein the label is from 200 to 5,000,000, (5) the label according to (1), wherein the monocrystalline inorganic fiber is a potassium titanate whisker, and (6) the monocrystalline inorganic. The label according to item (1), wherein the average fiber length of the fibers is 200 μm or less and 3 times or more the average fiber diameter, may be used.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The label of the present invention comprises (A) a cured silicone resin powder, (B) an uncured silicone resin, and (C) a monocrystalline inorganic fiber, and the component (A), (B) Ingredients and
The heat-resistant adhesive is applied to a label substrate in which the ratio of the component (C) to the total amount of the component (A) is 5 to 50% by weight, the component (B) is 15 to 90% by weight, and the component (C) is 5 to 80% by weight. An agent is adhered. In the present invention, the cured silicone resin powder used as the component (A) is a powder obtained by polymerizing and curing a compound having an organopolysiloxane structure, and such a cured silicone resin powder is And a powdered cured straight silicone resin and a powdered cured modified silicone resin. In the present invention, as the cured silicone resin powder as the component (A), one type can be used alone, or two or more types can be used in combination. Among these, a solvent-insoluble cured straight silicone resin powder obtained by crosslinking and curing a silicone resin containing a straight silicone resin as a main component until it becomes insoluble in a diluting solvent used in label production such as xylene is particularly preferably used. be able to.

A cured straight silicone resin is a crosslinked cured product of an organopolysiloxane having a hydrocarbon group as a main organic group, and includes a resin having a hydroxyl group. The hydrocarbon group is an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and in the present invention, a cured resin having an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Straight silicone resin powder can be suitably used. All of these hydrocarbon groups may be the same, or two or more hydrocarbon groups may be mixed. 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. it can. Carbon number 6
Examples of the aromatic hydrocarbon group of -12, for example, phenyl group, methylphenyl group, ethylphenyl group, butylphenyl group, naphthyl group, styryl group, allylphenyl group,
And a propenylphenyl group. The cured silicone resin powder used in the present invention preferably has an average particle size of 0.01 to 500 μm, and 0.1 to 2 μm.
More preferably, it is 00 μm. If the average particle size of the cured silicone resin powder is less than 0.01 μm, the viscosity of the resin liquid at the time of producing the film increases, and the handling property may be deteriorated. If the average particle size of the cured silicone resin powder exceeds 500 μm, the film surface may have poor smoothness.

In the present invention, the uncured silicone resin used as the component (B) is used by mixing with a cured silicone resin powder, and plays a role as a binder. Such an uncured silicone resin is added to a resin solution for producing a label film, and is cross-linked and cured during the production and use of the label film, so that the label film containing the cured silicone resin powder and the monocrystalline inorganic fiber. To form Such an uncured silicone resin is an uncured polymer compound having an organopolysiloxane structure, and examples thereof include an uncured straight silicone resin and an uncured modified silicone resin. These uncured silicone resins are silicone resins that are cured by heating, standing at room temperature or adding a catalyst, and can be used as they are or as a resin solution dissolved in a solvent, but can be easily formed into a film when producing a label. Therefore, it is preferable to use as a resin solution dissolved in a solvent. In the present invention, the uncured straight silicone resin used as the uncured silicone resin is an organopolysiloxane having a hydrocarbon group as a main organic group, and includes a resin having a hydroxyl group. The hydrocarbon group is an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In the present invention, the hydrocarbon group has 1 to 5 carbon atoms, or has 6 to 1 carbon atoms.
An uncured straight silicone resin having two aromatic hydrocarbon groups can be suitably used. All of these hydrocarbon groups may be the same, or two or more hydrocarbon groups may be mixed. 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. it can. Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a butylphenyl group, a naphthyl group, a styryl group, an allylphenyl group, and a propenylphenyl group. .

In the present invention, the uncured modified silicone resin used as the uncured silicone resin is an organopolysiloxane containing an organic group other than a hydrocarbon group,
For example, methoxy group-containing silicone resin, ethoxy group-containing silicone resin, epoxy group-containing silicone resin, alkyd resin-modified silicone resin, acrylic resin-modified silicone resin, polyester resin-modified silicone resin,
An epoxy resin-modified silicone resin can be used. These uncured modified silicone resins, for example,
A method of reacting a hydroxyl group contained in a straight silicone resin with an organic compound having a functional group such as a carboxyl group, an acid anhydride group, a hydroxyl group, an aldehyde group, an epoxy group, or a chloride group capable of reacting with the hydroxyl group, a vinyl group A method of copolymerizing a straight silicone resin having an unsaturated hydrocarbon group such as a compound having an unsaturated double bond and a modified silane compound obtained by reacting the silane compound with another organic compound by hydrolysis. It can be obtained by a method of condensation or co-condensation. The organic compound to be reacted may be a low molecular compound or a high molecular compound such as a resin. In the present invention, the uncured silicone resin as the component (B) can be used alone or in combination of two or more. Among these uncured silicone resins, the uncured straight silicone resin is particularly preferably used because it is hardly discolored by heating. The uncured silicone resin used in the present invention has a weight average molecular weight of 2
It is preferably from 500 to 5,000,000, and 500
More preferably, it is ２2,000,000. If the weight-average molecular weight of the uncured silicone resin is less than 200, the strength of the label may be reduced. If the weight-average molecular weight of the uncured silicone resin exceeds 5,000,000, the viscosity of the resin liquid becomes too high when processing the label base material, which may make handling difficult.

In the present invention, the monocrystalline inorganic fiber used as the component (C) is a fiber made of an inorganic single crystal, such as a silicon carbide whisker, a silicon nitride whisker, an alumina whisker, a titanate whisker,
Examples include zinc oxide whiskers, magnesia whiskers, aluminum borate whiskers, wollastonite, and the like. All of the single crystalline inorganic fibers mentioned here have an average fiber length of 5 times or more the average fiber diameter. In the present invention, one kind of single crystalline inorganic fiber as the component (C) can be used alone, or two or more kinds can be used in combination. Among these single crystalline inorganic fibers, potassium titanate whiskers, which are a kind of titanate whiskers, can be particularly preferably used.
In the present invention, the monocrystalline inorganic fiber has an average fiber length of 2
Preferably, the average fiber length is 10 μm or less.
More preferably, it is 0 μm or less. If the average fiber length of the monocrystalline inorganic fibers exceeds 200 μm, the sharpness of the printed pattern may be impaired. The average fiber length of the monocrystalline inorganic fibers is preferably at least three times the average fiber diameter, and more preferably at least five times the average fiber diameter. If the average fiber length of the monocrystalline inorganic fibers is less than three times the average fiber diameter, the strength of the film may be reduced.

In the present invention, the ratio of the cured silicone resin powder of the component (A) to the total amount of the (A) cured silicone resin powder, the (B) uncured silicone resin and the (C) single crystalline inorganic fiber in the resin liquid. Is from 5 to 50% by weight, more preferably from 10 to 40% by weight. When the proportion of the cured silicone resin powder of the component (A) is less than 5% by weight,
If the condition is more than 50%, powder wiping is likely to occur, and if the ratio of the cured silicone resin powder of the component (A) exceeds 50% by weight, the viscosity of the resin liquid becomes high and the handling property when producing a film may be deteriorated. There is. In the present invention, the component (A), the component (B) and the component (C) relative to the total amount of the component
The proportion of the uncured silicone resin as the component (B) is from 15 to 90% by weight, and more preferably from 20 to 80% by weight.
If the proportion of the uncured silicone resin as the component (B) is less than 15% by weight, the strength of the film may be reduced.
If the proportion of the uncured silicone resin (B) exceeds 90% by weight, the heat resistance of the label may be insufficient. In the present invention, the ratio of the monocrystalline inorganic fiber of the component (C) to the total amount of the components (A), (B) and (C) is 5 to 8
0% by weight, more preferably 10 to 70% by weight. When the proportion of the monocrystalline inorganic fiber of the component (C) is less than 5% by weight, the heat resistance of the label may be insufficient.
When the proportion of the monocrystalline inorganic fiber of the component (C) exceeds 80% by weight, the flexibility of the label may be reduced.

In the present invention, the flexibility, printing characteristics, heat resistance, and the like of the label substrate obtained by filming a resin solution containing the components (A), (B) and (C) as essential components are described. For the purpose of improving physical properties such as tensile strength, various additives can be further added. Examples of such additives include a crosslinking agent for a silicone resin, a plasticizer, and an inorganic pigment. Examples of the crosslinking agent for the silicone resin include boric acid compounds such as boric acid, borates and borate esters, and organic compounds such as organic tin compounds, organic lead compounds, organic zinc compounds, organic aluminum compounds, and organic titanium compounds. Metal compounds and the like can be mentioned. By adding a crosslinking agent for these silicone resins, the strength of the label can be improved. The amount of the crosslinking agent added to the silicone resin depends on the components (A), (B) and
It is preferably at most 10 parts by weight, more preferably at most 5 parts by weight, based on 100 parts by weight of the total amount of the component (C). When the amount of the silicone resin crosslinking agent added is (A)
If the total amount of the components, (B) and (C) exceeds 10 parts by weight based on 100 parts by weight, the label may be fragile.

Examples of the plasticizer include an aliphatic carboxylic acid ester, an aromatic carboxylic acid ester and a phosphoric acid ester. Examples of the aliphatic carboxylate include methyl laurate, butyl oleate, diethylene glycol dilaurate, di (2-ethylbutoxyethyl) adipate, phenyl oleate and the like, and aromatic carboxylate Examples thereof include dimethyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate, dilauryl phthalate, and oleyl benzoate.Examples of phosphate esters include tricresyl phosphate and phosphoric acid Trioctyl and the like can be mentioned.
By adding these plasticizers, the flexibility of the label can be further improved. The amount of plasticizer added is (A)
The amount is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of the components, the components (B) and (C). If the amount of plasticizer added is
If the total amount of the components (A), (B) and (C) exceeds 20 parts by weight with respect to 100 parts by weight, the flexibility of the label becomes too large, and the label peels off from the release paper used as the backing paper. It may be difficult.

The inorganic pigment is preferably a pigment that does not discolor at a high temperature of 300 ° C. or higher. Examples of such inorganic pigments include coloring pigments such as zinc oxide, aluminum oxide, aluminum hydroxide, lithopone, titanium oxide, chromium oxide, manganese oxide, nickel titanium yellow, chromium titanium yellow, red iron oxide, and raster pigment. The extender can include microsilica, calcium carbonate, and the like. By adding these pigments, the contrast of printing can be increased and the adhesion of printing ink can be improved. The amount of the pigment added is (A) component, (B) component and
It is preferably at most 20 parts by weight, more preferably at most 10 parts by weight, based on 100 parts by weight of the total amount of the component (C). When the amount of the pigment exceeds 20 parts by weight based on 100 parts by weight of the total amount of the components (A), (B) and (C), when the label goes through a high temperature exceeding 600 ° C.,
There is a possibility that dusting is likely to occur and the feature of the present invention that the dusting phenomenon is small is impaired.

In the present invention, the uncured silicone resin used as the component (B) is often commercially available as a solution containing a solvent. However, in order to facilitate the film-forming step, a solvent for dilution and dispersion is further added. Can be added. The solvent for dilution and dispersion preferably has a boiling point of 0 to 300 ° C, more preferably 25 to 200 ° C. As such a solvent for dilution and dispersion,
For example, aliphatic hydrocarbons such as hexane, octane, decane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and naphthalene; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; methanol, ethanol, and 2-ethylhexanol Alcohols, ethers such as ethylene glycol monomethyl ether 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 can be particularly preferably used. The amount of the solvent for dilution and dispersion is preferably not more than 500 parts by weight, and more preferably not more than 200 parts by weight, based on 100 parts by weight of the total of the components (A), (B) and (C). Is more preferable. When the amount of the solvent for dilution and dispersion is (A) component, (B)
500 per 100 parts by weight of the total amount of the component and the component (C)
If the amount is more than the weight part, it takes only time to dry the label substrate, and no further effect is recognized, which may be economically disadvantageous.

In the present invention, when preparing the label base material constituting the label body, first, the cured silicone resin powder as the component (A), the uncured silicone resin as the component (B), and the component (C). The monocrystalline inorganic fibers are mixed alone or, if necessary, with other additives and solvents, at room temperature or under heating. At this time, mixing can be carried out using a disperser such as a disperser, a ball mill, a sand mill, a roll mill, and a homogenizer. The mixture can be coated or printed on a release paper or a mold coated with 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 1,0.
It is preferably 00 μm. In the present invention, there is no particular limitation on the pressure-sensitive adhesive to be adhered on the label substrate constituting the label body, and a known heat-resistant pressure-sensitive adhesive can be adhered, which is disclosed in Japanese Patent No. 2614022. An adhesive containing a metal powder and a silicone resin can be particularly preferably used. In order to attach the pressure-sensitive adhesive to the label substrate constituting the label main body, for example, the pressure-sensitive adhesive can be applied onto the label substrate produced by the above-described method and dried. Alternatively, on the contrary, the mold is coated with a release paper or a release agent, by a known coating method or printing method, an adhesive is applied or printed, dried at room temperature or under heating, and then The label base material constituting the label body produced in advance can be pressure-bonded.
Although there is no particular limitation on the amount of the pressure-sensitive adhesive adhered, it is usually preferable that the pressure-sensitive adhesive layer has a thickness of 0.5 to 500 μm.

[0016]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The following components were used in Examples and Comparative Examples. (A) Cured silicone resin powder Silicone resin powder A1: Toray Dow Corning Silicone Co., Ltd., Trefil R-900, amorphous silicone resin powder, particle size distribution 3 to 80 μm. Silicone resin powder A2: Toray Dow Corning Silicone Co., Ltd., Trefil R-902, amorphous silicone resin powder, particle size distribution 1 to 40 μm. Silicone resin powder A3: Toray Dow Corning Silicone Co., Ltd., Trefil R-930, spherical silicone resin powder, particle size distribution 0.7 to 1.4 μm. (B) Uncured silicone resin Silicone resin B1: Shin-Etsu Chemical Co., Ltd., straight silicone resin, KR-255, weight average molecular weight 300,
000, 50% by weight xylene solution. Silicone resin B2: Shin-Etsu Chemical Co., Ltd., straight silicone resin, KR-271, weight average molecular weight 600,
000, 50% by weight xylene solution. Silicone resin B3: Shin-Etsu Chemical Co., Ltd., straight silicone resin, KR-212, weight average molecular weight 1,50
0, 70% by weight xylene solution. (C) Single crystalline inorganic fiber potassium titanate whisker: Otsuka Chemical Co., Ltd., TISM
O TYPE D, average fiber length 17 μm, average fiber diameter 0.
5 μm. (Others) Polymetallocarbosilane: Ube Industries, Ltd., Vn100. Glass fiber: Asahi Fiber Glass Co., Ltd., GF-C15
OA, average fiber length 70 μm, average fiber diameter 11 μm. In Examples and Comparative Examples, the evaluation of the label was performed by the following method. (1) Flexibility test Ten plain labels were peeled off from release paper, and one on each side of ten glass tubes with a diameter of 10 mm such that the major axis direction of the glass tube and the long side of the label were parallel. Pasted. A fragile label with poor flexibility cannot follow the curvature of the glass tube and cracks occur. The bonding performance is evaluated based on the number of occurrences of the cracks. The evaluation criteria are as follows. ：: All 10 sheets can be pasted. Δ: Cracks occur on 1 to 5 sheets out of 10 sheets. ×: Cracks are generated on 6 or more of the 10 sheets, or they are rigid and cannot be attached. (2) Heat resistance test In the same manner as in the case of the flexibility test, five glass tubes to which one plain label was attached were placed at 500 ° C. or 600 ° C.
After heating for an hour, the temperature is cooled to room temperature, and the appearance is observed to evaluate the heat resistance. The evaluation criteria are as follows. ：: No abnormal appearance such as yellowing, peeling, cracks, etc. occurs in all five sheets. Δ: One out of five sheets had abnormal appearance such as yellowing, peeling and cracking. ×: Two or more of the five sheets had abnormal appearance such as yellowing, peeling, and cracks. (3) Powdering test For a glass tube on which a plain label was applied and subjected to a heat resistance test, a cellophane tape was thoroughly adhered to the label surface with a finger, and after peeling off, the powder or fine label adhered to the cellophane tape was removed. Observe the amount of debris and evaluate the dusting. The evaluation criteria are as follows. ：: No powder or fine label fragments adhered to the cellophane tape. Δ: Powder or fine label fragments are slightly adhered to the cellophane tape. ×: A large amount of powder or fine label fragments adhered to the cellophane tape. Example 1 (Preparation of release paper with adhesive) Straight silicone resin [Shin-Etsu Chemical Co., Ltd., KR-
255, 50% by weight xylene solution] 80 g, straight silicone resin [Shin-Etsu Chemical Co., Ltd., KR-212, 7]
0% by weight xylene solution] 17 g, stainless steel powder [Tosei Chemical Co., Ltd., stainless steel flake SP Ace @ FK05]
100 g, 3 g of boric acid and 120 g of xylene in a capacity of 50
The mixture was placed in a 0 ml four-necked flask, stirred at room temperature for 2 hours at 400 rpm using a stirrer with a turbine blade, and then mixed at 3,000 rpm for 10 minutes using an auto-homomixer (Special Kika Co., Ltd.). Thus, a diluent of the adhesive was prepared. This adhesive diluent was applied to a release paper having a thickness of 50 μm using a bar coater, dried for 2 hours by blowing air at 80 ° C., and then cooled to prepare a release paper with an adhesive. Example 2 Silicone resin powder A1 [Toray
Dow Corning Silicone Co., Ltd., Trefil R-90
0, amorphous silicone resin powder, particle size distribution 3 to 80μ
m] 21 g, silicone resin B1 (Shin-Etsu Chemical Co., Ltd., KR-255, 50% by weight xylene solution) as a component (B) 84 g and silicone resin B3 [Shin-Etsu Chemical Co., Ltd .;
KR-212, 70% by weight xylene solution] 10 g, (C)
Potassium titanate whisker [Otsuka Chemical
Co., Ltd., TISMO TYPE D] 30 g and xylene 5
8 g was placed in a 500 ml four-necked flask, and the mixture was stirred at 20 ° C. using a stirrer with a turbine blade at 400 rpm.
For 2 hours, and then mixed at 3,000 rpm for 10 minutes using an auto-homomixer [Special Kika Co., Ltd.].
Thereafter, the mixture was filtered through a 100-mesh sieve and defoamed under reduced pressure to prepare a silicone resin liquid for a film. The silicone resin liquid for a film is applied to a template paper with a bar coater to a thickness of 80 μm using a bar coater, dried by blowing air at 80 ° C. for 2 hours, and then cooled to form a label substrate constituting a label body. Produced. This label substrate was superimposed on the release paper with adhesive prepared in Example 1 and
After performing cold pressing under normal pressure for 60 minutes at room temperature under a pressure of kg / cm ² , the blank was cut into a size of 10 mm × 50 mm to prepare a plain label. The 10 plain labels were peeled off from the release paper, and the labels were affixed one by one to the side surfaces of 10 glass tubes having a diameter of 10 mm such that the major axis direction of the glass tubes and the long sides of the labels were parallel. All ten sheets could be pasted. Five glass tubes to which the plain label was attached were heated at 500 ° C. and five at 600 ° C. for 1 hour, respectively, and then cooled to room temperature. Neither the plain label heated at 500 ° C. nor the plain label heated at 600 ° C. had any appearance abnormality such as yellowing, peeling or cracking. Also, the glass tube heated at 500 ° C.
When the cellophane tape was applied to the label of the glass tube heated in the above step and peeled off, no adhering matter was observed on the cellophane tape. Examples 3 to 6 In the same manner as in Example 2, four kinds of silicone resin liquids for films were prepared according to the composition shown in Table 1. Using these resin liquids, in the same manner as in Example 2, a label base material constituting the label body was prepared, bonded to a release paper with an adhesive, and cut to prepare a plain label. A flexibility test, a heat resistance test, and a dusting test were performed on these plain labels in the same manner as in Example 2. Comparative Example 1 A plain label was produced using a resin solution containing no component (A). Silicone resin B1 [Shin-Etsu Chemical Co., Ltd., KR-255, 50% by weight xylene solution] 1 as a component (B)
00g and silicone resin B3 [Shin-Etsu Chemical Co., Ltd., KR
-212, 70% by weight xylene solution] 7.1 g, potassium titanate whisker as component (C) [Otsuka Chemical Co., Ltd.
TIMMO TYPE D] 45 g and xylene 50.9
g, a silicone resin liquid for film was prepared in the same manner as in Example 2. Further, the same operation as in Example 2 was repeated using this silicone resin liquid for a film to produce a plain label having a size of 10 mm × 50 mm.
The 10 plain labels are peeled from the release paper, and the diameter is 10 mm.
When one of each of the glass tubes was adhered to the side surfaces of ten glass tubes such that the major axis direction of the glass tube and the long side of the label were parallel, all ten sheets could be adhered. Five glass tubes to which the plain label was attached were heated at 500 ° C. and five at 600 ° C. for 1 hour, respectively, and then cooled to room temperature. All of the plain labels heated at 500 ° C had no appearance abnormality such as yellowing, peeling, and cracking, but one of the plain labels heated at 600 ° C peeled partially and the other two Cracks had occurred. Also, 500
When the cellophane tape was applied to the label of the glass tube heated at ℃ and peeled off, no deposit was observed on the cellophane tape, but the label heated at 600 ℃ had a small amount of fine label fragments adhered. . Comparative Examples 2 to 5 In the same manner as in Comparative Example 1, four types of silicone resin liquids for films were prepared according to the composition shown in Table 2. Using these resin liquids, in the same manner as in Comparative Example 1, a label base material constituting a label body was prepared, bonded to a release paper with an adhesive, and cut to prepare a plain label. A flexibility test, a heat resistance test, and a dusting test were performed on these plain labels in the same manner as in Comparative Example 1. Comparative Example 6 A flexibility test, a heat resistance test, and a powdering test were attempted using a commercially available heat-resistant ceramic label [Sigma Max, Ceralabel-Green 450], but all of the 10 labels were glass tubes. The heat resistance test and the dusting test could not be performed. Table 1 shows the composition of the resin liquids of Examples 2 to 6, and Table 2 shows the composition of the resin liquids of Comparative Examples 1 to 5. Evaluation results of the labels of Examples 2 to 6 and Comparative Examples 1 to 6 Are shown in Table 3.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

As is evident from the results in Table 3, all the labels of Examples 2 to 6 of the present invention can be attached to a glass tube having a diameter of 10 mm, and are excellent in flexibility. Further, even when heated at 500 ° C. or 600 ° C. for 1 hour, the appearance is excellent and the heat resistance is excellent. Further, the powdering phenomenon after the heat resistance test hardly occurs. On the other hand, the label of Comparative Example 1 using a resin liquid containing no cured silicone resin powder as the resin component of the film constituting the label body can withstand up to 500 ° C., but has abnormal appearance at 600 ° C. And a slight dusting occurs. The label of Comparative Example 2 using aluminum oxide, which is an inorganic powder, instead of the cured silicone resin powder, does not cause abnormal appearance even at 600 ° C.
A slight dusting occurs at 500 ° C, and a large amount of powder adheres when heated to 600 ° C. Further, the label of Comparative Example 3 using glass fiber which is an amorphous inorganic fiber instead of the monocrystalline inorganic fiber, and the label of Comparative Example 4 using titanium oxide which is an inorganic powder have heat resistance. Insufficient, and the dusting phenomenon is also intense. Furthermore, the label of Comparative Example 5 using a resin solution containing no cured silicone resin powder and containing polymetallocarbosilane and aluminum oxide as an inorganic powder did not cause abnormal appearance even at 600 ° C. At ℃, slight dusting already occurred, 6
When heated to 00 ° C., a large amount of powder adheres. Commercially available heat-resistant ceramic label [Sigma Co., Ltd., Cera Label-
In Comparative Example 6 using Green 450], all ten labels could not be attached to a glass tube having a diameter of 10 mm, and it can be seen that this label fundamentally lacks flexibility.

[0021]

The label of the present invention has excellent flexibility and can be attached to a surface having a small radius of curvature.
Even when heated to a high temperature of 0 ° C. for 1 hour, it has excellent heat resistance without causing any abnormal appearance or dusting.

Claims (2)

[Claims] 1. A composition comprising (A) a cured silicone resin powder, (B) an uncured silicone resin and (C) a monocrystalline inorganic fiber, and the total of the components (A), (B) and (C) Component (A) is 5 to 50% by weight, component (B) is 15 to 9
A label characterized by comprising a heat-resistant adhesive adhered to a label base material containing 0% by weight and 5 to 80% by weight of the component (C). 2. The label according to claim 1, wherein the heat-resistant adhesive is a silicone-based adhesive containing metal powder.