JP2002268554A - Printing sheet for baking and baking sheet thereof - Google Patents

Abstract

(57) [Summary] [Problem] An aluminum product which can be easily attached to an adherend made of a flexible material such as a rolled foil by giving information on the spot at the site or the like, for example, at 530 ° C. for 10 hours or more. Development of printing sheets for printing that can withstand the annealing conditions. A thermal transfer ink comprising an ink containing a metal oxide type colorant and an organic binder on a printing sheet (1) obtained by keeping at least a mixture using an inorganic powder and a silicon-containing binder in a sheet form. it to impart information (3), said silicon-containing binder trimethylsiloxy silicic acid or the general formula: R ₃ SiO- (wherein R is a compound group.) and monofunctional M units represented by , Si
(O-) tetrafunctional stoving printed sheet and baked for printing sheet comprising a polymer of Q units represented by ₄ by firing aluminum products (4) to the adhesive to 200 ° C. over a temperature A baked sheet that is baked.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing sheet for printing which is capable of forming a fired sheet having excellent reflectance and is suitable for forming a management label or the like of an aluminum product.

[0002]

2. Description of the Related Art Heretofore, as a management label in a manufacturing process of an aluminum product, a label obtained by applying a heat-resistant paint to a metal plate or performing laser etching has been known. However, in the case of labels mainly made of metal plates, it is necessary to take measures such as riveting when attaching to products such as aluminum slabs. There were difficult problems.

[0003]

According to the present invention, it is possible to easily attach to an adherend made of a flexible material such as a rolled foil by giving information on the occasion at the site or the like. The objective is to develop a printing sheet for printing that can withstand the annealing conditions of aluminum products.

[0004]

According to the present invention, there is provided a printing sheet obtained by preserving at least a mixture using an inorganic powder and a silicon-containing binder in a sheet form, wherein the silicon-containing binder is trimethyl. Shirokishikei acid or the general formula: R ₃ SiO- (. wherein R is a compound group) and monofunctional M units represented by, Si (O
-) with comprising a polymer of tetrafunctional Q units represented by _4, baking said thermal transfer ink information is characterized by comprising the ink to metal oxide coloring agent and an organic binder component The present invention provides a printed sheet for printing and a baked sheet obtained by bonding the printed sheet for printing to an aluminum product and firing it at a temperature of 200 ° C. or more.

[0005]

According to the present invention, various and flexible printing sheets for printing can be formed on the spot or the like by applying ink information by the thermal transfer method, and the printing sheets can be formed on the curved surface of the adherend. Also, it can be baked as a fired sheet in which the applied information is well preserved under heat treatment by being closely adhered, and the workability in mounting is excellent. In addition, the formed fired sheet, the silica generated by changing the silicon-containing binder by firing is sintered and strongly binds and holds the inorganic powder, and is excellent in chemical resistance, heat resistance, weather resistance, reflectance, etc. For example, it can be used as a management label or the like that withstands various annealing conditions in the manufacturing process of aluminum products.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A printing sheet for printing according to the present invention is
At least a printing sheet obtained by preserving a mixture using an inorganic powder and a silicon-containing binder in a sheet form is provided with thermal transfer ink information, and the silicon-containing binder is trimethylsiloxysilicic acid or a general formula: R ₃ SiO. −
(Where R is a compound group) and a monofunctional M unit represented by Si (O-) _{4 and} a tetrafunctional Q unit represented by Si (O-) ₄ .
The thermal transfer ink information is composed of an ink containing a metal oxide type colorant and an organic binder as components. An example is shown in FIG. 1
Denotes a printing sheet, and 3 denotes thermal transfer ink information. Also 2
Is an adhesive layer provided as required, and 4 is an adherend. In the illustrated example, the printing sheet for printing is temporarily attached to the adherend 4 via the adhesive layer 2. However, in the case of forming a fired sheet by firing, the organic components such as the adhesive layer disappear and the printing is performed. The fired body of the printing sheet for printing is in a state of being baked on the adherend.

The printing sheet only needs to have the shape-retaining layer in the form of a sheet, and can be formed in an appropriate form. As an example, a form comprising the shape retaining layer itself (FIG. 1), and as shown in FIG.
And a form having an adhesive layer. The reinforcing form includes a method of providing a shape-retaining layer on a reinforcing substrate as shown in FIG. 2, a method of impregnating the reinforcing substrate with a material for forming a shape-retaining layer, a method of interposing a reinforcing substrate in the shape-retaining layer, and the like. It may be formed by an appropriate method. As the reinforcing base material, an appropriate one such as a resin coating layer or a film, a perforated base material such as a fiber cloth or a nonwoven fabric, or the like can be used.

The reinforcing substrate may be formed of a material which disappears during heat treatment such as a polymer made of polyester, polyimide, fluororesin or polyamide, or does not disappear by heat treatment such as glass, ceramic or metal. It may be formed of a material. A preferred reinforcing substrate is a low-decomposition type polymer such as ethyl cellulose which is excellent in tensile strength and comprises a coating layer or a film. The thickness of the reinforcing base material can be determined as appropriate.
-100 μm, preferably 3-50 μm, particularly preferably 5-25 μm.

The inorganic powder used for forming the shape-retaining layer is used for improving heat resistance (usually about 600 ° C. or less, preferably about 800 ° C. or less) and for forming the ground color of the fired sheet.
Therefore, any suitable inorganic powder such as metal powder or ceramic powder can be used. The particle size of the inorganic powder is 50 μm or less,
In particular, the thickness is generally 0.05 to 20 μm, but is not limited thereto. Adhering the inorganic powder to a flake base such as mica and blending it as a flake-like powder is effective for improving the reflectance or hiding power (hiding the ground color of the adherend).

[0010] Examples of commonly used inorganic powders include:
White substances such as silica, titania, alumina, zinc white, zirconia, calcium oxide, mica, potassium titanate, and aluminum borate are exemplified. Further, metal compounds such as carbonates, nitrates and sulfates which are oxidized at a firing temperature or lower to become such oxidized white ceramics may also be mentioned. Needless to say, needle-like crystals such as potassium titanate and aluminum borate can be preferably used in terms of whiteness, sintering strength and the like.

Red substances such as manganese oxide / alumina, chromium oxide / tin oxide, iron oxide, cadmium sulfide / selenium sulfide, blue substances such as cobalt oxide, zirconia / vanadium oxide, chromium oxide / divanadium pentoxide, and chromium oxide・ Cobalt oxide ・ Iron oxide ・ Manganese oxide and chromate,
Black substances such as permanganate, yellow substances such as zirconium / silicon / praseodymium, vanadium / tin, chromium / titanium / antimony, green substances such as chromium oxide, cobalt / chromium, alumina / chromium, aluminum / manganese / iron /
Pink colored substances such as silicon and zirconium are also examples of inorganic powders.

As the silicon-containing binder, trimethylsiloxysilicic acid or a monofunctional M unit represented by the general formula: R ₃ SiO— and a tetrafunctional Q unit represented by Si (O—) ₄ For example, an appropriate resin known as a tackifier of a silicone-based pressure-sensitive adhesive, which is composed of a polymer (MQ resin) having the above formula, may be used. In the general formula, for example, R is an aliphatic hydrocarbon group such as a methyl group, an ethyl group or a propyl group, an aromatic hydrocarbon group such as a phenyl group, an organic group such as an olefin group such as a vinyl group, or a vinyloxy group. It may be a compound group having an appropriate structural unit such as a hydrolyzable group. The silicon-containing binder that can be preferably used has excellent shape retention.

For forming a printing sheet, for example, one or more of inorganic powder and silicon-containing binder are mixed by a ball mill or the like using an organic solvent or the like as necessary, and the mixed solution is required by an appropriate method. Depending on the method, it can be carried out by a method of spreading on a supporting material such as a reinforcing base material or a separator and drying. In this case, the ratio of the inorganic powder and the silicon-containing binder used can be appropriately determined according to the handleability and strength of the printing sheet, the strength of the fired sheet, the hiding power, and the like. From the viewpoint of compatibility between the degree of coloring such as white color after sintering and the strength, 1 to 1000 parts by weight, preferably 20 to 200 parts by weight, particularly 40 to 120 parts by weight of inorganic powder is used per 100 parts by weight of the silicon-containing binder. Is preferred.

As the above-mentioned necessary organic solvent, an appropriate one can be used. Generally, toluene, xylene, butyl carbitol, ethyl acetate, butyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone and the like are used. The mixed liquid is not particularly limited, but is preferably prepared so that the solid content concentration is 5 to 85% by weight from the viewpoint of expandability and the like. At the time of its preparation, an appropriate additive such as a dispersant, a plasticizer, a combustion aid and the like can be blended as needed.

The method of developing the mixed liquid is optional, but a method excellent in layer thickness controllability such as a doctor blade method or a gravure roll coater method is preferable. It is preferable to perform a sufficient defoaming treatment by using an antifoaming agent together so that no air bubbles remain in the spread layer. The thickness of the printing sheet or the shape-retaining layer to be formed can be determined as appropriate, but is generally 5 μm to 5 mm, preferably 1 μm to 5 mm.
It is 0 μm to 1 mm, especially 20 to 200 μm.

In the formation of the above-mentioned shape-retaining layer, for example, silicone rubber, a cellulose-based polymer, a hydrocarbon-based polymer, a vinyl-based or Styrene-based polymers, acetal-based polymers and butyral-based polymers, acrylic polymers and polyester-based polymers, urethane-based polymers and cellulose-based polymers, and various kinds of organic compounds such as waxes and waxes can be added as necessary. Such a compounding agent may be used alone or in combination of two or more.

It is particularly preferable to use a silicone rubber in combination for improving flexibility and chemical resistance. Any suitable silicone rubber can be used without any particular limitation. Various modified silicone rubbers such as phenol-modified products, melamine-modified products, epoxy-modified products, polyester-modified products, acryl-modified products and urethane-modified products can also be used. Silicone rubbers that can be preferably used have excellent shape retention and flexibility.

The amount of the silicone rubber used is from 1 to 1000 parts by weight, preferably from 5 to 500 parts by weight, especially from 10 to 100 parts by weight of the silicon-containing binder, from the viewpoint of improving the chemical resistance.
~ 200 parts by weight are preferred. When silicone rubber is used in combination, the use ratio of the inorganic powder described above is based on the total amount of the silicon-containing binder and the silicone rubber, from the viewpoint of handleability and strength of the printing sheet, strength of the fired sheet, hiding power, and the like. preferable.

On the other hand, it is particularly preferable to use a cellulosic polymer such as ethyl cellulose in combination from the viewpoints of the fixing property of the ink by the thermal transfer method, the improvement of the strength of the printing sheet, and the baking property by baking. The amount of the organic compound such as the above-mentioned cellulosic polymer other than the silicone rubber used is
Per 100 parts by weight of a silicon-containing binder, and in the case of a silicone rubber combined use, per 100 parts by weight thereof
1 to 1000 parts by weight, preferably 20 to 200 parts by weight, especially 4
The amount is generally, but not limited to, 0 to 150 parts by weight.

The printing sheet may be formed in a porous form for the purpose of smoothly volatilizing the decomposition gas by heating. Incidentally, when a temporary adhesive layer is provided, for example, the printing sheet for printing may swell due to the decomposition gas generated by the heating, and this can be prevented by using a porous printing sheet. The formation of the porous printing sheet is performed by an appropriate method such as a method of forming a large number of fine holes in the printing sheet by a punching method or the like, a method of using a perforated base material such as a woven fabric or a nonwoven fabric as a reinforcing base material, or the like. be able to.

The printing sheet for printing can be formed by applying thermal transfer ink information 3 to the print sheet 1 as shown in the example of FIG. 1, and in addition to the thermal transfer ink information, engraving information comprising holes or irregularities. It is also possible to combine appropriate information elements such as form information obtained by punching a sheet or a sheet into an appropriate form. The above-described thermal transfer ink information can be provided by using a thermal transfer printer and an ink sheet, whereby arbitrary ink information can be provided on an occasional basis, with high accuracy, and efficiently.

The ink for forming the thermal transfer ink information includes a metal oxide type coloring agent composed of an oxide of an appropriate metal such as iron, nickel, chromium, cobalt, or copper and an organic binder in terms of heat resistance and the like. Is used.
The organic binder exhibits such a colorant holding function, and an appropriate organic binder such as a wax or a resin known in a thermal transfer system can be used. More preferably, a resin binder is used. Further, an ink containing glass frit or the like may be used for the purpose of improving fixing power by heat treatment.
The ink sheet can be obtained, for example, by holding the ink on a supporting substrate made of a film, cloth, or the like.

The thermal transfer ink information to be applied to the printing sheet is arbitrary, and for example, appropriate ink information such as print information, a picture pattern, and a barcode pattern may be applied. When an identification label such as a management label is formed, it is preferable that a good contrast or a difference in color tone is formed between the fired sheet and the ink information after the heat treatment. The step of applying the thermal transfer ink information to the printing sheet may be performed before or after the printing sheet is temporarily attached to the adherend. The method of temporarily attaching to the body is customary.

The printing sheet for baking can be preferably used for the purpose of temporarily attaching it to an adherend, heating it, and baking and fixing the heat-treated body (baked body) of the printing sheet for baking to an adherend under heat treatment. . In some cases, the temporary adhesion can be performed by the adhesive force of the printing sheet itself, but an adhesive layer can be provided as necessary for the purpose of improving the temporary adhesive force and the like. The adhesive layer can be provided at an appropriate stage until the printing sheet is temporarily attached to the adherend and subjected to heat treatment. Therefore, it can be provided before printing information is given to the printing sheet to form the printing sheet for printing, or it can be provided after the printing sheet for printing is provided.

For forming the adhesive layer, an appropriate adhesive substance such as a rubber-based, acrylic-based, silicone-based or vinylalkyl ether-based adhesive can be used. The attachment of the adhesive layer
A method of applying an adhesive substance to a printing sheet or a printing sheet for printing by an appropriate coating method such as a doctor blade method or a gravure roll coater method, or a printing sheet having an adhesive layer provided on a separator according to the above. Alternatively, it can be carried out by an appropriate method such as a method of transferring to a printing sheet for printing.

The pressure-sensitive adhesive layer may be provided in an interspersed state by an appropriate coating method such as a rotary screen method for the purpose of smoothly volatilizing the decomposition gas during the heat treatment. The thickness of the adhesive layer can be determined according to the intended use of the adherend and the like. Generally 1 to 500 μm, especially 3 to 100
μm, especially 5 to 50 μm. It is preferable that the provided adhesive layer is covered with the separator 21 or the like as in the example of FIG. 2 to prevent contamination or the like until the adhesive layer is temporarily attached to the adherend. In order to temporarily attach the printing sheet for printing to the adherend, an automatic bonding method using a robot or the like can be employed in addition to manual work.

The heating treatment of the printing sheet for printing temporarily attached to the adherend can be performed under appropriate heating conditions depending on the heat resistance of the adherend. Generally 1200 ° C or less, especially 20
The heating temperature is 0 to 700 ° C, particularly 350 to 600 ° C. Organic components such as the adhesive layer disappear by heat treatment,
The silicon-containing binder or the like forming the printing sheet is cured while being fused with the information of the thermal transfer ink, is formed into a baked sheet, and is baked and adhered to the adherend.

Accordingly, the printing sheet for printing can be used to paint various articles such as ceramics, glass products, ceramic products, metal products, and enameled products, and to provide identification marks composed of coloring or color-specific information and bar codes. Can be preferably used for various purposes. In particular, it can be preferably used in the annealing step of various aluminum products such as slabs and rolled foils because of exhibiting the above-mentioned thermal characteristics. In this case, the printing sheet for baking is adhered to the aluminum product, and 2 in the manufacturing process.
By baking while using a heat treatment at a temperature of 00 ° C. or more, it can be fixed to the surface of the aluminum product. The adherend may have an arbitrary form such as a flat form or a curved form such as a container.

[0029]

Example 1 100 parts of MQ resin (parts by weight, hereinafter the same), 17 parts of silicone rubber having a weight average molecular weight of about 300,000 (all manufactured by Shin-Etsu Chemical Co., Ltd.), 60 parts of potassium titanate, and 60 parts of ethyl cellulose were used. The dispersion was uniformly mixed with toluene, and the dispersion was applied on a 75 μm-thick polyester film by a doctor blade method and dried to form a 60 μm-thick shape-retaining layer, thereby obtaining a printing sheet.

On the other hand, a toluene solution containing 100 parts of polybutyl acrylate having a weight average molecular weight of about 1,000,000 was applied by a doctor blade method on a 70 μm thick glassine paper separator treated with a silicone-based release agent and dried. Then, an adhesive layer having a thickness of 20 μm was formed, which was adhered to the surface of the shape-retaining layer, and the polyester film was peeled off to obtain a printing sheet with an adhesive layer.

Then, thermal transfer ink information consisting of a bar code is given to the shape retaining layer of the printing sheet using a thermal transfer printer and an ink ribbon holding a resin-based ink containing a metal oxide type black pigment, A printing sheet for printing was obtained.

Example 2 A printing sheet and a printing sheet for printing were obtained in the same manner as in Example 1 except that aluminum borate was used instead of potassium titanate.

Comparative Example 1 A printing sheet and a printing sheet for printing were obtained in the same manner as in Example 1 except that silica powder (Aerosil) was used instead of the MQ resin.

Comparative Example 2 A printing sheet and a printing sheet for printing were obtained in the same manner as in Example 1 except that silicone rubber was used instead of the MQ resin.

Comparative Example 3 A printing sheet for printing was obtained in the same manner as in Example 1 except that an ink ribbon using carbon was used instead of the metal oxide type black pigment.

Evaluation Test The separator was peeled off from the printing sheet for printing obtained in each of the examples and comparative examples, and was temporarily attached to an aluminum slab via the adhesive layer, and annealed at 530 ° C. for 12 hours. A sintering strength was evaluated by a picking test using a cellophane-based adhesive tape, and the reflectance was evaluated by a bar code verifier. Further, the readability of the barcode was evaluated after the picking test. In the examples, the organic components in the ethyl cellulose and the adhesive layer of the printing sheet were burned off by the heat treatment. In the fired sheet, the MQ resin and / or the silicone rubber were changed into silica and remained as a cured product.

The results are shown in the following table. Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 sintered strength unchanged unchanged destruction destruction no change reflectivity (%) 80 50 80 80 80 readability Good Good - - printing annihilation

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a printing sheet for printing.

FIG. 2 is a cross-sectional view of an example of a printing sheet.

[Explanation of symbols]

 1: Printing sheet 11: Shape-retaining layer 12: Reinforcement substrate 2: Adhesive layer 3: Thermal transfer ink information 4: Adherend

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Makoto Kai 1-2-1, Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation F-term (reference) 2H111 AA01 AA11 BA33 BA53 CA03 CA04 CA30 CA31 CA42 4J039 AB12 BA13 BA25 BE01 CA09 EA37 FA02 GA06

Claims (2)

[Claims] 1. A printing sheet obtained by preserving at least a mixture using an inorganic powder and a silicon-containing binder in the form of a sheet, and imparting thermal transfer ink information to the printing sheet, wherein the silicon-containing binder is trimethylsiloxysilicic acid or formula:
It is composed of a polymer of a monofunctional M unit represented by R ₃ SiO— (where R is a compound group) and a tetrafunctional Q unit represented by Si (O—) ₄ . And a printing sheet for printing, wherein the thermal transfer ink information comprises an ink containing a metal oxide type colorant and an organic binder as components. 2. A fired sheet obtained by bonding the printed sheet for printing according to claim 1 to an aluminum product and firing at a temperature of 200 ° C. or higher.