JP2000212304A - Sheet for printing and printed sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sheet for printing capable of extemporaneously applying information, fixing the resultant sheet to an adherend under heat treatment and forming a baked sheet excellent in chemical, heat and weather resistances or hiding power or reflectance, etc., such as a control label effectively utilizable from, e.g. the production of a cathode-ray tube to its salvage while satisfying advantages such as fixability to curved surfaces, extemporaneous formability of various kinds of printed sheets required for the system of diversified small- quantity production in a job site, etc., and simple fixability to the adherend. SOLUTION: This sheet 1 for printing is obtained by retaining the shape of a mixture of at least an inorganic powder, an MQ resin and a melting point lowering agent for silica and, as necessary, at least one of a silicone rubber and a cellulosic polymer in combination into the form of the sheet. The printed sheet is prepared by applying ink information to the sheet 1 for printing by a heat transfer method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a printing sheet excellent in concealing power or reflectance and suitable for forming a management label and the like, and a thermal transfer type printing sheet using the same.

[0002]

2. Description of the Related Art Conventionally, as a printing sheet which can be used as a control label in a cathode ray tube manufacturing process, a glass-based green sheet provided with ink information containing glass powder and baked by firing, a polyorganosiloxane is used. There is known a sheet obtained by adding ink information to a sheet in which an inorganic powder is preserved (Japanese Patent Application Laid-Open No. 7-334).
088, Japanese Patent Application No. 8-228667, Patent No. 265
No. 4735, WO93 / 07844).

[0003] However, it has been found that the management label cannot be used until the recycling step of collecting reworkable parts that can be reused from an adherend such as a cathode ray tube. By the way, in the above-mentioned cathode ray tube, the rework parts are collected through a salvage process of immersing in hot nitric acid to separate the panel and the funnel.In that case, the ink information of the management label given to the cathode ray tube is lost, and the management label is lost. Cannot be used to manage rework parts.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a variety of printing sheets that can be attached to an adherend under heat treatment by adding information to the surface of the printing sheet, which is necessary for a curved surface sticking property and a high-mix low-volume production system. The chemical resistance, heat resistance, weather resistance, and concealing power, such as management labels that can be used effectively from the production of CRTs to their salvage, while satisfying the advantages such as the flexibility of forming and the easy adhesion to the adherend. Another object is to develop a printing sheet capable of forming a fired sheet having excellent reflectance and the like.

[0005]

According to the present invention, at least an inorganic powder and M
A printing sheet, characterized in that a mixture of at least one of a silicone rubber and a cellulosic polymer is formed in a sheet form using Q resin and a silica melting point depressant, if necessary. An object of the present invention is to provide a printing sheet characterized by adding ink information by a thermal transfer method to the sheet.

[0006]

The printing sheet according to the present invention is flexible and can form a wide variety of printing sheets by giving ink information by an appropriate method such as a thermal transfer method, and is suitable for a curved adherend. , And can be easily fixed as a fired sheet in which the applied information is well preserved under heat treatment.
In addition, the formed fired sheet, the silica generated by changing the MQ resin by firing is firmly sintered via a depressant of silica melting point, strongly binds and holds the inorganic powder, and has chemical resistance, heat resistance, It is excellent in weather resistance, hiding power, reflectance and the like, and can be used as a management label and the like that can be effectively used from the manufacture of a CRT to its salvage.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION A printing sheet according to the present invention comprises a mixture of at least one of a silicone rubber and a cellulosic polymer, if necessary, using at least an inorganic powder, an MQ resin and a silica melting point depressant. The printed sheet has a shape-retaining layer formed by preserving the shape, and the printing sheet is obtained by adding ink information by a thermal transfer method to the shape-retaining layer. FIG. 1 shows an example of the print sheet. 1 is a printing sheet and 2 is ink information. Reference numeral 3 denotes an adhesive layer provided as needed, and reference numeral 4 denotes an 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 composed of the shape retaining layer itself (FIG. 1), and as shown in FIG.
2 and a form having an adhesive layer.

In the above-mentioned reinforcing mode, as shown in FIG. 2, a method of providing a shape-retaining layer on a reinforcing substrate, a method of impregnating the reinforcing material with a material for forming a shape-retaining layer, and a method of interposing a reinforcing substrate in the shape-retaining layer It may be formed by an appropriate method such as a method. As a reinforcing base material, a resin coating layer or film, fiber or cloth, non-woven fabric,
An appropriate material such as a metal foil or a net 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.

The inorganic powder used for forming the shape-retaining layer is used to improve heat resistance (generally, about 500 ° C. or less, preferably about 800 ° C. or less) and to form a ground color of a printed sheet.
Therefore, appropriate powder such as metal powder and ceramic powder can be used. The particle size of the inorganic powder is generally 50 μm or less, particularly 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-shaped powder is effective in improving the hiding power or the reflectance.

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 temperature not higher than the temperature at which the printing sheet is subjected to heat treatment to become such an oxidized white ceramic can also be mentioned. Above all, 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 are also examples of the inorganic powder.

Further, 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 / silicon /
Pink colored substances such as zirconium are also examples of the inorganic powder.

As the MQ resin, a general formula: R ₃ S, which is known as a tackifier of a silicone-based pressure-sensitive adhesive or the like, is used.
a monofunctional M unit represented by iO- and Si (O-) ₄
An appropriate polymer consisting of a polymer with a tetrafunctional Q unit represented by In the general formula, R is, for example, 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 vidroxyl group. Having an appropriate structural unit such as a hydrolyzable group such as The MQ resin that can be preferably used has excellent shape retention.

As the silica melting point depressant, an appropriate substance capable of lowering the melting point of silica can be used. Incidentally, examples thereof include alkali metals such as potassium, sodium, and lithium. The alkali metal can be blended in the form of a metal powder or the like, but in the present invention, it is preferable that the alkali metal is dispersed as evenly as possible throughout the entirety. As a result, it can be compounded as a compound which is easily available as fine particles. The form of the alkali metal compound is arbitrary, and may be an appropriate compound such as a hydroxide or a carbonate.

The printing sheet is formed by, for example, one or two of inorganic powder, MQ resin and silica melting point depressant.
The seeds or more are mixed by a ball mill or the like using an organic solvent or the like as necessary, and the mixed solution is spread on a support material such as a reinforcing base material or a separator as necessary and dried by a method such as drying. be able to.

In the above description, the proportion of the inorganic powder and the MQ resin used depends on the handleability of the printing sheet, the strength of the printing sheet, and the like.
It can be appropriately determined according to the strength of the fired sheet, the hiding power, and the like. Generally, 10 to 5 parts per 100 parts by weight of MQ resin
00 parts by weight, preferably 20 to 350 parts by weight, especially 30 to 10 parts by weight
0 parts by weight of inorganic powder is used.

The amount of the silica melting point depressant used can be appropriately determined according to the strength of the obtained fired sheet.
That is, the silica melting point depressant is used when the MQ resin is transformed into fine silica particles by sintering of the organic group such as a methyl group bonded to silicon when the printed sheet is fired at about 400 ° C. or more as described above. In addition, it functions to lower the melting point of the silica to increase the sintering strength.

When a depressant having a melting point of silica is not added, the surface hardness based on the pencil hardness of the sintered sheet is poor due to poor sintering power, the surface is easily broken by mechanical impact force, and ink information is burned out. Although it is about 4H, which is easy, the surface hardness of 9H or more corresponding to a ceramic label can be increased by adding 4000 ppm of KOH to the printing sheet.

Accordingly, the purpose of the silica melting point depressant can be achieved with a trace amount of 0.01 ppm or more of the printing sheet based on the water displacement extraction method. Controlled. The particle size of the silica fine particles formed by the alteration of the MQ resin is also related to the strength of the fired sheet, and the particle size is theoretically predicted to be about 1 nm. % And a sintered sheet that is strongly sintered even at a firing temperature of 500 ° C. or less.

In consideration of the particle size of the silica fine particles and the lowering of the firing temperature, the mixing amount of the silica melting point depressant, which is preferable from the viewpoint of the strength of the obtained fired sheet and the formability of the printing sheet, is set to MQ resin. 0.1 parts per 100 parts by weight
ppm or more, especially 50 to 10,000 ppm, especially 100 to 50 ppm
00 ppm.

As the above-mentioned organic solvent as required, an appropriate one can be used, and generally, toluene, xylene, butyl carbitol, ethyl acetate, butyl cellosolve acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. are used. The mixed solution has a solid content concentration of 5 to 85 from the viewpoint of, for example, but not limited to, developability.
It is preferable to prepare so that it may be% by weight. In the preparation, an appropriate additive such as a dispersant, a plasticizer, and a combustion aid can be added as needed.

The developing method is preferably a method excellent in layer thickness controllability such as a doctor blade method or a gravure roll coater method. 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 is appropriately determined, but is generally 5 μm to 5 mm, preferably 10 μm to 1 mm, and particularly preferably 20 μm to 1 mm.
It is 200 μm.

The printing sheet according to the present invention may be formed in a porous form for the purpose of smoothly volatilizing the decomposition gas by heating. By the way, when a temporary adhesive layer is provided, the printing sheet 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, for example, by
As shown in FIG. 3, a method of forming a large number of fine holes 13 in the printing sheet 1 by a punching method or the like, a method of using a woven or nonwoven fabric, a metal foil or a net having a large number of fine holes as a reinforcing base material, or the like. It can be performed by an appropriate method such as.

The above-mentioned shape-retaining layer is made of, for example, silicone rubber, cellulose polymer, hydrocarbon polymer, vinyl or styrene for the purpose of improving chemical resistance such as flexibility and heat-resistant nitric acid resistance and ink fixing property. If necessary, an organic compound such as a system polymer, an acetal polymer or a butyral polymer, an acrylic polymer or a polyester polymer, a urethane polymer or a cellulose polymer, or various waxes or waxes can be added.

It is particularly preferable to use a silicone rubber in combination to improve flexibility and heat-resistant nitric acid resistance. As the silicone rubber, an appropriate one can be used, and there is no 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, particularly from 10 to 200 parts by weight, per 100 parts by weight of the MQ resin, from the viewpoint of improving the chemical resistance such as heat nitric acid resistance. 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 MQ resin and the silicone rubber, such as the handleability of the printing sheet, the strength of the printing sheet, the strength of the fired sheet, and the hiding power. Preferred from the point of view.

On the other hand, it is particularly preferable to use a cellulosic polymer such as ethyl cellulose in view of improving the fixing property of the ink by the thermal transfer method and improving the strength of the printing sheet. The amount of the above-mentioned organic compound used other than silicone rubber is 5 parts by weight per 100 parts by weight of MQ resin, and when combined with silicone rubber, 100 parts by weight thereof.
It is generally, but not limited to, -200 parts by weight, especially 10-100 parts by weight.

The printing sheet according to the present invention is temporarily attached to an adherend as it is or as a print sheet to which information is added, and heated, and the printing sheet or the heat-treated print sheet is adhered under heat treatment. It can be preferably used for fixing to the body. At the time of the heat treatment, a method may be employed in which an adherend is attached to a printing sheet, and this is heated to adhere the adherend to the adherend via the heat-treated body.

The printing sheet or printing sheet according to the present invention can be temporarily adhered to an adherend by its own adhesive strength, but if necessary, an adhesive layer may be provided for the purpose of improving the temporary adhesive strength. It can also be provided. The adhesive layer can be provided at an appropriate stage until a printing sheet or the like is temporarily attached to an adherend and subjected to heat treatment. Therefore, it can be provided in advance before giving information to the printing sheet and making it into a printing sheet,
It can also be provided after forming a print sheet.

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 is performed by applying an adhesive substance to a printing sheet or a printing sheet by an appropriate coating method such as a doctor blade method or a gravure roll coater method, or an adhesive layer provided on a separator according to the above. Can be carried out by an appropriate method according to a method of forming an adhesive tape or the like, such as a method of transferring the same to a printing sheet or a printing sheet.

The pressure-sensitive adhesive layer may be provided in a dotted state for the purpose of smoothly volatilizing the decomposition gas during the heat treatment. In that case, it is more preferable that the printing sheet has the above-described porous form. FIG. 4 illustrates the printing sheet 1 in which the adhesive layers 31 are provided in a dotted state. The dot-shaped adhesive layer can be formed by a coating method such as a rotary screen method.

The thickness of the adhesive layer to be provided can be determined according to the purpose of use and the like, but is generally 1 to 500 μm, preferably 5 to 20 μm.
0 μm. The provided adhesive layer is preferably covered with a separator or the like until the adhesive layer is temporarily attached to the adherend to prevent contamination and the like. For the temporary attachment of the printing sheet or the printing sheet to the adherend, an automatic bonding method using a robot or the like can be employed.

The printing sheet can be formed by an appropriate method such as a method of providing ink information or engraving information comprising holes or irregularities to the printing sheet, or a method of punching the printing sheet into an appropriate form. It is also possible to form a print sheet composed of a composite of the above-mentioned information elements and a composite sheet of information formed by other various methods.

The ink information can be provided by an appropriate printing method such as a handwriting method, a coating method using a pattern mask, a transfer method of a pattern provided on transfer paper, or a forming method by a printer. In particular, a printing method using a printer, particularly a thermal transfer printer, is more preferable in that arbitrary ink information can be provided on an occasional basis with high accuracy and efficiency.

As the ink, a coloring agent such as a pigment,
An appropriate material using a heat-resistant coloring agent such as an inorganic material can be used, and a glass frit or the like may be contained for the purpose of improving fixing power by heat treatment. An ink sheet such as a print ribbon to be applied to a thermal transfer printer or the like can be obtained, for example, by adding a binder such as wax or a polymer to the ink and holding the ink on a supporting base made of a film or cloth. Therefore, a known ink or its ink sheet can be used by a thermal transfer method or the like.

The ink information to be applied is arbitrary, and appropriate ink information such as, for example, printing information, a picture pattern, and a bar code pattern may be applied. When forming an identification label such as a management label, a good contrast between the printing sheet and the ink information after the heat treatment,
It is preferable that a difference in color tone is formed.

The step of giving the ink information or form to the printing sheet may be before or after the printing sheet is temporarily attached to the adherend. When ink information is formed by a printer, a method of temporarily attaching a print sheet to an adherend as a print sheet to which ink information has been added in advance is generally used.

The heat treatment of the printing sheet or the printing sheet temporarily attached to the adherend can be performed under appropriate heating conditions depending on the heat resistance of the adherend. Generally 1200 ° C
Hereinafter, the heating temperature is set to 200 to 650 ° C, particularly 350 to 550 ° C. By the heat treatment, the organic components such as the adhesive layer disappear, and the MQ resin or the like forming the printing sheet hardens while being fused with the ink information, forms a baked sheet, and adheres to the adherend.

The printing sheet or printing sheet according to the present invention can be applied to various articles such as ceramics, glass products, ceramic products, metal products, enameled products, etc., and can be distinguished from information such as coloring or color-coded information and bar codes. It can be preferably used for various purposes such as marking.

Among other things, since it has excellent chemical resistance, such as being resistant to immersion in hot nitric acid and retaining good ink information, for example, from the production of a cathode ray tube, it is recycled to rework parts. It can be preferably used for forming a management label until it is collected. The adherend may have an arbitrary form such as a flat form or a curved form such as a container.

[0044]

EXAMPLE 1 130 parts (parts by weight, hereinafter the same) of MQ resin, 30 parts of silicone rubber (all manufactured by Shin-Etsu Chemical Co., Ltd.), 0.4 part of potassium hydroxide, 80 parts of potassium titanate, and 60 parts of ethyl cellulose 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 65 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 coated by a doctor blade method on a 70 μm-thick glassine paper separator treated with a silicone release agent and dried. Thus, 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, ink information consisting of a bar code is applied to the shape retaining layer of the printing sheet by using a commercially available ink ribbon holding a wax-based ink containing a metal oxide-based black pigment and bismuth glass and a thermal transfer printer. Then, a printed sheet was obtained.

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

Example 3 The procedure of Example 1 was repeated except that potassium hydroxide was not used.
A printing sheet and a printing sheet were obtained.

Example 4 Example 1 except that the silicone rubber was replaced by MQ resin.
A printing sheet and a printing sheet were obtained in accordance with

Example 5 Example 1 except that the MQ resin was replaced by silicone rubber
A printing sheet and a printing sheet were obtained in accordance with

Evaluation test The separator was peeled off from the printed sheet obtained in the above example, and was temporarily attached to a glass plate via the adhesive layer, and was heat-treated at 470 ° C. for 30 minutes (in air). A glass plate to which a fired sheet having clear information of a bar code was adhered was obtained, and was subjected to the following tests. In addition, the organic components in the ethyl cellulose, the adhesive layer, and the like 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.

Pencil hardness The pencil hardness of the fired sheet surface was examined in accordance with JIS K5400.

Sintering strength The surface of the fired sheet was rubbed with a cotton cloth to check the fixing power of the ink information and the fixing power to the glass plate, and evaluated according to the following criteria. Good: When the ink information maintains the same readability as before the test without the falling off of the fired sheet. Poor: When the fired sheet is missing and the ink information becomes illegible.

Reflectance The reflectance of the fired sheet on a white background was measured at a wavelength of 400 to 80.
The light of 0 nm was examined.

Chemical resistance The fired sheet was placed in a 15% nitric acid solution at 80 ° C. with a glass plate for 2 hours.
After immersion for a minute, the sample was taken out and evaluated by the same method as in the sintering strength test described above.

The above results are shown in the following table. Example 1 Example 2 Example 3 Example 4 Example 5 Pencil hardness 9H or more 9H or more 4H 9H or more 3H Sintering strength Good Good Good Good Bad Reflectivity (%) 80 50 80 80 80 Chemical resistance Good Good Blurring Discoloration Blurring: Pattern blur Sharp Nijimi: Pattern Nijimi

[Brief description of the drawings]

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

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

FIG. 3 is a plan view of another example of a printing sheet.

FIG. 4 is a cross-sectional view of still another example of a printing sheet.

[Description of Signs] 1: Printing sheet 11: Shape-retaining layer 12: Reinforcement base material 13: Fine pores 2: Ink information layer 3: Adhesive layer 31: Adhesive layer distributed in a dot shape 4: Adherend

 ──────────────────────────────────────────────────の Continuing on the front page F term (reference) 4F071 AA09 AA65 AB01 AB06 AB11 AD01 AF30 AH19 BA03 BB02 BC01 4F100 AA00A AA18 AA34 AA36A AB09A AJ04A AJ06 AK01A AK25 AK52A AN02A AR00B BA02 J01JE90H06J01

Claims (5)

[Claims] 1. A printing sheet comprising a mixture of at least inorganic powder, MQ resin, and a silica melting point depressant in a sheet form. 2. The printing sheet according to claim 1, wherein at least one of a silicone rubber and a cellulosic polymer is used in combination. 3. The printing sheet according to claim 1, wherein the inorganic powder is a needle-like crystal, and the depressant having a silica melting point is an alkali metal or a compound thereof. 4. The printing sheet according to claim 1, wherein the sheet has an adhesive layer on one surface. 5. The printing sheet according to claim 1, wherein
A printing sheet provided with ink information by a thermal transfer method.