JP2001115111A - Releasable sheet and pressure-sensitive adheive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a releasable sheet or a pressure-sensitive adhesive tape which are stabilized in the performance such as a desired releasability, coefficient of friction, writing properties, and printability using a heat transfer system. SOLUTION: A release agent composition is a blend of a polydimethylsiloxane with a polymeric resin, and a release sheet is obtained by coating the release agent composition on at least one side of a base material to form a release agent layer having an organic Si content at a depth of 5 nm in the surface layer (measured by electron spectroscopy for chemical analysis (ESCA)), of 5-30 atomic %. The polymeric resin is a cellulose derivative, a thermoplastic resin and/or a thermoplastic elastomer, and the release sheet is heat transfer- printable. A pressure-sensitive adhesive tape is provided with a pressure-sensitive adhesive layer on the opposite side of the release agent layer of the release sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an extremely shallow surface layer of a release agent layer obtained by applying a release agent composition obtained by blending polydimethylsiloxane (hereinafter also simply referred to as silicone) and a polymer resin to at least one surface of a substrate. And a pressure-sensitive adhesive tape characterized in that a pressure-sensitive adhesive layer is provided on the surface of the peelable sheet opposite to the release agent layer, wherein the content of organic Si is in a specific range.

[0002]

2. Description of the Related Art Generally, a release sheet is provided with a release agent layer on at least one side of a substrate in order to protect the surface of an adhesive layer such as a label until use. Further, the pressure-sensitive adhesive tape has a pressure-sensitive adhesive layer provided on one surface of a substrate and a release agent layer provided on the other surface. As the release agent, a long-chain alkyl group-containing compound, a silicone-modified resin-based release agent, a silicone-based release agent, and the like are mainly used. In particular, the silicone-based release agent has excellent release properties with respect to an adhesive. It is most often used at present.

However, the above-mentioned silicone-based release agent has a low critical surface tension on the release agent layer surface, so that it is impossible to write on the release agent layer surface with magic or the like or to perform printing by a thermal transfer method, and further, the coefficient of friction is low. Is small and slippery, so if you put your foot on the peelable sheet that has been left over, it may slip and fall, and in the winding form, finishing loss due to misalignment in the width direction or loss in secondary processing may occur. there were. Also, when used for adhesive tape,
Since the back surface of the tape is slippery, there is a drawback in that when the cardboard is packed and stacked and used, the load easily collapses. Further, since the silicone-based release agent excels in its releasability (too light), when a label having a weak adhesive strength is adhered, the label is easily peeled off from the release sheet before use, or the back surface is not easily adhered with the adhesive tape. Could not be pasted on.

[0004] On the other hand, there is one coated with a long-chain alkyl group-containing compound as a release agent. The release agent layer provided with the long-chain alkyl group-containing compound is characterized in that it has a high coefficient of friction on the release surface, is hard to slip, and can be written with oily magic or the like. However, the long-chain alkyl group-containing compound has a release force that is too heavy when compared with a silicone-based release agent, or has poor heat resistance, and becomes severely released when exposed to a high temperature while being bonded to the adhesive layer. There are problems such as abnormal peeling. Most of the long-chain alkyl group-containing compounds had poor printability by a thermal transfer method. That is, the transferability of the ink to the release agent surface was not always satisfactory, and the adhesion of the ink to the release agent surface was almost nonexistent.

As described above, the silicone-based release agent and the long-chain alkyl group-containing compound have advantages and disadvantages, respectively, and a release sheet having a release agent layer and a pressure-sensitive adhesive tape using the same have been demanded. . In addition, even if an attempt is made to print on the release agent layer surface of a conventional release sheet or adhesive tape by a thermal transfer method, the ink is not transferred well, or even if the ink is transferred, it easily falls off, making it virtually impossible to print. Therefore, a peelable sheet having both peelability and printability and an adhesive tape using the same have been required.

The present inventor has already disclosed in Japanese Patent Application No. 10-56489.
In the above item, by limiting the mass ratio of a specific silicone and an organic resin having a glass transition point in a specific range, or three components of a specific silicone and a cellulose derivative and a reactive organic resin-based release control agent as essential components,
By limiting the mass ratio, a release agent in which the contact angle of the release agent layer surface and the release force of the pressure-sensitive adhesive layer to the release agent layer surface which are further coated with a release agent mainly composed of the above two or three components are limited to a specific range. Propose layers. By providing the release agent layer, there is a writing property, non-slip property,
The adhesive tape which can be laminated was obtained.

However, in order to apply the above-mentioned proposed invention to use as a release sheet, a release agent composition obtained by blending polydimethylsiloxane and a polymer resin is prepared by changing the blending ratio of the two and changing the writability. An attempt was made to adjust the balance between the coefficient of friction, the peeling force, and the like, but the desired performance was not obtained in some cases. For example, even if the blending ratio of the polymer resin is increased to give the writability, the non-slip property, and the appropriate releasability, almost the same quality may be obtained regardless of the blending ratio. Furthermore, even when the same release agent formulation is used, the release agent composition may be applied to a substrate, and the writeability after drying, the coefficient of friction, or the physical properties such as the release force for the same adhesive may change,
In some cases, certain quality could not be obtained.

[0008] The present inventor has disclosed in Japanese Patent Application No. 11-1727.
No. 58, A: mass ratio of polymer having a specific repeating unit to B: organopolysiloxane B / (A +
A thermal transfer recording material provided with a recording layer containing a composition whose main component was adjusted so that B) was 0.005 to 0.3 was proposed. However, since the above-mentioned proposed invention is applied and used as a releasable sheet capable of thermal transfer printing, B
Although an attempt was made to adjust the thermal transfer printability and the releasability by changing the mass ratio represented by / (A + B), the intended performance could not be obtained in some cases. Further, even when the mass ratio represented by B / (A + B) is the same, a certain quality may not be obtained in some cases.

[0009]

Accordingly, the present invention provides
A release agent composition which solves the above-mentioned drawbacks and is obtained by blending polydimethylsiloxane and a polymer resin, wherein the release agent composition is applied to at least one surface of a substrate, and the surface of the release agent layer in the extreme surface layer It is an object of the present invention to obtain a peelable sheet or pressure-sensitive adhesive tape whose properties are controlled and whose performance such as intended peeling force, friction coefficient, writability, and printability by a thermal transfer method is stable.

[0010]

In order to solve the above-mentioned problems, the present invention provides a release agent composition obtained by blending polydimethylsiloxane and a polymer resin, wherein the release agent composition is used as a base material. An ESCA (Electron Spectrosc) of a release agent layer coated on at least one surface
opy for Chemical Analysis
s) A peelable sheet characterized in that the organic Si content at a surface layer depth of 5 nm according to the method is 5 to 30 Atomic%, and an adhesive layer is provided on the surface of the peelable sheet opposite to the release agent layer. It is intended to provide an adhesive tape characterized in that:

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In order to solve the above-mentioned problems, the present inventors have developed a release agent composition in which polydimethylsiloxane and a polymer resin are blended. By limiting the organic Si content in the extreme surface layer of the release agent layer applied to at least one side to a specific range, the surface properties of the release agent layer such as the release force, the friction coefficient, the writing property, and the printability by the thermal transfer method can be easily improved. The present inventors have found that a peelable sheet or a pressure-sensitive adhesive tape having the desired quality can be obtained stably and arbitrarily, and have completed the present invention.

In the present invention, the substrate is not particularly restricted but includes, for example, kraft paper, glassine paper, woodfree paper, coated paper, crepe paper, synthetic paper, impregnated paper, cast paper, polymer film and the like. The stopper layer may or may not be provided, but in the case of a paper base material, a filler material is often used in order to suppress the penetration of the release agent composition.

As the filler layer, a layer containing a pigment and / or an adhesive as a main component is used. Examples of the adhesive include polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, polyacrylate, starches, cellulose derivatives, urethane. Resins, acrylic resins, polyester resins, alkyd resins, melamine resins, styrene-butadiene copolymer latex emulsions, styrene-acrylic copolymer latex emulsions, and acrylate resin-based resins can be used alone or in combination.

Examples of pigments include calcium carbonate, kaolin, aluminum hydroxide, heavy calcium carbonate, light calcium carbonate, titanium oxide, talc, satin white,
Inorganic pigments such as calcium sulfate, barium sulfate, zinc oxide, and silica, and organic pigments such as polypropylene resin, polyethylene resin, styrene resin, acryl-styrene resin, urea formalin resin, melamine-formalin resin, and benzoguanamine resin are used alone or in combination. Can be used.

From the viewpoint of relatively low cost, there is also a method of laminating polyethylene on a substrate (hereinafter also referred to as polylaminate). Although this method is useful for preventing the release agent coating liquid from seeping into the substrate, it is not preferable when the releasable sheet or the adhesive tape is recycled and used.

As a release agent, polydimethylsiloxane is used, and its reaction type includes an addition type and a condensation type.
The reaction type is not particularly limited, but an addition reaction type silicone capable of performing a curing reaction with low energy (low temperature, short time) is preferable. When an addition-reaction type silicone is used, it contains a functional group such as a vinyl group or a hexenyl group, and reacts with the functional group to cure the silicone-based release agent (curing).
A cross-linking agent (SiH).

In general, the cured coating strength changes depending on the crosslinking density of the silicone polymer. For example, a low crosslinking density results in a relatively soft coating, while a high crosslinking density results in a hard coating. The adjustment of the coating film strength can be performed in accordance with the desired product performance.

Further, the polymer resin blended with the above-mentioned polydimethylsiloxane has a performance contradictory to the performance (low critical surface tension, slip property, easy peelability) of the polydimethylsiloxane, and has a writing property, a non-slip property. There is no particular limitation as long as it is capable of imparting properties, for example, cellulose derivatives such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, benzyl cellulose, aminoethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, polymethyl methacrylate , Polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate and other polymethacrylic acid esters or polymethacrylic acid derivatives, polystyrene resin (PS), acryloyl Tolyl / styrene copolymer resin (A
S), an acrylonitrile / butadiene / styrene copolymer resin (ABS), a polyurethane resin, and a polyvinyl acetate resin. In terms of dispersibility with silicone or a silicone solution, curability of a release agent, etc. Cellulose derivatives are more preferred.

On the other hand, in order to obtain a releasable sheet and an adhesive tape on which the release agent layer can be printed by a thermal transfer method, the above-mentioned polymer resin is preferably a thermoplastic resin and / or a thermoplastic elastomer. A long chain alkyl compound obtained by reacting a thermoplastic resin or a thermoplastic elastomer with a polyurethane resin, a polyester resin, a polyamide resin, an ethylene-vinyl acetate copolymer, a vinyl acetate (co) polymer and an alkyl isocyanate,
More preferably, it is made of at least one material selected from polyisobutylene, butyl rubber, brominated butyl rubber, chlorinated butyl rubber, polyisoprene, and polybutadiene.

Further, an organohydrogenpolysiloxane as a crosslinking agent and a catalyst are added to form a coating film of the polydimethylsiloxane. Further, a silane coupling agent for improving the adhesion to the base material, or a resin-based release control agent for controlling the release force to the pressure-sensitive adhesive layer, or an auxiliary agent such as silica may be added.

However, as described in claim 1, the release agent layer of the present invention is mainly composed of a polydimethylsiloxane component and a polymer resin, and the amount of the auxiliary added is based on the total mass of the release agent. On the other hand, it does not exceed 50%. Further, the amount of the resin-based release control agent among the assistants is preferably 35% or less based on the total mass of the release agent. 35%
Exceeding the range is not preferred because the curability of the release agent is reduced, or the release agent is heavily released when treated at a high temperature.

When the addition reaction type silicone is used,
The ratio of the organohydrogenpolysiloxane to the alkenyl group is preferably organohydrogenpolysiloxane / alkenyl group = 1 or more. By the way, if it is less than 1, the curability decreases, which is not preferable.

In general, organic resin-based release control agents include a non-reactive agent having no functional group and a reactive agent having a functional group. The former has a high peeling effect but does not undergo a curing reaction, and therefore has a large amount of transfer to the silicone, and has disadvantages such as a decrease in the residual adhesive force of the pressure-sensitive adhesive and a large speed dependency.

On the other hand, since the latter reacts, the migration of silicone is small and the rate dependence is small. Therefore, the reactive organic resin-based release control agent contains a vinyl group or a hexenyl group as a functional group contributing to the reaction. (C) It is preferable to use one having a unit. CH ₂ = CH (CH ₂ ) _x (CH ₃ ) ₂ SiO _1/2 (c) where x represents an integer of x = 0 or 4.

The catalyst of the addition reaction type silicone is not particularly limited as long as it is a known platinum-based catalyst or a compound into which a platinum-based catalyst is introduced, but chloroplatinic acid, a complex salt of chloroplatinic acid and an olefin, alcohols and the like can be used. And the like. The amount of the catalyst to be added varies depending on the type of the base material and the curing conditions (drying temperature, drying time, drying air flow), but is about 0.5 to 10 parts by mass with respect to 100 parts by mass of the silicone.

By incorporating the polymer resin into the polydimethylsiloxane, the release agent film is formed into a Umimi structure of the polymer resin and silicone, and the polymer resin portion is subjected to heavy peeling, oil-based ink absorption, friction, and the like. It is considered to exhibit the property (increase in the coefficient of friction), and the quality differs depending on the distribution state of both in the surface layer.

When a thermoplastic resin and / or a thermoplastic elastomer is used as the polymer resin, the silicone resin layer mainly exhibits releasability at room temperature, and the thermoplastic resin and / or thermoplastic elastomer layer at the time of heating. It is considered that the portion is softened or melted, and the ink layer of the ink ribbon is transferred and fixed. That is, in order to exhibit thermal transfer printability, the polymer resin is preferably a thermoplastic resin and / or a thermoplastic elastomer, and the use of a thermosetting resin is not preferred because the thermal transfer printability is lost.

The release agent composition comprising a blend of the above-mentioned polydimethylsiloxane and a polymer resin is applied to at least one surface of a substrate to form a release agent layer of ESCA (Electro).
n Spectroscopy for Chemical
When the organic Si content at the surface layer of 5 nm according to the (Al Analysis) method is 5 to 30 Atomic%, an appropriate peeling force such that the writing property, non-slip property, adhesive label, and the like intended by the present invention is not easily peeled off is obtained. Can be In addition, if a thermoplastic resin and / or a thermoplastic elastomer is used as the polymer resin, printing can be performed by a thermal transfer method. The organic Si content can be experimentally obtained by the photoelectron spectroscopy (ESCA) using X-ray excitation, and the total number (total number of atoms) of various types of atoms that can be measured by elemental analysis by the ESCA is 100. Calculate as the ratio of In the present invention, ESCAL
Using AB250 (manufactured by VG, UK), MgK-α (X
Line) used, CAE = 100 eV, STEP = 999.6
33meV, SCANS = 2, TIME = 49.2s,
The value measured when the photoelectron take-up angle (θ) = 30 ° (measurement depth: 5 nm). Percentage of the ratio of the number of organic Si atoms to the total number of organic Si atoms on the layer surface [X = (the number of organic Si atoms at a certain depth of the release agent layer / the total number of atoms at a certain depth of the release agent layer)]
× 100 (%)].

By the way, if it is less than 5 Atomic%, the writing property,
Although non-slip properties can provide excellent performance, the ink layer is excessively transferred during thermal transfer printing, making it difficult to accurately record and determine the intended information, and the peeling force becomes too heavy In addition, the pressure-sensitive adhesive layer is not easily peeled off from the release sheet, is difficult to be rewound with an adhesive tape, and cannot be used because it cannot be rewound. On the other hand, if it exceeds 30 Atomic%, it is not preferable because there are problems such as insufficient writing performance, printability by a thermal transfer method, and non-slip property, or the adhesive layer is easily peeled off from the release sheet. However, when the polymer resin itself has almost no releasability, for example, when a cellulose derivative or the like is used, the organic Si content is 10 Atomic.
% Is preferable.

The relationship between the mass ratio of polydimethylsiloxane to the polymer resin and the content of organic Si in the surface layer of the release agent layer of 5 nm is the same under the same processing conditions (drying temperature, drying time, processing speed, coating amount) and the same processing machine. Then, although there is some reproducibility, if any of the above conditions changes, the organic Si content changes even with the same composition, and the desired writing property, non-slip property, and releasability may not be obtained.

For example, even when the proportion of the polymer resin is high, if the release agent is applied and then slowly put into an oven and dried, the organic Si content in the surface layer 5 nm of the release agent layer can be increased. Even if the ratio of the molecular resin is small, the organic Si content in the surface layer 5 nm of the release agent layer can be reduced by drying immediately after application of the release agent.

That is, when the release agent composition comprising a blend of polydimethylsiloxane and a polymer resin is applied to a substrate, the functional properties (writability, non-slip property, moderate release property) of the release agent layer are determined by The most dominant effect of the mass ratio between dimethylsiloxane and the polymer resin is, as described above, the organic Si at the surface layer of 5 nm.
By adjusting the content of the organic Si in the surface layer of 5 nm, it is possible to obtain surface properties having intended functionality.

With respect to the depth for specifying the organic Si content of the release agent layer, the relationship between the organic Si content in the depth direction and the surface characteristics is determined by considering the influence of the depth of the surface layer by the ESCA analysis. As a result of the investigation, it was found that a correlation was obtained between the organic Si content at a surface layer depth of about 5 nm and the surface characteristics (writability, thermal transfer printability, non-slip property, and peelability). The conclusion to determine the content was reached. That is, in a measurement of a layer shallower than the surface layer 5 nm (less than 5 nm from the outermost layer) or a layer deeper than 5 nm, a correlation between the organic Si content and the surface characteristics cannot be obtained. The reason is that the analysis in a layer shallower than 5 nm in the surface layer has a large error in
It is presumed that this is because a layer deeper than nm has too little distance from the outermost layer and has little influence on the properties of the release agent layer in reality.

The polydimethylsiloxane and the polymer resin are dissolved in a single or mixed organic solvent such as toluene, n-hexane, ethyl acetate, cyclohexane, and n-heptane, or both are emulsified, or both are mixed, or both are mixed. Is diluted with a single or mixed solution of water, IPA, ethanol, methanol, or the like, or applied as it is, and dried. The release sheet or the pressure-sensitive adhesive tape of the present invention can obtain the desired quality by the organic Si content in the extreme surface layer of the release agent layer, and the solid content application amount of the release agent composition is not particularly limited, but is uniform. Taking into account the proper coating surface, the curability of silicone, etc., the amount is preferably 0.05 to 5.0 g / m ² .

The coating method of the release agent is not limited at all, and examples thereof include a gravure direct method, a gravure reverse method, a bar or rod coating, and a three-roll coating. The curing temperature varies depending on the type of silicone to be applied and the structure and performance of the drying device, but is preferably from 70 to 140C.

On the other hand, the pressure-sensitive adhesive used for the pressure-sensitive adhesive tape is not particularly limited. For example, a natural rubber-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive or the like is used as an elastomer component, and a tackifying resin is used. If necessary, additives such as a softening agent, an antioxidant, a crosslinking agent, and a pigment are appropriately added.

In particular, when importance is attached to the adhesive strength, it is more preferable to use an inexpensive natural rubber-based pressure-sensitive adhesive. In order to smooth the rewinding force of the pressure-sensitive adhesive tape or to obtain a product excellent in weather resistance, an acrylic resin is used. It is preferable to use a system-based adhesive.

In the present invention, if the pressure-sensitive adhesive tape has a peeling force of 30 to 200 N / m, there is no substrate breakage (interlayer cracking) when the pressure-sensitive adhesive tape is rewound, so that the adhesive tape can be laminated and pasted. And the adhesive tape which has smooth peeling can be obtained. If it is less than 30 N / m, the laminating property becomes poor, and the tape may rise from the back surface of the adhesive tape with the passage of time. On the other hand, if it exceeds 200 N / m, abnormal peeling may occur at the time of rewinding. May be difficult to rewind, or the substrate may be broken (interlaminar cracking). Here, the peeling force refers to JIS-Z-023.
7 is a value obtained on the basis of FIG.

The amount of the adhesive applied varies depending on the type of the adhesive, but is preferably ²⁰ to 70 g / m ² ,
~60g / m ² is more preferable. When the coating amount is less than 20 g / m ² , the sealing property of the cardboard or the like may be deteriorated, and when it exceeds 70 g / m ² , the anchoring property of the adhesive may be deteriorated and the adhesive may protrude from the tape end surface. Or an adhesive may remain on an adherend such as a cardboard.

The coating method of the pressure-sensitive adhesive is not limited at all, and examples thereof include a comma coating method, a reverse coating method, a gravure coating method, a reverse gravure method, a kiss coating method, a knife coating method, a bar coating method and a process paper. And a transfer method of transferring a material applied by a method.

[0041]

EXAMPLES The present invention will be described in more detail with reference to the following examples, which, of course, are not intended to limit the present invention. In the Examples and Comparative Examples, “parts” and “%” indicate “parts by mass” and “% by mass” of solid components or active ingredients, respectively, unless otherwise specified.

Example 1 50 parts of SBR (L-1571, manufactured by Asahi Kasei), 50 parts of kaolin (manufactured by Engelhard, HT clay) on one side of high quality paper (Oji Paper: 64 g / m ² ) as a base material, A filler layer comprising 0.5 parts of a foaming agent (manufactured by San Nopco, Nopco 1407K) and 0.9 part of a lubricant (manufactured by San Nopco, Nopcoat C104) was provided so that the coating amount was 7 g / m ² , A material subjected to a super calender treatment so as to have a smoothness of 520 seconds was used. As a release agent, 70 parts of an addition reaction type silicone (BY24-400, manufactured by Dow Corning Toray Co., Ltd., solid content concentration: 30%, functional group: vinyl group)
Ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45
~ 55cps 5% in Toluene + Ethanol (80:20) Sol.at2
(5 ° C) was dissolved in toluene as a solvent. A platinum-based curing catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) was added to 100 parts of the blend.
A part of the mixed solution was used as a release agent coating solution, which was coated with a test coater at a processing speed of 10 m / min so as to have a solid content of 0.3 g / m ² on the filling layer surface of the base material and dried ( Release time from the coating head to the oven: about 1.1 seconds, maximum oven temperature of 130 ° C., drying time 25 seconds) and a release layer having a release layer with an organic Si content of 17.3% at a surface layer of 5 nm. A functional sheet was obtained.

Example 2 Using the base material described in Example 1, a release agent coating solution composed of the same blend as in Example 1 was applied to the filling layer surface of the base material by hand coating to obtain a solid content of 0.3 g / m ^2. After 10 seconds, the film was placed in a dryer and dried at 110 ° C. for 40 seconds to obtain a release sheet having a release layer having a surface layer of 5 nm and having an organic Si content of 26.3%. .

Example 3 An addition reaction type silicone (BY24-4) was used as a release agent.
00, Toray Dow Corning Co., Ltd., solid content concentration 30%, functional group: vinyl group) 50 parts ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps 5% in Tolue
ne + Ethanol (80:20) Sol.at 25 ° C.) was added to 50 parts of the blend and dissolved in toluene as a solvent. A mixed solution obtained by adding 2 parts of a platinum-based curing catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) to 100 parts of the blend was used as a release agent coating liquid, and this was used as an actual coater (two coating heads). (Hereinafter, A is closer to the oven and B is farther from the oven) at a processing speed of 160 m / min so that the solid content becomes 0.3 g / m ² on the filling layer surface of the base material described in Example 1. Coating and drying (time from coating head A to entering oven:
About 0.2 seconds, oven maximum temperature 130 ° C, drying time 8
Sec), the organic Si content at the surface layer of 5 nm obtained in 11.3%
A release sheet having a release layer was obtained.

Example 4 An addition reaction type silicone (BY24-4) was used as a release agent.
00, Toray Dow Corning Co., Ltd., solid content concentration 30%, functional group: vinyl group) 50 parts ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps 5% in Tolue
ne + Ethanol (80:20) Sol.at 25 ° C.) was added to 50 parts of the blend and dissolved in toluene as a solvent. A mixed solution obtained by adding 2 parts of a platinum-based curing catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) to 100 parts of the blend was used as a release agent coating liquid.
The solid content was 0.1 m / min on the filling layer surface of the substrate described in Example 1.
Organic Si with a surface layer of 5 nm obtained by coating and drying (time from coating head B to oven: about 5 seconds, maximum oven temperature 100 ° C., drying time 15 seconds) to 3 g / m ^2. A release sheet having a release layer with a content of 18.2% was obtained.

Example 5 100 parts of natural rubber (RSS # 3), 90 parts of a petroleum resin as a tackifier [Quinton S-100, softening point 94
° C, manufactured by Zeon Corporation], 25 parts of a terpene-based liquid softening resin as a softening agent [Dimaron, manufactured by Yashara Chemical Co., Ltd.],
0.8 parts of crosslinking agent [Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.], 1 part of antioxidant [Nocrack NS-
5, manufactured by Ouchi Shinko Chemical Co., Ltd.] in toluene, and coating and drying the solution on the surface opposite to the release agent layer surface of the release sheet described in Example 1 so as to obtain 40 g / m ^2. The tape was wound up to obtain an adhesive tape.

Example 6 Cast paper (manufactured by Oji Paper Co., Ltd .: N mirror, glossy surface smoothness: 3300 seconds) was used as a base material. As a release agent, 10 parts of an emulsion type silicone (X52-195, manufactured by Shin-Etsu Chemical Co., Ltd., solid content concentration 40%, functional group: vinyl group)
A blend was added to which 90 parts of an emulsion type long-chain alkyl compound (K-256, manufactured by Chukyo Yushi Co., Ltd., solid content concentration: 20%) was added, and the mixture was diluted with water and IPA. Further, a curing catalyst (CAT-PM) was added to 100 parts of the mixed solution.
(A-10A, Shin-Etsu Chemical Co., Ltd.) was used as a release agent coating solution, and this was coated with a test coater at a processing speed of 10 m / min. 6g
/ M ² and drying (time from coating head to oven: about 1.1 seconds, maximum oven temperature 1)
(30 ° C., drying time: 25 seconds) to obtain a release sheet having a release layer having an organic Si content of 6.0% at a surface layer of 5 nm.

Example 7 Cast paper (manufactured by Oji Paper Co., Ltd .: N mirror gloss)
(Surface smoothness: 3300 seconds). Thermoplastic elastomer
As polyisobutylene (VISTANEXMML-
100, manufactured by Tonex Corporation)
(SD-7220, manufactured by Toray Dow Corning Inc., solid content
Concentration: 30%, functional group: vinyl group) 20 parts in order.
Dissolve in toluene and further add platinum-based catalyst (SRX-21
2, Toray Dow Corning)
The liquid was used as a release agent coating liquid.
A solid content of 1.0 g is applied to the filling layer surface of the substrate at a working speed of 10 m / min.
/ M ^TwoCoating and drying (orb from coating head
Time to enter: about 1.1 seconds, maximum oven temperature 1
30 ° C., drying time 25 sec)
A release sheet having a release layer having a Si content of 26.6%
Obtained.

Example 8 An acrylic pressure-sensitive adhesive (BPS-5673, manufactured by Toyo Ink Co., Ltd.) was applied as a pressure-sensitive adhesive on the surface of the release sheet described in Example 6 opposite to the release agent layer surface so as to have a concentration of 25 g / m ^2.・ The dried product was wound up to obtain an adhesive tape.

COMPARATIVE EXAMPLE 1 Using the base material described in Example 1, a release agent coating liquid composed of the same blend as in Example 1 was applied to the filling layer surface of the base material by hand coating to obtain a solid content of 0.3 g / m ^2. After 10 seconds, the film was put into a drier and dried at 100 ° C. for 60 seconds to obtain a release sheet having a release layer having an organic Si content of 31.2% at a surface layer of 5 nm and obtained. .

Comparative Example 2 An addition reaction type silicone (BY24-4) was used as a release agent.
00, Toray Dow Corning Co., Ltd., solid content concentration 30%, functional group: vinyl group) 50 parts ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps 5% in Tolue
ne + Ethanol (80:20) Sol.at 25 ° C.) was added to 50 parts of the blend and dissolved in toluene as a solvent. A mixed solution obtained by adding 2 parts of a platinum-based curing catalyst (SRX-212, manufactured by Toray Dow Corning Co., Ltd.) to 100 parts of the blend was used as a release agent coating liquid.
The coating and drying (coating head A) was carried out so that the solid content becomes 0.3 g / m ^{2 at the} filling layer surface of the substrate described in Example 1 at 0 m / min.
From the time of entering the oven: about 0.2 seconds, the maximum temperature of the oven is 150 ° C., and the drying time is 7 seconds.
To obtain a release sheet having a release layer having an organic Si content of 9.2%.

Comparative Example 3 Using the base material described in Example 1, a long-chain alkyl pendant polymer [Piroyl 1010, on the other hand, manufactured by YAS Co., Ltd.] was dissolved in toluene as a release agent. Is applied to the surface of the filling layer so as to have a solid content of 0.1 g / m ² , immediately put into a dryer (time to enter the dryer: about 3 seconds), and dried at 100 ° C. for 30 seconds to obtain a surface layer. 5
A release sheet having a release layer having an organic Si content of 0% in nm was obtained. Then, natural rubber (RSS # 3) 100
Parts, 90 parts of a petroleum-based resin as a tackifier [Quinton S
-100, softening point 94 ° C., manufactured by Zeon Corporation), 25 parts of a terpene liquid softening resin as a softening agent [Dimaron, manufactured by Yashara Chemical Co., Ltd.], 0.8 part of a crosslinking agent [Millionate M]
R-100, manufactured by Nippon Polyurethane Co., Ltd.] and a composition consisting of 1 part of an antioxidant [Nocrack NS-5, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.] are dissolved in toluene, and the above composition is peeled to 40 g / m ^2. The coated and dried product was rolled up on the surface opposite to the release agent layer side of the adhesive sheet to form an adhesive tape.

Comparative Example 4 100 parts of natural rubber (RSS # 3), 90 parts of a petroleum resin as a tackifier [Quinton S-100, softening point 94
° C, manufactured by Zeon Corporation], 25 parts of a terpene-based liquid softening resin as a softening agent [Dimaron, manufactured by Yashara Chemical Co., Ltd.],
0.8 parts of crosslinking agent [Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.], 1 part of antioxidant [Nocrack NS-
5, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.] in toluene, and applying it to the surface opposite to the release agent layer surface of the release sheet described in Comparative Example 1 so as to obtain 40 g / m ² and drying. The tape was wound up to obtain an adhesive tape.

Comparative Example 5 Cast paper (manufactured by Oji Paper Co., Ltd .: N mirror gloss)
(Surface smoothness: 3300 seconds). Thermoplastic elastomer
As polyisobutylene (VISTANEXMML-
100, manufactured by Tonex Corporation)
(SD-7220, manufactured by Toray Dow Corning Inc., solid content
Concentration: 30%, functional group: vinyl group) in order of 40 parts.
Dissolve in toluene and further add platinum-based catalyst (SRX-21
2, Toray Dow Corning)
The liquid was used as a release agent coating liquid.
A solid content of 1.0 g is applied to the filling layer surface of the substrate at a working speed of 10 m / min.
/ M ^TwoCoating and drying (orb from coating head
Time to enter: about 1.1 seconds, maximum oven temperature 1
30 ° C., drying time 25 sec)
A release sheet having a release layer having a Si content of 32.4%
Obtained.

Comparative Example 6 Cast paper (manufactured by Oji Paper Co., Ltd., N mirror glossy surface smoothness: 3300 seconds) was used as a base material. As a thermoplastic elastomer, polyisobutylene (VISTANEXMML-
100 parts, manufactured by Tonex Corporation, 98 parts of silicone (SD-7220, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%, functional group: vinyl group) are dissolved with toluene in order of 2 parts, and then platinum-based Catalyst (SRX-212,
A mixed solution obtained by adding 0.05 parts of Toray Dow Corning Co., Ltd.) was used as a release agent coating solution, and this was applied to the filling layer surface of the base material described in Example 1 at a processing speed of 160 m / min using an actual coater. Surface layer 5 obtained by coating and drying (time from coating head A to enter oven: about 0.2 seconds, oven maximum temperature 130 ° C., drying time 8 seconds) to 0.6 g / m ^2.
A release sheet having a release layer having an organic Si content of 4.3% in nm was obtained.

The peelable sheet and the pressure-sensitive adhesive tape obtained in each of the above Examples and Comparative Examples were evaluated by the following methods, and the results were shown in Tables 1 (peelable sheet) and Table 2 (peelable). Sheet) and Table 3 (adhesive tape). <Curability> The curability of the release agent was evaluated by applying the release agent to a substrate, drying and applying the release agent, and rubbing with the pad of a finger to evaluate the drying conditions under which the curability was good. ◎: good curability at 120 ° C. × 30 seconds (base temperature 85 ° C.) or less ○: good curability at 130 ° C. × 30 seconds (base temperature 90 ° C.) or less △; 140 ° C. × 30 seconds (base temperature 95 ° C) or less and good curability (practical use limit) ×; poor curability even at 140 ° C x 30 seconds (base temperature 95 ° C)

<Residual Adhesion Ratio> An adhesive tape (polyester tape No. 31B manufactured by Nitto Denko Corporation) is adhered to the surface of the release agent layer of the peelable sheet or the adhesive tape, and adhered by a rubber roll, and then a load of 25 g / cm ² is applied. 7 with
After leaving at 0 ° C. for 20 hours, the adhesive tape was peeled off from the release layer surface, left at room temperature for 1 hour or more, then stuck on the polished surface of a stainless steel plate, and peeled at 180 ° at 0.3 m / min. Force (A), an adhesive tape (Nitto 31B) was stuck to the Teflon sheet, and adhered tightly with a rubber roll. After applying a load of 25 g / cm ² at 70 ° C.
After leaving for 0 hour, the adhesive tape was peeled off from the surface of the release layer, left at room temperature for 1 hour or more, adhered to the polished surface of a stainless steel plate, and peeled at 180 m at 0.3 m / min. ) Is measured, and the ratio of (A) to (B) (A
/ B) × 100 was determined as the residual adhesion rate (%).

<Writability> After writing the oil-based magic on the surface coated with the release agent, the time until the magic did not fall off when wiped off with a paper waste was measured and evaluated. A: Magic does not fall when wiped 0 to 10 seconds after writing with magic. ；: Magic does not fall off when wiped 11 to 30 seconds after writing with magic. Δ: Magic does not fall off when wiped 31 to 60 seconds after writing with magic (practical use limit). ×: Magic does not fall off when wiped for 61 seconds or more after writing with magic. Or even if you wipe off more than 61 seconds after writing, the magic drops.

<Thermal transfer printing property>
ATAMAX barcode label printer [Pro
Digi Plus Linerless] and a commercially available ink ribbon as an ink ribbon (product name: FSR-S
A, obtained from Fujikopian Co., Ltd.), a barcode was printed on the release agent layer surface of the release sheet, and (i) ink transferability (ii) ink adhesion was visually evaluated as printability.

<Evaluation Criteria> (i) Transferability: The transferability of the ink during printing is clear. ○ △: The transferability of the ink during printing is almost clear. Δ: The transferability of the ink during printing is slightly unclear (the practical use limit). Δ ×: The transferability of the ink during printing is unclear. ×: no transferability of ink during printing. Or, excessive ink is transferred during printing. (Ii) Adhesion ○: There is almost no peeling of the ink even when a mending tape is applied to the printed surface and peeled off. Δ: There was slight peeling of the ink when the mending tape was applied to the printed surface and peeled off (the practical use limit). ×: When the mending tape was applied to the printed surface and peeled off, the ink was peeled off.

<Peeling Force> A pressure-sensitive adhesive tape (New Delta Tape: manufactured by Oji Chemical Co., Ltd.) was applied with a pressure-sensitive adhesive applied surface to a release-agent applied surface according to JIS-Z-0237.
/ Min 180 ° peel force was measured in a tensile test.

<Coefficient of Dynamic Friction> The coefficient of kinetic friction in the horizontal direction between the release-treated surface of the release sheet or the pressure-sensitive adhesive tape and the same release-treated surface was measured by a friction coefficient test method according to JIS-P-8147.

<Label Peeling> A self-adhesive label (OK Rear Tack: obtained from Oji Tack Sales Co., Ltd.) was affixed to the release agent layer surface of the release sheet by hand compression at a temperature of 22 ° C. and a relative humidity of 65.
%, The number of labels that were naturally peeled off when allowed to stand for 7 days was measured. The number of samples was 20 and the degree of peeling was also observed. ；: No label was peeled off. X: No label was peeled off, but less than 3 labels floated from the peelable sheet (practically poor). XX: There are three or more labels floating or labels peeled off.

<Label Peeling> A self-adhesive label (OK rear tack: obtained from Oji Tack sales) is attached to the release agent layer surface of the peelable sheet by hand pressure bonding, and after leaving it under an environment of a temperature of 22 ° C. and a humidity of 65% for 7 days. The workability when peeling off the label by hand was evaluated. Ten samples were taken, and the peelable sheet and the pressure-sensitive adhesive label were also observed when peeled off. ；: The label can be easily peeled off. Δ: Slightly difficult to peel (practical use limit). X: It is difficult to peel off, and part of the pressure-sensitive adhesive layer has been transferred to the release agent layer. Or, it does not come off.

<Overlapping property> An adhesive tape was attached to an exterior cardboard box (K-7 reinforced corrugated cardboard) specified in JIS-P-3902, and then an adhesive tape was attached on the back of the adhesive tape, followed by overlapping. The time until the peeled adhesive tape was peeled was measured. The number of samples was 20, and the number of pieces peeled every time was evaluated as a measured value. ；: No one sheet was peeled off after 7 days. Δ: Five or less sheets peeled after 7 days (practical use limit). ×: 10 or less peeling after 7 days. XX: All peeled off within 3 hours.

<Rewinding property of pressure-sensitive adhesive tape> The workability in rewinding the produced pressure-sensitive adhesive tape was evaluated. ；: Good workability △: slightly poor workability (no practical problem) ×: poor workability (practical problem)

<Heat resistance of pressure-sensitive adhesive tape> Regarding the heat resistance of the pressure-sensitive adhesive tape, the obtained pressure-sensitive adhesive tape was left in an environment of 80 ° C. for 2 days, and then subjected to a bending angle continuous peeling tester (manufactured by Tester Sangyo).
The presence or absence of substrate destruction was visually observed with respect to the unwinding property when peeling was performed at a peeling speed of 30 m / nin. ；: No breakage of the base material, suitable for practical use △; no breakage of the base material, but a large force for unwinding,
Difficult to rewind (practical use limit) ×: Substrate destruction occurs and is not practically suitable

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

As is clear from Table 1, the peelable sheets as in Examples 1 to 4 have a writing property, a non-slip property, an appropriate peeling property such that the label does not peel off, and when the label is peeled off. Had excellent performance without peeling of the substrate. Further, as apparent from Table 3, Example 6,
The releasable sheet No. 7 had an appropriate releasability and printability by a thermal transfer method in addition to the writing property and the non-slip property. Further, the pressure-sensitive adhesive tape prepared in Example 5 of Table 2 has a writing property,
It had non-slip properties and lamination properties, and was also excellent in heat resistance. Furthermore, the pressure-sensitive adhesive tape produced in Example 8 had both an appropriate rewinding property and printability by a thermal transfer method.

In Comparative Example 1 in Table 1, the writing property and the non-slip property were poor, and the label was peeled off. Further, in Comparative Example 2, the label was difficult to peel off because the peeling force was heavy, and when peeled off, a part of the pressure-sensitive adhesive layer was transferred to the release sheet. In Comparative Example 5 in Table 3, the writing property and the thermal transfer printing property were inferior, and in Comparative Example 6, the ink transfer property in the thermal transfer printing was excessive and information printed accurately could not be recognized. Further, the pressure-sensitive adhesive tape prepared in Comparative Example 3 in Table 2 has writability, non-slip property, and laminating property, but has a high peeling force and poor rewinding property, and the pressure-sensitive adhesive tape may be rewound after heat treatment. could not.
On the other hand, the pressure-sensitive adhesive tape produced in Comparative Example 4 was poor in writability and non-slip properties, and did not have lamination property.

[0073]

According to the present invention, the writability is improved by limiting the organic Si content in the outermost layer of the release agent layer in which a release agent composition obtained by blending polydimethylsiloxane and a polymer resin is provided on a substrate. It is possible to easily control the surface properties such as printability, coefficient of friction, and releasability by the thermal transfer method, and it is possible to provide a stable releasable sheet or adhesive tape according to the target quality. It greatly contributes to

Claims (7)

[Claims] 1. A release agent composition comprising a blend of polydimethylsiloxane and a polymer resin, wherein the release agent composition is applied to at least one surface of a substrate, and the release agent layer has an ESCA.
(Electron Spectroscopy fo
organic Si content at a depth of 5 nm of the surface layer is 5 to 30 At by a Chemical Analysis (r Chemical Analysis) method.
omic%. 2. The peelable sheet according to claim 1, wherein the polymer resin is a cellulose derivative. 3. A pressure-sensitive adhesive tape, wherein a pressure-sensitive adhesive layer is provided on the surface of the release sheet according to claim 1 opposite to the release agent layer. 4. The peelable sheet according to claim 1, wherein the polymer resin is a thermoplastic resin and / or a thermoplastic elastomer, and is heat transfer printable. 5. A long chain obtained by reacting said thermoplastic resin or thermoplastic elastomer with a polyurethane resin, a polyester resin, a polyamide resin, an ethylene-vinyl acetate copolymer, a vinyl acetate (co) polymer and an alkyl isocyanate. At least one selected from an alkyl compound, polyisobutylene, butyl rubber, brominated butyl rubber, chlorinated butyl rubber, polyisoprene, and polybutadiene
The releasable sheet according to claim 5, wherein the releasable sheet is made of a kind of material. 6. A pressure-sensitive adhesive tape, wherein a pressure-sensitive adhesive layer is provided on a surface of the release sheet according to claim 5 opposite to the release agent layer. 7. JI of said pressure-sensitive adhesive layer with respect to said release agent layer
Peeling force based on SZ-0237 is 30 to 200 N / m
The pressure-sensitive adhesive tape according to claim 3, wherein: