JPH11228924A - Adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain good properties concerning laminating, writing with a magic pen and non-slipping by disposing an adhesive agent layer on one side of a tape base material and a releasing agent layer containing an addition reaction type or condensation reaction type silicone and an organic resin mixed in a specific ratio on the other side thereof. SOLUTION: A releasing agent layer contains the components A and B, the weight ratio of A:B being in the range from 30:70-80:20, wherein the component A is an addition reaction type silicone from a compound represented by formula I (R is CH3 or contains 0.4-5 mol.% of a compound represented by formula II; y is 0 or 4; and m+n>=100), an organohydrodiene polysiloxane having not less than 3 hydrogen atoms bonded to silicon in a molecule and a platinum- based catalyst as major components or a condensation reaction type silicone from a compound represented by formula III (at least one of R1 -R4 is an oxyalkylene group; and m+n>=10), an organohydrodiene polysiloxane having not less than 3 hydrogen atoms bonded to silicon in a molecule and an organic acid metal-based catalyst as major components and the component B is an organic resin having a glass transition temperature of 300-450 K (preferably a cellulose derivative).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adhesive tape. More specifically, the present invention relates to an adhesive tape which is excellent in so-called three-functionality, which is excellent in lamination property, magic writing property (printing property), non-slip property, and heat resistance.

[0002]

2. Description of the Related Art In general, a pressure-sensitive adhesive tape is used in which a pressure-sensitive adhesive layer is provided on one surface of a substrate and a long-chain alkyl group-containing compound or a silicone-based release agent layer is provided on the other surface. The pressure-sensitive adhesive tape having a silicone-based release layer has the largest production volume, particularly among packaging tapes, because the tape is lightly developed, has good workability, and is inexpensive.
It is mainly used for sealing cardboard.

However, among the above-mentioned constitutions, the adhesive tape using a silicone-based release agent has drawbacks that it cannot be laminated and pasted, that the back surface of the tape is slippery, so that the load easily collapses, and that characters cannot be written on the back surface of the tape. was there.

In order to solve these drawbacks, there is a method in which a compound having a long-chain alkyl group is applied as a release agent.
The pressure-sensitive adhesive tape using the long-chain alkyl group-containing compound as a release agent has a high friction coefficient on the release surface, is not slippery, can be pasted on the release surface, and can be written with oily magic or the like. However, the long-chain alkyl group-containing compound has poor heat resistance as compared with a silicone-based release agent, causes heavy release at a high temperature and causes a release abnormality.For example, a kraft paper substrate obtained by extruding and laminating a polyolefin-based resin is used. However, there is a problem that interlayer cracking of the substrate occurs. In particular, in the case of a combination with a pressure-sensitive adhesive containing synthetic rubber or natural rubber as a main component, peeling was heavy, and interlayer cracking caused by heavy peeling at a high temperature occurred at a relatively low temperature. In addition, even when a film made of polypropylene, polyethylene, or the like is used as a base material, the film is heavily peeled after heat treatment, and requires a great deal of force to rewind by an operator, or cannot be used as a tape without rewinding. is there.

In Japanese Patent Publication No. 51-20205, a combination of a release agent layer made of a low-density polyethylene resin and a polyacrylate adhesive is further disclosed in Japanese Patent Publication Nos. 57-45789 and 57-45790. In the above, the combination of a release agent layer made of a low-density resin containing an ethylene / propylene copolymer resin and / or an ethylene-1-butene random copolymer as a main component and a polyacrylate-based pressure-sensitive adhesive makes the long-chain alkyl group-containing A kraft pressure-sensitive adhesive tape has been provided which has solved interlayer cracking at a high temperature when a compound is used.

However, the combination of the release agent layer made of the low-density resin and the polyacrylate pressure-sensitive adhesive has poor adhesive strength as compared with the rubber-based pressure-sensitive adhesive.
There are drawbacks such as a little inferior in practical aspects such as cardboard sealing property and lamination property, and high cost.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks, and provides an adhesive tape having a specific release agent layer and an adhesive in combination so as to have an adhesive property, non-slip property,
An object of the present invention is to provide a pressure-sensitive adhesive tape that is stably excellent in writability and the like and that has excellent heat resistance.

[0008]

That is, in order to solve the above-mentioned problems, the present invention provides a tape base material having a release agent layer mainly composed of the following two components of component A and component B on one surface of a tape base material.
In the pressure-sensitive adhesive tape provided with a pressure-sensitive adhesive layer on the other surface of the substrate, the weight ratio of the A component and the B component,
It is intended to provide a pressure-sensitive adhesive tape characterized in that A: B = 30: 70 to 80:20. A component: selected from (1) or (2). (1) Addition-reaction type silicone having the following (i) to (iii) as main components, (i)

Embedded image In the formula, R: CH ₃ or (CH ₂ ) y CH = CH _{2 where} (CH ₂ ) y CH = CH ₂ is 0.4 to 5.0 mol%
And y is an integer of 0 or 4. m + n represents an integer of 100 or more. (Ii) an organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms in one molecule, (iii) a platinum-based curing catalyst, (2) (i
v) a condensation reaction type silicone containing (vi) to (vi) as a main component,
(Iv)

Embedded image In the formula, at least one of R _{1 to} R ₄ is an oxyalkylene group, and m + n represents an integer of 10 or more. (V) an organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms in one molecule, (vi) a metal-organic acid salt-based curing catalyst, and a B component having a glass transition point (Tg) of 300 ° K to 450 °
An organic resin that is K;

Further, in order to solve the above-mentioned problems, the present invention provides a silicone-based release agent layer on one side of a pressure-sensitive adhesive tape substrate, wherein the release agent layer comprises (a) an addition-reaction silicone,
(B) a cellulose derivative, and (c) a reactive organic resin-based release control agent having the following unit (c) as essential components, and component (a) contained in the release agent layer is 20 to
80% by weight, 15 to 45% by weight of the component (b), 2 to 35% by weight of the component (c), and an adhesive layer provided on the other surface of the base material. Provide tape. CH ₂ = CH (CH ₂ ) x (CH ₃ ) ₂ SiO _1/2 (C) where x is an integer of 0 or 4.

[0010] In the above-mentioned structure of the release agent layer, the contact angle (weight ratio of water to ethanol is 1: 1) of the surface of the release agent layer having a melamine clump pack as a substrate and a release agent layer provided on the substrate.
(Measured after 30 seconds with a drop amount of 5 μl) in the range of 55 to 75 °, and the peeling force of the pressure-sensitive adhesive layer to the release agent layer surface in accordance with JIS Z 0237 is 100.
More preferably, it is で 500 gf / 25 mm.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The pressure-sensitive adhesive tape of the present invention has a release agent layer mainly composed of two components of a specific silicone and a specific organic resin on one surface of a base material, or a specific silicone and a cellulose derivative and a specific organic resin. It is characterized in that a release agent layer essentially including a release control agent is provided, and an adhesive is provided on the other surface of the substrate. As the adhesive tape, there are mainly those using paper, cloth, and film, but the base material on which the release agent layer of the present invention is provided is particularly effective when the base material is paper, and thus the base material is paper. The adhesive tape will be described.

In order to solve the above-mentioned problems, the present inventors have already disclosed in Japanese Patent Application No. 9-192481 a method in which a specific amount of a specific cellulose derivative is introduced into a condensation-reacting silicone release agent. In Japanese Unexamined Patent Publication No. 9-223537, by introducing a specific amount of a cellulose derivative into an addition-reaction-type silicone-based release agent, not only excellent heat resistance but also superpositional adhesion, excellent non-slip properties, and excellent writing properties are obtained. As the tape, a kraft adhesive tape was provided.

The kraft pressure-sensitive adhesive tape proposed above can provide a kraft pressure-sensitive adhesive tape excellent in the intended heat resistance and also excellent in the three functions of lamination property, non-slip property, and writing property. However, depending on the type of silicone used and the combination of the cellulose derivative, large variations occur in the heat resistance and / or trifunctionality.

In the present invention, in order to solve these problems, the weight ratio of a specific silicone to an organic resin having a glass transition point in a specific range is limited, or a specific silicone, a cellulose derivative and a reactive organic resin are used. The contact angle of the release agent layer surface coated with a release agent mainly composed of the above two or three components and the pressure-sensitive adhesive layer with respect to the release agent layer surface by limiting the weight ratio to the three components of the system release control agent as essential components. By providing a release agent layer whose release force is limited to a specific range, an adhesive tape having stable quality can be obtained, and the present invention has been completed.

In the present invention, the substrate is not particularly limited, and examples thereof include kraft paper, glassine paper, woodfree paper, coated paper, crepe paper, synthetic paper, impregnated paper, and the like. For example, kraft paper treated with melamine clupak is used because the strength of the base material is relatively high compared to the low cost, and in order to prevent the penetration of the silicone-based release agent coating liquid, the surface on which the silicone-based release agent is formed Preferably, a sealing layer is provided. For example, a relatively inexpensive polyolefin resin extruded and laminated, or a coating liquid composed of a pigment, an adhesive, etc. without using a polyolefin resin to facilitate recycling and reuse, may be used. No.

The filling layer used for the base material is not particularly limited, but when kraft paper is used, for example, a polyethylene resin (hereinafter simply referred to as polylami) is preferable in that a relatively inexpensive and smooth surface can be obtained. The thickness of the poly-laminate layer is preferably 5 to 30 μm, more preferably 10 to 30 μm.
-25 μm is more preferable.

As the release agent, a silicone release agent is used in order to improve the heat resistance of the pressure-sensitive adhesive tape, and its reaction type includes an addition type and a condensation type. The reaction type is not particularly limited, but in recent years, addition reaction type silicones capable of curing at low energy (low temperature, short time) are mainly used. When an addition-reaction silicone is used, the cured coating strength generally 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. .

For example, in the formula (A), (CH ₂ ) yCH =
If the content of CH ₂ is less than 0.4 mol%, the curability is lowered and the rewinding force of the pressure-sensitive adhesive tape is undesirably heavy. On the other hand, when the content exceeds 5.0 mol%, the pot life of the release agent becomes short, which is not preferable. Further, the curability (reactivity) and adhesion of the silicone are changed by changing the type of the functional group. For example, as disclosed in Japanese Patent Publication No. 5-23308, silicone having a hexenyl group introduced therein has higher reactivity than that using a vinyl group and can be cured at a low temperature in a short time. This is useful for reducing damage to the On the other hand, although the adhesiveness is often not yet clarified, generally, if the reactivity is too high, the adhesiveness with the substrate tends to decrease, so that either the vinyl group or the hexenyl group is generally used. It is difficult to mention that it is better to use a functional group.

Further, in order to impart laminating property, non-slip property, and writing property, the silicone-based release agent contains a specific amount of an organic resin having a glass transition point (Tg) of 300 to 450 ° K. An organohydrogenpolysiloxane, which is a crosslinking agent, and a catalyst are added to form a film. Further, a silane coupling agent may be added to improve the adhesion to the base material, or a resin-based release control agent or an auxiliary agent such as silica may be added to control the release force from the adhesive tape.

However, as described in claim 1, the release agent layer of the present invention mainly comprises a silicone component and an organic resin having a specific glass transition point. No more than 50% of the total weight of the agent. Further, the amount of the resin-based release control agent among the assistants is preferably 35% or less based on the total weight of the release agent. If it exceeds 35%, the curability of the release agent is lowered, or the release property is unfavorably increased due to heavy release after heat treatment.

By incorporating an organic resin having a specific glass transition point into the silicone, the coating film of the release agent is formed into a sea urchin structure between the organic resin and the silicone. It is considered to exhibit frictional properties (increase in friction coefficient).

The organic resin is not particularly limited as long as it is dispersible or dissolvable in the silicone or the silicone solution and has a glass transition point in the range of 300 to 450 ° K. Examples thereof include methyl cellulose, ethyl cellulose, and ethyl hydroxyethyl cellulose. , Cellulose derivatives such as benzylcellulose, aminoethylcellulose, carboxymethylcellulose and carboxyethylcellulose; polymethacrylic esters such as polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate and polyisopropyl methacrylate, or polymethacrylic acid derivatives Resin, polystyrene resin (PS), acrylonitrile / styrene copolymer resin (A
S), acrylonitrile / butadiene / styrene copolymer resin (ABS), polyurethane-based resin, polyvinyl acetate-based resin, exhibiting good dispersibility with silicone or silicone solution, curability of release agent, and lamination property. From the viewpoint of making the reaction, a cellulose derivative is more preferable.

The glass transition point can be determined experimentally by DSC (differential scanning calorimeter), and the following Fox equation (1 / Tgm = Σwi / Tgi, Tgm: glass transition point of composite component; wi: weight fraction of each component, Tg
i: glass transition point of each component). If an organic resin having a glass transition point Tg of less than 300 ° K is used, the heat resistance of the release agent is deteriorated, and the tape is subjected to heavy peeling or interlayer cracking of the substrate. on the other hand,
It is not preferable to use an organic resin having a glass transition point of more than 450 ° K, since the dispersibility with silicone or a silicone solution may be deteriorated, or the coating formed by the release agent may become brittle. A more preferred glass transition point is 300 to 400K.

The weight ratio of the component A and the component B is A: B = 3
0:70 to 80:20, preferably A: B = 4
0:60 to 80:20. If the component B is less than 20% of the total weight of the component A and the component B, the release force between the release agent layer and the pressure-sensitive adhesive layer cannot be sufficiently obtained, the lamination property becomes insufficient, and the non-slip property and the writing It is not preferable because the property is poor.

On the other hand, when the component B exceeds 70% of the total weight of the component A and the component B, the viscosity of the release agent solution becomes high and the coating property is deteriorated, or the release force is high and the release is made heavy and the adhesive tape is wound. When the tape is returned, it is difficult to peel off the tape from its own back surface, which may cause lifting of the poly-laminate portion or cracking between layers, which is not preferable.

[0026] The addition reaction type silicone according to claim 2 contains a functional group such as a vinyl group or a hexenyl group, and reacts with the functional group to cure (cure) the silicone-based release agent. (SiH).

The amount of the crosslinking agent is preferably from 1 to 10 based on 1 functional group. If it is less than 1, the curing reaction of the silicone-based release agent does not completely proceed, resulting in poor curing (smear).
On the other hand, if it exceeds 10, the cross-linking agent remains unreacted, and as a result, the peeling property is impaired, and peeling becomes heavy.

The silicone-based release agent contains a specific amount of a cellulose derivative in order to impart laminating property, non-slip property, and writing property. In some cases, the coating property of the agent may deteriorate, and the amount of the agent added is limited. As a result, a reactive organic resin-based release control agent is added in order to compensate for the insufficient lamination property.

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 drawback that the heavy peeling effect is high, but the curing reaction does not occur, so that the amount of transferred silicone is large, the residual adhesive strength of the adhesive is reduced, or the speed dependency is large, and it is difficult to peel off at the speed of rewinding the adhesive tape. .

On the other hand, since the latter reacts, the transfer of silicone is small and the speed dependency is small, so that unnecessary force is not required when rewinding the adhesive tape. The reactive organic resin-based release control agent has the following unit (c) containing a vinyl group or a hexenyl group as a functional group contributing to the reaction. CH ₂ = CH (CH ₂ ) x (CH ₃ ) ₂ SiO _1/2 (C) where x is an integer of 0 or 4.

Further, an organohydrogenpolysiloxane as a crosslinking agent and a catalyst are added to the silicone-based release agent to form a coating film. Further, a silane coupling agent may be added to improve the adhesion to the base material, or an auxiliary agent such as silica may be added to control the peeling force from the adhesive tape.

When a specific cellulose derivative is contained in the release agent, the release agent coating forms a Umimi structure of the organic resin and silicone, and the cellulose derivative has heavy release and absorbs oily ink and friction. (Increase in friction coefficient).

The cellulose derivative is not particularly limited as long as it can be dispersed or dissolved in the silicone or the silicone solution. For example, methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose,
Benzyl cellulose, aminoethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose and the like, compatibility with silicone, curability of the release agent,
Ethyl cellulose and ethyl hydroxyethyl cellulose are more preferable from the viewpoint of exhibiting the laminating property.

The organic resin-based release control agent has good heat resistance similarly to silicone. However, the organic resin-based release control agent partially covers the methyl group on the surface where the silicone exhibits release properties, or partially removes the methyl group. It is said that self-crosslinking increases the crosslink density, thereby reducing (losing) the inherent releasability of the silicone and causing heavy release. The curability and adhesion of the silicone and the coating properties of the release agent The amount of the cellulose derivative to be added is limited to maintain the same, and is used to compensate for the insufficient lamination property.

Further, the contact angle of each release agent layer surface (using a solution in which the weight ratio of water and ethanol is 1: 1 and using a dropping amount of 5 μm)
1 measured after 30 seconds) can be used as a measure of the wetting of the release agent layer surface in the present invention. By setting the contact angle to 55 to 75 degrees, the release agent layer and the pressure-sensitive adhesive layer Pressure-sensitive adhesive tape having good peeling force (overlapping property), a coefficient of friction of the release agent layer (non-slip property), good writability, workability during rewinding, and excellent heat resistance.

That is, the trifunctionality, unwinding property and heat resistance of the produced adhesive tape are maintained in a well-balanced manner by setting the contact angle to 55 to 75 degrees. It can be freely controlled by changing the type of each component of the invention, the mixing ratio of each component, and the like. In the release agent layer of the first aspect, for example, in order to obtain an adhesive tape with smooth rewinding (light release), the ratio A / B should be close to 80/20 and the contact angle should be close to 75 degrees. In order to obtain an adhesive tape emphasizing the laminating property and the writing property, the ratio A / B may be adjusted to a ratio close to 30/70 and the contact angle may be adjusted to close to 55 degrees.

Furthermore, the component (a) contained in the release agent layer of claim 2 is 20 to 80% by weight, and the component (b) is 15 to 4%.
It is necessary that the content be 5% by weight and the component (c) be 2 to 35% by weight. (A) If the addition type silicone is less than 20% by weight, any of the above-mentioned phenomena, such as heavy release of peeling force, deterioration of heat resistance, reduction of curability, or reduction of residual adhesive rate, occurs. Not preferred. on the other hand,
If the content exceeds 80% by weight, any of the three functionalities of laminating property, writing property and non-slip property is not sufficiently exhibited, which is not preferable. The relationship between each component and the contact angle is such that the contact angle increases as the component (a) or (c) having a low surface tension (hard to wet) increases. However, the effect is generally higher for the component (a) having a higher molecular weight. On the other hand, as the component (b) having a high surface tension (easily wettable) increases, the contact angle decreases. From such a relationship between each component and the contact angle, the contact angle can be controlled by changing the weight% occupied by each component.

If the contact angle is less than 55 degrees, the wettability of the release agent layer becomes too high (easy to get wet), so that the adhesive may adhere to the release agent layer surface more than necessary. The effect is particularly remarkable when the pressure-sensitive adhesive tape is heat-treated, and it is not preferable because the pressure-sensitive adhesive tape becomes heavily peeled (heat resistance is deteriorated), and the tape becomes difficult to be rewound or cannot be rewound.

On the other hand, if it exceeds 75 degrees, the wettability of the release agent layer becomes too low (it becomes difficult to wet), so that the pressure-sensitive adhesive does not easily adhere to the release agent layer and the lamination property becomes insufficient. Further, for the same reason, the oil absorbing property on the surface of the release agent layer is poor, and the writing property is poor.

When the content of the organic resin (b) in the release agent layer is less than 15% by weight, non-slip properties and writing properties are poor. It is not preferable because the workability is deteriorated, the peeling force becomes heavy peeling, the tape is hardly peeled off from its own back surface when the adhesive tape is rewound, and a polylaminate portion may float or an interlayer crack may occur.

Further, (c) if the amount of the organic resin-based release control agent is less than 2% by weight, the lamination property is insufficient even when the amount of the organic resin is relatively large (close to 45% by weight). On the other hand, if it exceeds 35% by weight, the curability of the release agent is lowered, and the residual adhesive strength is lowered, which is not preferable. Specific examples of the reactive organic resin-based release control agent that satisfies this condition include: SD- manufactured by Dow Corning Toray Co., Ltd.
7292.

The crosslinking agent is not particularly limited as long as it is at least three organohydrogenpolysiloxanes in one molecule. For example, trimethylsiloxy group end-blocking methylhydrogenpolysiloxane, cyclic methylhydrogenpolysiloxane And dimethylhydrogensiloxy group terminal-blocked dimethylsiloxane / methylhydrogensiloxane copolymer.

On the other hand, the catalyst for the addition reaction is not particularly limited as long as it is a known platinum-based catalyst or a compound into which a platinum-based catalyst has been 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 varies depending on the type of the base material and the curing conditions (drying temperature, drying time, drying air volume). When the polyethylene laminate layer is used as the filling layer, the amount of the catalyst is 100% by weight of the silicone-based release agent. Parts to 0.5 to 10 parts by weight.

The condensation reaction type catalyst is not particularly limited as long as it is a known organic acid metal salt, and examples thereof include dibutyltin diacetate, dibutyltin diurarate, zinc naphthoate and iron octoate. The amount of the catalyst added depends on the type of the base material, the curing conditions (drying temperature, drying time,
Although it depends on the amount of drying air, the amount of addition when the polyethylene laminate layer is used as the filling layer is 1 to 10 parts by weight based on 100 parts by weight of the silicone-based release agent.

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. Said A
(I) (ii) (iii) or (i)
v) The mixing ratio of the components (v) and (vi) is not particularly limited, but 0.5 to 20 parts by weight of the component (ii) or (v) per 100 parts by weight of the component (i) or (iv). Parts, (iii) or 0.2 to 20 parts by weight of the component (vi). (I) Specific examples of the addition reaction type silicone containing (ii) as a main component include a silicone release agent: BY24-312, manufactured by Toray Dow Corning Co., Ltd., BY
24-400, manufactured by Toray Dow Corning, KS-370
3, manufactured by Shin-Etsu Chemical Co., Ltd., and specific examples of the condensation reaction type silicone containing (iv) and (v) as main components include silicone release agent: BY24-036, manufactured by Toray Dow Corning Co., Ltd. You.

The silicone release agent is, for example, toluene
, N-hexane, ethyl acetate, cyclohexane, n-
Dissolve in single or mixed organic solvent such as heptane and apply
Dried. The coating amount of the release agent is 0.05 to 2.0 g / m
^TwoIs preferred, and 0.1 to 1.5 g / m^TwoIs more preferred.
0.05g / m^TwoLess than, uniform peelability as tape
No performance can be obtained, resulting in heavy peeling and partial interlayer cracking
2.0 g / m2 ^TwoExceeding the hardness of silicone
It is not preferable because the conversion property becomes worse.

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 coating, and a three-roll coating. The curing temperature varies depending on the type of silicone applied and the drying device, but is preferably 70 to 140 ° C.

The pressure-sensitive adhesive 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, a tackifying resin, and if necessary, a softening agent. Additives such as an agent, an antioxidant, a crosslinking agent and a pigment.

It is more preferable to use an inexpensive natural rubber-based pressure-sensitive adhesive which has a high adhesive strength especially when the lamination property is emphasized. It is preferable to use an acrylic pressure-sensitive adhesive having a relatively lower adhesive strength than the pressure-sensitive adhesive.

In the present invention, in order to obtain a pressure-sensitive adhesive tape having a desired laminating property, free of floating of the poly-tape or interlayer cracking when rewinding the pressure-sensitive adhesive tape, and having a smooth peeling, the pressure-sensitive adhesive tape and the silicone-based adhesive tape are used. If the peeling force with the release agent-applied surface is 100 to 500 gf / 25 mm, the intended lamination can be performed, and an adhesive tape free of poly-floating or interlayer cracking when rewinding the adhesive tape can be obtained. If it is less than 100 gf / 25 mm, the adhesive strength to the back surface is weak, the lamination property is poor, and the tape may rise from the back surface over time, while the other 5
If it exceeds 00 gf / 25 mm, peeling abnormalities may occur at the time of rewinding, making it difficult to peel off the tape from its own back surface, causing the polylaminate to float or causing interlayer cracking. Here, the peeling force is JIS Z
This is a value obtained based on 0237.

When the cardboard boxes to which the adhesive tape has been applied are stacked and carried, in order to prevent collapse of the load, the desired non-slip property is attained if the dynamic friction coefficient between the surfaces of the silicone release agent layers is 0.20 or more. An applied adhesive tape can be obtained. If it is less than 0.20, the surfaces of the silicone-based release agent layers are liable to slip with each other and the collapse of the load is apt to occur. Here, the dynamic friction coefficient is J
This is a value obtained based on ISP 8147.

Further, the surface of the silicone-based release agent of the pressure-sensitive adhesive tape of the present invention is characterized in that it has an oil-based magic writing property. This is achieved by forming the release agent layer of the present invention together with the above-mentioned coefficient of kinetic friction.

The amount of the adhesive applied depends 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 method of applying 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.

[0055]

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 weight” and “% by weight” unless otherwise specified.

Example 1 Polyethylene-laminated kraft paper (a laminate obtained by laminating a polyethylene film of 20 μm on 73 g / m ² of melamine curl pack) was used as a base material. Release agent (BY24-312, manufactured by Toray Dow Corning Co., Ltd., solid content concentration 30%, functional group: vinyl group, molecular weight (m + n): 1)
03-106) In 40 parts, B component: Tg is about 316 ° K
Ethyl cellulose (powder reagent, manufactured by Tokyo Chemical Industry Co., Ltd., 4
5-55cps 5% in Toluene + Ethanol (80:20) Sol.a
(A: B = 40: 60)
Was 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 mixture was used as a release agent coating liquid, and the solid solution became 0.3 g / m ^2. And dried to obtain a release layer having a contact angle of 63.3 degrees. Natural rubber (RSS #) is used as an adhesive to be applied to the surface opposite to the release agent application surface.
3) 100 parts, 90 parts of a petroleum resin as a tackifier [Quinton S-100, softening point 94 ° C, ZEON CORPORATION
, 25 parts of a terpene-based liquid softening resin as a softening agent [Dimaron, manufactured by Yasuhara Chemical Co., Ltd.], a crosslinking agent 0.8
A composition comprising [Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.] and 1 part of an antioxidant [Nocrack NS-5, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.] was dissolved in toluene, and this was solidified. Coating to 40 g / m ²
The dried product was wound up to obtain an adhesive tape.

Example 2 Component A as release agent: 60 parts of an addition reaction type silicone release agent (BY24-312, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), and component B: Tg of about 316 ° K. Ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45
~ 55cps 5% in Toluene + Ethanol (80:20) Sol.at25
(A: B = 60: 40) to which 40 parts of (C) was added and dissolved in toluene. 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 mixture was used as a release agent coating liquid, and this was used as a solid content of 0.1 part.
Contact angle 6 obtained by coating and drying to 3 g / m ²
An adhesive tape was produced in the same manner as in Example 1 except that an 8.5-degree peeling layer was used.

Example 3 Component A as release agent: 75 parts of addition-reaction type silicone release agent (BY24-312, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%) and component B: Tg of about 316 ° K. Ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45
~ 55cps 5% in Toluene + Ethanol (80:20) Sol.at25
C), a mixture (A: B = 75: 25) to which 25 parts was added,
It was dissolved with 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 mixture was used as a release agent coating liquid, and the solid solution became 0.3 g / m ^2. A pressure-sensitive adhesive tape was produced in the same manner as in Example 1, except that a release layer having a contact angle of 73.0 ° obtained by coating and drying was used.

Example 4 Component A as release agent: Silicone release agent of addition reaction type (KS-3703, manufactured by Shin-Etsu Chemical Co., Ltd., solid content: 30)
%, Functional group: vinyl group, molecular weight (m + n): 103-1
06) 60 parts of ethyl cellulose having a Bg component: Tg of about 316 ° K (powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55)
cps 5% in Toluene + Ethanol (80:20) Sol.at25 ℃)
The mixture to which 40 parts were added (A: B = 60: 40) was dissolved with toluene as a solvent. A mixed solution obtained by adding 2 parts of a platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) to 100 parts of the mixture was used as a release agent coating liquid, and the solid content was adjusted to 0.3 g / m ^2. An adhesive tape was prepared in the same manner as in Example 1 except that a release layer having a contact angle of 72.0 ° obtained by coating and drying was used.

Example 5 Component A as a release agent: Condensation reaction type silicone release agent (BY24-036, manufactured by Toray Dow Corning Co., Ltd., solid content concentration 30%, molecular weight 102 to 105), 60 parts of component B, Tg Is about 316 ° K (powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps 5% in Tolue
A mixture (A: B = 60: 40) to which 40 parts of ne + Ethanol (80:20) Sol.at 25 ° C. was added was dissolved with toluene as a solvent. A tin-based curing catalyst (SR
X-67, manufactured by Dow Corning Toray Co., Ltd.) was used as a release agent coating solution, and the solid solution was 0.3 g / m2.
^A pressure-sensitive adhesive tape was produced in the same manner as in Example 1, except that a release layer having a contact angle of 73.8 ° obtained by coating and drying so as to obtain No. 2 was used.

Example 6 Component A as a release agent: 60 parts of an addition reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), component B: Tg of about 364 ° K Acrylonitrile / styrene copolymer resin (AS)
A mixture (A: B = 75: 2) to which 0 parts and 20 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) is further added.
5) was dissolved in toluene / DMF / MEK as a solvent. A platinum-based catalyst (SRX-2) was used for 100 parts of the mixture.
12, a product of Toray Dow Corning Co., Ltd.) was used as a release agent coating solution, which was coated and dried to a solid content of 0.3 g / m ² to obtain a contact angle of 60.2. A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that a release layer was used.

Example 7 Component A as a release agent: 70 parts of an addition reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), and component B: Tg of about 378 ° K. (A: B = 78: 22) to which 20 parts of a polymethyl methacrylate resin of the formula (1) and 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) are added. ) Was dissolved in toluene / THF / MEK as a solvent. A mixed solution obtained by adding 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) to 100 parts of the mixture was used as a release agent coating liquid so that the solid content became 0.3 g / m ^2. Example 1 except that a release layer having a contact angle of 64.8 ° obtained by coating and drying was used.
An adhesive tape was produced in the same manner as in Example 1.

Example 8 As a pressure-sensitive adhesive, a general-purpose emulsion-type pressure-sensitive adhesive (HVC-62) containing a polyacrylate as a main component was used.
80, manufactured by Toa Gosei Co., Ltd.), and an adhesive tape was produced in the same manner as in Example 1 except that a material coated and dried so as to have a solid content of 40 g / m ² was used.

Example 9 Component A: 60 parts of an addition-reaction type silicone release agent (BY24-312, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%) as a release agent, and Component B: Tg of about 316 ° K. Ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45
~ 55cps 5% in Toluene + Ethanol (80:20) Sol.at25
° C) 30 parts, a release control agent (BY2
4-843, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content concentration: 50%).
7: 33.3) was dissolved in toluene as a solvent. A platinum-based curing catalyst (PL-50) was used with respect to 100 parts of the mixture.
T, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a release agent coating solution, which was coated and dried to a solid content of 0.3 g / m ² to obtain a contact angle of 69.9. A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that a release layer was used.

Example 10 A polyethylene-laminated kraft paper (a laminate obtained by laminating a polyethylene film of 20 μm on 73 g / m ² of melamine pack) was used as a base material. In 60 parts of a silicone release agent (BY24-400, manufactured by Dow Corning Toray Co., Ltd., solid content concentration: 30%), component (b): ethyl cellulose (powder reagent, manufactured by Tokyo Chemical Industry Co., Ltd., 45 to 55 cps)
5% in Toluene + Ethanol (80:20) Sol.at25 ℃） 30
Parts, (c) component: 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Dow Corning Toray Co., Ltd., solid content concentration: 70%), and the mixture was dissolved in toluene as a solvent.

To 100 parts of the mixture, a platinum-based catalyst (S
RX-212, manufactured by Dow Corning Toray Co., Ltd.) was used as a release agent coating liquid, and 0.3 g of a solid content was obtained.
/ M ^2, and dried to obtain a release layer having a contact angle of 58.6 °. 100 parts by weight of natural rubber (RSS # 3) as an adhesive applied to the surface opposite to the release agent-coated surface, and 90 parts by weight of a petroleum-based resin as a tackifier [Quinton S-10]
0, softening point 94 ° C., manufactured by Zeon Corporation], 25 parts by weight of a terpene-based liquid softening resin as a softener [Dimaron, manufactured by Yashara Chemical Co., Ltd.], 0.8 parts by weight of a cross-linking agent [Millionate MR-100, Japan Polyurethane Co., Ltd.]
A composition comprising 1 part by weight of an antioxidant [Nocrack NS-5, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.] is dissolved in toluene,
This was applied and dried so as to have a solid content of 40 g / m ² and wound up to obtain an adhesive tape.

Example 11 Component (a) as a release agent: 75 parts of an addition-reaction type silicone-based release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid content: 30%), and component (b): ethyl cellulose ( Powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps
5% in Toluene + Ethanol (80:20) Sol.at 25 ° C)
Parts, (c) component: 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%), and the mixture was dissolved in toluene. A platinum-based catalyst (SRX-21) was used for 100 parts of the mixture.
2, Toray Dow Corning Co., Ltd.) A mixed solution obtained by adding 2 parts of the mixture was used as a release agent coating solution, which was coated and dried so as to have a solid content of 0.3 g / m ^2, and a contact angle of 62.4 ° was obtained. An adhesive tape was produced in the same manner as in Example 1 except that the release layer was used.

Example 12 Component (a) as a release agent: 50 parts of an addition-reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), and component (b): ethyl cellulose ( Powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps
5% in Toluene + Ethanol (80:20) Sol.at25 ℃） 40
Part, (c) component: A mixture to which 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) was added was dissolved with toluene as a solvent. A mixed solution in which 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) was added to 100 parts of the mixture was used as a release agent coating solution, and this was used as a solid content of 0.1 part.
Contact angle 5 obtained by coating and drying to 3 g / m ²
An adhesive tape was produced in the same manner as in Example 1 except that the release layer was used twice.

Example 13 As a release agent, component (a) was added to 40 parts of an addition-reaction-type silicone release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid content: 30%), and component (b) was ethyl cellulose ( Powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps
5% in Toluene + Ethanol (80:20) Sol.at25 ℃） 30
Part, component (c): A mixture obtained by adding 30 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) was dissolved with toluene as a solvent. A mixed solution in which 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) was added to 100 parts of the mixture was used as a release agent coating solution, and this was used as a solid content of 0.1 part.
Contact angle 5 obtained by coating and drying to 3 g / m ²
An adhesive tape was produced in the same manner as in Example 1 except that a 7.0-degree release layer was used.

Example 14 Component (a) as a release agent: 75 parts of an addition-reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), and component (b): ethyl cellulose ( Powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps
5% in Toluene + Ethanol (80:20) Sol.at25 ℃） 20
Parts, (c) component: A mixture to which 5 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) was added was dissolved with toluene as a solvent. A mixed solution in which 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) was added to 100 parts of the mixture was used as a release agent coating solution, and this was used as a solid content of 0.1 part.
Contact angle 6 obtained by coating and drying to 3 g / m ²
An adhesive tape was produced in the same manner as in Example 1, except that a 0.9-degree release layer was used.

Example 15 Component (a) as a release agent: 70 parts of an addition-reaction type silicone release agent (BY24-312, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), and component (b): ethyl cellulose ( Powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps
5% in Toluene + Ethanol (80:20) Sol.at25 ℃） 20
Part, (c) component: A mixture to which 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) was added was dissolved with toluene as a solvent. A mixed solution in which 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) was added to 100 parts of the mixture was used as a release agent coating solution, and this was used as a solid content of 0.1 part.
Contact angle 7 obtained by coating and drying to 3 g / m ²
An adhesive tape was prepared in the same manner as in Example 1 except that a 2.0-degree release layer was used.

Example 16 Component (a) as a release agent: 60 parts of an addition reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid concentration: 30%), and component (b): ethylhydroxyl Ethyl cellulose (powder reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)
A mixture obtained by adding 30 parts and (c) component: 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) was dissolved in toluene as a solvent. To 100 parts of the mixture, 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray) were added.
The mixed solution added was used as a release agent coating liquid, and this was applied except that a release layer having a contact angle of 59.0 ° obtained by coating and drying this so as to have a solid content of 0.3 g / m ² was used. An adhesive tape was produced in the same manner as in Example 1.

Example 17 As a pressure-sensitive adhesive, a general-purpose emulsion-type pressure-sensitive adhesive (HVC-62) containing a polyacrylate as a main component was used.
80, manufactured by Toa Gosei Co., Ltd.) and coated and dried so as to have a solid content of 40 g / m ² , to prepare an adhesive tape in the same manner as in Example 10.

Comparative 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, and this was coated to a solid content of 0.1 g / m ^2. -An adhesive tape was produced in the same manner as in Example 1 except that a release layer having a contact angle of 55.0 degrees obtained by drying was used.

Comparative Example 2 Component A as a release agent: 20 parts of an addition reaction type silicone release agent (BY24-312, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content concentration: 30%), and component B: Tg of about 3
16 ° K ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps 5% in Toluene + Ethanol (80: 2
0) A mixture to which 80 parts of Sol.at (25 ° C.) was added (A: B = 2)
0:80) was dissolved in toluene as a solvent. A platinum-based curing catalyst (SRX-212,
A mixed solution obtained by adding 2 parts of Toray Dow Corning Co., Ltd.) was used as a release agent coating solution, which was coated and dried to a solid content of 0.3 g / m ² to obtain a contact angle of 57.4 °. An adhesive tape was produced in the same manner as in Example 1 except that a release layer was used.

Comparative Example 3 As a release agent, 90 parts of component A: an addition-reaction-type silicone release agent (BY24-312, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content concentration: 30%), and component B: Tg of about 316 ° K ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps 5% in Toluene + Ethanol (8
0:20) Mixture (A: B = 9) to which 10 parts of Sol.at 25 ° C. was added.
0:10) was dissolved in toluene as a solvent. A platinum-based curing catalyst (SRX-212,
A mixed solution obtained by adding 2 parts of Toray Dow Corning Co., Ltd.) was used as a release agent coating solution, which was coated and dried so as to have a solid content of 0.3 g / m ² and had a contact angle of 76.7 °. An adhesive tape was produced in the same manner as in Example 1 except that a release layer was used.

Comparative Example 4 Component A: 45 parts of addition reaction type silicone release agent (BY24-312, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content concentration: 30%) as a release agent, and Component B: Tg of about 3
16 ° K ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps 5% in Toluene + Ethanol (80: 2
0) A mixture containing 5 parts of Sol.at 25 ° C.) and 50 parts of a release control agent (BY24-843, manufactured by Toray Dow Corning Silicone Co., solid content concentration 50%) as an additive (A:
B = 90: 10) was dissolved in toluene as a solvent.
A platinum-based curing catalyst (SRX-2) was used for 100 parts of the mixture.
12, a product of Toray Dow Corning Co., Ltd.) was used as a release agent coating solution, which was coated and dried so as to have a solid content of 0.3 g / m ^2, and a contact angle of 64.1 was obtained. A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that a release layer was used.

Comparative Example 5 Component A as a release agent: 70 parts of an addition-reaction type silicone release agent (BY24-312, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%) and component B: Tg of about 265 ° K. A mixture (A: B = 78: 22) containing 20 parts of a polypropylene resin and 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Dow Corning Toray Co., Ltd., solid content concentration: 70%) was added to a solvent. As toluene / TH
It was dissolved in a mixed solvent of F / MEK. A mixed solution obtained by adding 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray) to 100 parts of the mixture was used as a release agent coating liquid,
An adhesive tape was produced in the same manner as in Example 1 except that a release layer having a contact angle of 74.8 ° obtained by applying and drying this so as to have a solid content of 0.3 g / m ² was used.

Comparative Example 6 Component A as a release agent: 70 parts of an addition-reaction type silicone release agent (BY24-312, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), and component B: Tg of about 502 ° K. (A: B = 78: 22) obtained by adding 20 parts of a polymethacrylic resin of the formula (1) and 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%). , Toluene / TH as solvent
It was dissolved in a mixed solvent of F / MEK. A mixed solution obtained by adding 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray) to 100 parts of the mixture was used as a release agent coating liquid,
An adhesive tape was prepared in the same manner as in Example 1 except that a release layer having a contact angle of 72.2 ° obtained by applying and drying this to a solid content of 0.3 g / m ² was used.

Comparative Example 7 Component A as release agent: Addition-reaction type silicone release agent (SD-7220, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content concentration 30%, functional group: vinyl group, molecular weight (m
+ N): 10 ³ to 10 ⁶ ) 100 parts were dissolved with toluene as a solvent, and further a platinum-based curing catalyst (SRX-212,
Example 2 except that 2 parts of Toray Dow Corning Co., Ltd.) were added, and this was applied and dried so as to have a solid content of 0.3 g / m ² and had a contact angle of 79.8 °. In the same manner as in Example 1, an adhesive tape was produced.

Comparative Example 8 Component (a) as a release agent: 20 parts of an addition-reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content: 30%), and component (b): ethyl cellulose (Powder reagent, Tokyo Chemical Industry Co., Ltd., 45-
55cps 5% inToluene + Ethanol (80:20) Sol.at25
C), and the mixture to which 80 parts were added was dissolved with toluene as a solvent. A platinum-based catalyst (SRX
-212, manufactured by Toray Dow Corning Co., Ltd.) was used as a release agent coating liquid, and the solid content was 0.3 g / m 2.
^A pressure-sensitive adhesive tape was produced in the same manner as in Example 1, except that a release layer having a contact angle of 52.7 ° obtained by coating and drying to obtain a coating film of No. 2 was used.

Comparative Example 9 As a release agent, component (a): 90 parts of an addition-reaction type silicone release agent (BY24-162, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content concentration: 30%);
Ethyl cellulose (powder reagent, Tokyo Chemical Industry Co., Ltd., 45
~ 55cps 5% in Toluene + Ethanol (80:20) Sol.at25
C.) The mixture to which 10 parts were added was dissolved with toluene as a solvent. A platinum-based catalyst (SRX
-212, manufactured by Toray Dow Corning Co., Ltd.) was used as a release agent coating liquid, and the solid content was 0.3 g / m 2.
^A pressure-sensitive adhesive tape was prepared in the same manner as in Example 1, except that a release layer having a contact angle of 72.9 ° obtained by coating and drying to obtain a coating film of No. 2 was used.

Comparative Example 10 Component (a) as a release agent: 80 parts of an addition reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Silicone Co., Ltd., solid content: 30%), component (c): reaction Organic Resin Release Control Agent (SD-729)
2, Toray Dow Corning, solid content concentration 70%) 20
The mixture to which the parts were added was dissolved with toluene as a solvent.
A platinum-based catalyst (SRX-21) was used for 100 parts of the mixture.
2, a product of Toray Dow Corning Co., Ltd.) was used as a release agent coating solution, which was coated and dried to a solid content of 0.3 g / m ² to obtain a contact angle of 76.9. A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that a release layer was used.

Comparative Example 11 As a release agent, component (a): 85 parts of an addition-reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), and component (b): ethyl cellulose ( Powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps
5% in Toluene + Ethanol (80:20) Sol.at25 ℃） 5 parts,
(C) Component: A mixture to which 10 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) was added, and the mixture was dissolved in toluene as a solvent. A mixed solution in which 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) was added to 100 parts of the mixture was used as a release agent coating solution, and this was used as a solid content of 0.1 part.
Contact angle 7 obtained by coating and drying to 3 g / m ²
An adhesive tape was produced in the same manner as in Example 1 except that the release layer was used twice.

Comparative Example 12 Component (a) as a release agent: 50 parts of an addition-reaction type silicone release agent (BY24-400, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 30%), and component (b): ethyl cellulose ( Powder reagent, Tokyo Chemical Industry Co., Ltd., 45-55 cps
5% in Toluene + Ethanol (80:20) Sol.at25 ℃） 5 parts,
Component (c): A mixture to which 45 parts of a reactive organic resin-based release control agent (SD-7292, manufactured by Toray Dow Corning Co., Ltd., solid content concentration: 70%) was added and dissolved in toluene as a solvent. A mixed solution in which 2 parts of a platinum-based catalyst (SRX-212, manufactured by Dow Corning Toray Co., Ltd.) was added to 100 parts of the mixture was used as a release agent coating solution, and this was used as a solid content of 0.1 part.
Contact angle 7 obtained by coating and drying to 3 g / m ²
A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that the 6.1-degree release layer was used.

The pressure-sensitive adhesive tapes obtained in the above Examples and Comparative Examples were evaluated by the following methods, and the results were shown in Tables 1 and 2 respectively.
(Related to claim 2). <Curability> The curability of the silicone-based release agent was evaluated by applying the above-mentioned silicone-based release agent to a substrate, drying it, and rubbing it with the pad of a finger to improve the curability. ◎: 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, good curability ×; 140 ° C × 30 seconds (base temperature 95 ° C), poor curability

<Residual Adhesion Rate> An adhesive tape (polyester tape No. No. manufactured by Nitto Denko Corporation) was applied to the release agent layer of the adhesive tape.
31B) and stick it with a rubber roll.
After leaving for 20 hours at 70 ° C. while applying a load of 25 g / cm ^2, the adhesive tape was peeled off from the surface of the release layer, and allowed to stand at room temperature for 1 hour or more. Adhesive force (A) when peeled 180 ° per minute and adhesive tape on Teflon sheet (Nitto 31B)
Is adhered with a rubber roll, and then 25 g /
After leaving at 70 ° C. for 20 hours while applying a load of ² cm, the adhesive tape was peeled off from the release layer surface, left at room temperature for 1 hour or more, and then attached to the polished surface of a stainless steel plate.
Adhesive force when peeled 180 ° at 0.3 m / min (B)
And the ratio of (A) to (B) (A / B) × 100
Was determined as a residual adhesion rate (%).

<Contact Angle> 5 μl of a solution in which the weight ratio of water and ethanol was adjusted to 1: 1 was dropped on the release agent-coated surface of the substrate on the side of the polylaminate treatment, and the contact angle was measured after 30 seconds. did. (Measuring device: Kyowa Interface Science Co., Ltd., CA
-X type contact angle meter)

<Compatibility> After thoroughly stirring a silicone-based release agent solution obtained by dissolving the components (a), (b) and (c) in an organic solvent, take 300 ml into a beaker and separate the resin phase and the silicone phase. The time to perform was measured and evaluated. ○: Does not separate for more than one hour. ×: Separation is not performed for 1 hour or more, but the coating property is poor and not suitable for practical use. XX: phase separation within 1 hour, not practical.

<Back Peeling Force> A pressure-sensitive adhesive tape having a 180 ° peeling force was measured at a rate of 0.3 m / min 30 minutes after the adhesive-coated surface of the pressure-sensitive adhesive tape was adhered to the releasing agent-coated surface according to JIS Z 0237. .

<Coefficient of Dynamic Friction> The coefficient of kinetic friction in the horizontal direction between the release agent-treated surface of the adhesive tape and the same release agent-treated surface was measured by a friction coefficient test method in accordance with JIS P 8147.

<Writability> After writing the oily magic on the surface coated with the release agent, the time until the magic did not fall off when wiping with a Kimwipe was measured and evaluated. ◎: Magic does not drop when wiped with magic 0 to 10 seconds after writing ○: Magic does not fall when wiped with magic 11 to 30 seconds △; Wipes with magic 31 to 60 seconds after writing ×: Magic does not fall off when writing; Magic does not fall off when wiped with magic for 61 seconds or more

<Overlapping property> An adhesive tape was adhered to an exterior cardboard box (K-7 reinforced corrugated cardboard) specified in JIS P 3902. The time until the 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. ◎: None of the sheets peeled off after 1 day. ；: 5 or less peeled off after 1 day. △: 10 or less peeled off after 1 day. ×: All peeled off within 3 hours.

<Sealability> The workability when an adhesive tape was adhered to an exterior cardboard (K-7 reinforced cardboard) specified in JIS P 3902 was evaluated. ；: Good workability △: Somewhat good workability (practical use) ×: Poor workability (practical problem)

<Rewinding property of pressure-sensitive adhesive tape> The workability in rewinding the prepared 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).
With respect to the rewinding property at the time of peeling at a peeling speed of 30 m / nin, the floating of the laminate layer and the presence or absence of interlayer cracks of the substrate were visually observed. Here, the floating of the polyolefin-based resin layer (poly floating) indicates a state in which the laminate portion is pulled due to heavy peeling force and irregularities are generated on the surface. This is a phenomenon in which the film is not normally peeled between the substrate and the pressure-sensitive adhesive-coated surface, and cracks occur between layers of the base material. ；: Neither poly-floating nor interlayer cracking, suitable for practical use ×: No interlayer cracking, but poly-floating occurred, not suitable for practical use XX: Inter-layer cracking occurred, not suitable for practical use

[0097]

[Table 1]

[0098]

[Table 2]

As is clear from Tables 1 and 2, Examples 1 to
In the configuration of the present invention such as No. 17, the silicone was excellent in curability, was capable of being laminated and pasted, was excellent in non-slip properties, had good writing properties, and was excellent in heat resistance in the evaluation of rewinding.

In Comparative Examples 1 and 2 shown in Table 1, the peeling force at the time of rewinding is large, so that interlayer cracking occurs in Comparative Example 1 and poly floating occurs in Comparative Example 2. Comparative Example 2 has a high viscosity and is difficult to coat. Comparative Examples 3 and 7 are inferior in the three functions of the laminating property (back peeling force), the writing property, and the non-slip property. In Comparative Example 4, since the back surface peeling force is high, the rewinding property is poor, and interlayer cracking occurs even with heat resistance. In Comparative Example 5, since the Tg of the B component is low, poly-floating occurs due to heat resistance. In Comparative Example 6, the compatibility of the release agent solution was poor, and phase separation occurred within one hour, which was not suitable for practical use.

In Comparative Example 8 in Table 2, the unwinding property was inferior before the heat treatment, and in Comparative Examples 9 and 11, the three functions of the lamination property (backside peeling force), the writing property, and the non-slip property were inferior. Comparative Example 10 has good lamination property,
Poor non-slip properties. In Comparative Example 12, the writing property and the rewinding property were slightly inferior, and the heat resistance resulted in poly floating.

[0102]

According to the present invention, it is possible to provide a pressure-sensitive adhesive tape excellent in lapping property, non-slip property, writing property, etc., and excellent in heat resistance and workability.
It greatly contributes to the industry.

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[Procedure amendment]

[Submission date] April 14, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0056

[Correction method] Change

[Correction contents]

Example 1 Polyethylene-laminated kraft paper (a laminate obtained by laminating a polyethylene film of 20 μm on 73 g / m ² of melamine curl pack) was used as a base material. Release agent (BY24-312, manufactured by Toray Dow Corning Co., Ltd., solid content concentration 30%, functional group: vinyl group, molecular weight (m + n): 1
0 ³ to 10 ⁶ ) 40 parts of Ethyl cellulose having a Tg of about 316 ° K. (powder reagent, manufactured by Tokyo Chemical Industry Co., Ltd., 45 parts)
~ 55cps 5% in Toluene + Ethanol (80:20) Sol.at2
The mixture (A: B = 40: 60) to which 60 parts (5 ° C.) was added was 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 mixture was used as a release agent coating liquid, and the solid solution became 0.3 g / m ^2. And dried to obtain a release layer having a contact angle of 63.3 degrees. Natural rubber (RSS #) is used as an adhesive to be applied to the surface opposite to the release agent application surface.
3) 100 parts, 90 parts of a petroleum resin as a tackifier [Quinton S-100, softening point 94 ° C, ZEON CORPORATION
, 25 parts of a terpene-based liquid softening resin as a softening agent [Dimaron, manufactured by Yasuhara Chemical Co., Ltd.], a crosslinking agent 0.8
A composition comprising [Millionate MR-100, manufactured by Nippon Polyurethane Co., Ltd.] and 1 part of an antioxidant [Nocrack NS-5, manufactured by Ouchi Shinko Chemical Industry Co., Ltd.] was dissolved in toluene, and this was solidified. Coating to 40 g / m ²
The dried product was wound up to obtain an adhesive tape.

Claims (5)

[Claims] 1. A pressure-sensitive adhesive tape comprising a tape base material provided on one side with a release agent layer mainly composed of the following components A and B, and a pressure-sensitive adhesive layer provided on the other side of the base material. And the component B has a weight ratio of A: B = 30: 70 to 80: 2.
An adhesive tape characterized by being in the range of 0. Component A: (1) an addition-reaction silicone having the following components (i) to (iii) as main components: (i) In the formula, R: CH ₃ or (CH ₂ ) y CH = CH _{2 where} (CH ₂ ) y CH = CH ₂ is 0.4 to 5.0 mol%
And y is an integer of 0 or 4. m + n represents an integer of 100 or more. (Ii) an organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms in one molecule, (iii) a platinum-based curing catalyst, or
(2) Condensation reaction type silicone having the following (iv) to (vi) as main components: (iv) In the formula, at least one of R _{1 to} R ₄ is an oxyalkylene group, and m + n represents an integer of 10 or more. (V) an organohydrogenpolysiloxane having three or more silicon-bonded hydrogen atoms in one molecule, (vi) a metal salt curing catalyst of an organic acid, and a B component having a glass transition point (Tg) of 300 ° K or higher. 450 °
An organic resin that is K; 2. A pressure-sensitive adhesive tape substrate having a silicone-based release agent layer provided on one surface thereof, wherein the release agent layer comprises (a) an addition-reaction silicone, (b) a cellulose derivative, and (c) a reaction having the following units (c): The essential component is a three-component organic resin-based release control agent, and the component (a) contained in the release agent layer is 2%.
0 to 80% by weight, the component (b) is 15 to 45% by weight,
(C) An adhesive tape, wherein the component is 2 to 35% by weight and an adhesive layer is provided on the other surface of the base material. CH ₂ = CH (CH ₂ ) x (CH ₃ ) ₂ SiO _1/2 (C) where x is an integer of 0 or 4. 3. The contact angle of the release agent layer surface (using a solution in which the weight ratio of water to ethanol is 1: 1;
The pressure-sensitive adhesive tape according to claim 1 or 2, wherein (measured after seconds) is in the range of 55 to 75 degrees. 4. JIS of the pressure-sensitive adhesive layer with respect to the release agent layer surface
The peel force based on Z 0237 is 100 to 500 gf /
4. The device according to claim 1, wherein the length is 25 mm.
The adhesive tape according to item 1. 5. The method according to claim 1, wherein the base material is a melamine clump pack which has been subjected to a filling treatment.
The adhesive tape according to the item.