JP2001123130A - Adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive tape having neither bad influence on the human body nor environmental pollution, excellent curability, slight reduction in tack of adhesive, in bond strength, etc., repeated pasting properties, non-slip properties, etc., and excellent heat resistance. SOLUTION: This adhesive tape is obtained by providing one side of a substrate with a peel force adjuster-containing solventless silicone-based release agent and the other side with an adhesive agent layer and has <=20 mg/m2 amount of silicone transferred to the adhesive agent layer measured by a fluorescent X-ray measurement apparatus. The peel force adjuster-containing solventless silicone-based release agent comprises (a) a vinyl functional silicone resin- containing peel force adjuster controlled to have 100-5,000 mPa.s viscosity at 25 deg.C, (b) an alkenyl functional polyorganosiloxane having 50-20,000 mPa.s viscosity at 25 deg.C, (c) an organohydrogenpolysiloxane and (d) a platinum-based catalyst as main components. The weight ratio of the component (a) to the component (b) is 60:40 to 99:1 and the amount of the component (c) is adjusted to 1.0-50 pts.wt. based on 100 pts.wt. of the total of the components (a) and (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adhesive tape. More specifically, the present invention relates to a pressure-sensitive adhesive tape using a solvent-free silicone-based release agent, and more particularly to a pressure-sensitive adhesive tape which has little silicone transfer to the pressure-sensitive adhesive, has an overlapping property, a non-slip property, and is excellent in heat resistance.

[0002]

2. Description of the Related Art In general, a pressure-sensitive adhesive tape has a pressure-sensitive adhesive layer provided on one side of a substrate and a release agent layer provided on the other side. As the release agent, a long-chain alkyl group-containing compound, a silicone-based release agent, and the like are mainly used. Particularly, the silicone-based release agent exhibits excellent releasability from the pressure-sensitive adhesive, so that the tape is developed. Since it is light, has good workability, and is inexpensive, it has the largest production volume among packaging tapes and is mainly used for sealing cardboard.

However, among the above-mentioned constitutions, an adhesive tape using a silicone-based release agent cannot be laminated and pasted because it is too strong (too light) in its peelability, and it is necessary to pack cardboard or the like because the back surface of the tape is slippery. When used in a stack, there are drawbacks such as collapse of the load.

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 characteristic that it has high friction coefficient on the release surface and is hard to slip, and can be pasted on the release surface. However, the long-chain alkyl group-containing compound has poor heat resistance as compared with a silicone-based release agent, and when exposed to high temperatures while being bonded to the pressure-sensitive adhesive layer, the compound becomes heavily released and causes abnormal peeling. There's a problem. For example, in the case of using a kraft paper substrate obtained by extruding and laminating a polyolefin resin, there is a problem that interlayer cracking of the substrate occurs. In particular, in the case of a combination with an adhesive containing synthetic rubber or natural rubber as a main component, peeling was heavy, and phenomena such as interlayer cracking and substrate destruction due to heavy peeling at high temperatures occurred at relatively low temperatures.

Further, even when a film made of polypropylene, polyethylene, or the like is used as a base material, the film is heavily peeled off when stored at a high temperature or the like, and a great force is required for an operator to rewind, or the film can be unwound. There was a problem that it could not be used as a tape without it. As described above, the silicone-based release agent and the long-chain alkyl group-containing compound have advantages and disadvantages, respectively, and a pressure-sensitive adhesive tape which solves both disadvantages has been demanded.

The present inventor has already disclosed in JP-A-11-61062.
JP-A-11-228924 discloses a specific solvent-type silicone and a cellulose derivative and / or an organic resin having a glass transition point in a specific range, or a specific silicone and a cellulose derivative and a reactive organic resin-based release control agent. We have proposed an adhesive tape that has writability and non-slip properties and can be laminated and pasted by limiting the weight ratio of the three components as essential components.

However, the release agent proposed above is of a solvent type, and when a solvent type release agent is used, the solvent is dried,
In addition to the need for a large oven to evaporate, there are also concerns that the relatively high drying energy will increase production costs, and that solvent evaporation and scatter may cause adverse effects on the human body and environmental pollution. It had been.

[0008] Further, the adhesive tape can be pasted on the back surface,
In order to impart a non-slip property, the solvent type silicone has a Q unit of the formula SiO _4/2 (also referred to as SiO ₂ ) and / or
Or a T unit of the formula RSiO _3/2 , and further a formula R ₃ SiO _1/2
M units, and optionally wherein R ₂ consists of D units of SiO _2/2 peel strength modifier (peel strength modifier consisting of the M and Q units are commonly referred to as MQ resins) Is required. R in the formula is the same or different hydrocarbon group, and includes a methyl group, an ethyl group, a vinyl group, a hexenyl group, an ether group, and the like, and a methyl group and a vinyl group are preferred. In the case of a solvent type silicone release agent,
The release force modifier has an extremely low viscosity as compared with the base polyorganosiloxane, and a relatively large amount of the release force modifier must be added in order to increase the release force (to increase the release). However, there is a tendency that the decrease in the residual adhesion rate due to the transfer of the silicone to the pressure-sensitive adhesive layer is remarkably reduced with the addition amount. Due to a decrease in the residual adhesion rate, there are problems such as the inherent tackiness of the adhesive, the adhesive strength, and in some cases, even the holding power. The influence of the silicone transfer on the pressure-sensitive adhesive was particularly noticeable on the tack, and it was found that even a very small transfer amount had a large influence.

[0009]

Accordingly, the present invention provides
Solving the above disadvantages, there is no adverse effect on the human body or environmental pollution, etc., excellent curability, little decrease in tackiness of the adhesive, adhesive strength, etc., lamination property, non-slip property, and heat resistance It is an object to provide an excellent adhesive tape.

[0010]

That is, in order to solve the above-mentioned problems, the present invention provides a solvent-free silicone release agent containing a release force adjuster on one surface of a substrate, and on the other surface. The present invention relates to a pressure-sensitive adhesive tape provided with a pressure-sensitive adhesive layer, wherein the amount of silicone transferred to the pressure-sensitive adhesive layer measured by a fluorescent X-ray measuring device is 20 mg / m ² or less.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In order to solve the above-mentioned problems, the present inventor has provided a solventless silicone release agent containing a release force adjusting agent on one side of a substrate, and provided an adhesive on the other side. An adhesive tape provided with an adhesive layer, wherein the amount of silicone transferred to the adhesive layer measured by a fluorescent X-ray measurement device is 20 mg.
/ M ² or less, not only has no adverse effects on the human body or environmental pollution, but also impairs the inherent tack, adhesive strength, etc. of the adhesive, despite having laminating properties and non-slip properties. It has been found that an adhesive tape having no heat resistance and excellent heat resistance can be obtained, and the present invention has been completed.

[0012] The amount of silicone transfer is determined not only when the curability of the silicone-based release agent is insufficient, but also when a polyorganosiloxane having a low molecular weight or viscosity or a release force modifier or an additive is used or increased, or when the release agent is used. The amount is increased by using or increasing the amount of a polyorganosiloxane having no (less) alkenyl group or the like involved in the reaction or a release force regulator. Also,
It was found that the larger the viscosity difference between the polyorganosiloxane and the release force modifier, the greater the amount of silicone transfer.

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, cast paper, and polymer film. 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 material containing a pigment and / or an adhesive as a main component is used. As the adhesive, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, polyacrylate, starch, cellulose derivative, urethane resin, acrylic Resins, polyester resins, alkyd resins, melamine resins, styrene-butadiene copolymer latex emulsions, styrene-acryl copolymer latex emulsions, and acrylate resin-based resins can be used alone or in combination.

Examples of the pigment include inorganic pigments such as kaolin, aluminum hydroxide, heavy calcium carbonate, light calcium carbonate, titanium oxide, talc, satin white, calcium sulfate, barium sulfate, zinc oxide, silica, polypropylene resin and polyethylene resin. And organic pigments such as styrene resin, acrylic-styrene resin, urea formalin resin, melamine-formalin resin, benzoguanamine resin and the like can be used alone or in combination.

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 peelable sheet or the adhesive tape is recycled (used) as recycled pulp.

The release agent used in the pressure-sensitive adhesive tape of the present invention is a solvent-free silicone release agent containing a release force adjuster capable of imparting the adhesive tape with a laminating property and a non-slip property. The amount of silicone transferred to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape using a fluorescent X-ray measuring device is not particularly limited as long as it is 20 mg / m ² or less. Type silicone release agent is (a) 50-5000 mPa at 25 ° C.
A release force adjusting additive comprising a vinyl functional silicon resin adjusted to a viscosity of s, (b) 50-20 at 25 ° C.
An alkenyl-functional polyorganosiloxane having a viscosity of 000 mPa · s, (c) an organohydrogenpolysiloxane, and (d) a solventless silicone-based release agent containing a platinum-based catalyst as a main component are preferred.

If the amount of the silicone transferred to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape exceeds 20 mg / m ² , the tack and the adhesive strength inherent to the pressure-sensitive adhesive are reduced. This is not preferable because it causes problems such as peeling of the adhesive tape adhered to the substrate. The amount of transferred silicone is determined by a characteristic X-ray intensity (here, S.sub.S) measured using a plurality of standard samples (silicone-coated products) prepared in advance.
A calibration curve having a correlation coefficient of 0.99 or more was prepared from the relationship between iKα) and the amount of silicone by the least squares method, and the calibration was performed when SiKα of an unknown sample (here, the adhesive layer of the adhesive tape) was measured. It is calculated as the difference between the amount of silicone determined by the line and the amount of silicone determined by the same measurement method as described above for the pressure-sensitive adhesive layer (standard sample to which silicone has not been transferred) before coming into contact with the release agent layer. However,
The measurement of the pressure-sensitive adhesive layer is performed by irradiating X-rays from the surface of the pressure-sensitive adhesive applied to the base material from which the pressure-sensitive adhesive is exposed. The measurement device is RIX1000 manufactured by Rigaku Denki Kogyo Co., Ltd.
The measurement conditions were: analysis element: Si, spectral crystal: PET, X-ray tube target: Cr, X-ray tube voltage: 50 kV, X-ray tube current: 50 mA, measurement angle 2θ (SiKα, 109.04).
deg), PHA (peak height analyzer): (LU set value 10
0-300), measurement time: 40 seconds, sample folder 1
5φ.

The component (a) of the solvent-free silicone release agent containing a release force adjusting agent has a vinyl group in the molecule and is a release force adjusting agent for increasing the release force. The position is not particularly limited, but is preferably at least two or more from the viewpoint of reactivity and the like. If the number of vinyl groups is less than 2, the curability becomes poor, which is not preferable.

The viscosity at 25 ° C. is 50 to 500.
0 mPa · s is preferred, and more preferably 100 to 2
000 mPa · s. The viscosity mentioned here is JIS
It is a value measured at a test temperature of 25 ° C. based on a viscosity test method using a rotational viscometer of a liquid resin according to −K-7117. If the viscosity is less than 50 mPa · s, it may be easy to transfer to the pressure-sensitive adhesive layer, and if the viscosity is lower, it may be easy to volatilize and may not exhibit performance.
If it exceeds 000 mPa · s, the viscosity is too high, and it may be difficult to obtain a release agent for solventless coating, which is not preferable.

The component (b) is, for example, a polyorganosiloxane having an alkenyl group such as a vinyl group or a hexenyl group. The position of the alkenyl group in the molecule is not particularly limited. Preferably, there are at least two or more. If the number of vinyl groups is less than 2, the curability becomes poor, which is not preferable. The viscosity measured by the above method is preferably 50 to 20,000 mPa · s at 25 ° C., and more preferably 50 to 10,000 mPa · s. Viscosity is 5
If it is less than 0 mPa · s, it may be easy to transfer to the pressure-sensitive adhesive layer, or if it has a lower viscosity, it may be easily volatilized and may not exhibit its performance.
If it exceeds s, the viscosity is too high, and it is difficult to obtain a release agent for solventless coating, which is not preferable.

The method of adjusting the viscosity of the components (a) and (b) is not particularly limited, but is adjusted mainly by changing the molecular weight (or degree of polymerization) of the polymer. In addition, as described in Japanese Patent Publication No. 1-38414, C
There is a method of dispersing the component (a) in a nonvolatile unsaturated organic reactive diluent such as _(16-18) -α-olefin,
The above viscosity of the component (a) and the component (b) is (b) / (a) =
More preferably, it is in the range of about 0.1 to 100.
Incidentally, in the solvent-based silicone, the viscosity of the MQ resin corresponding to the component (a) of the present invention is extremely low as compared with the viscosity of the component (b), or the viscosity of the component (b) is extremely high.
That is, (b) / (a) = about 1000 to 50,000. Therefore, it is presumed that the component (a) having a low viscosity is easily transferred to the pressure-sensitive adhesive layer due to poor compatibility, which may be one of the factors for reducing the residual adhesion rate.

The component (c) serves as a crosslinking agent that reacts with the alkenyl groups of the components (a) and (b), and includes a hydrogen atom (SiH) bonded to a silicon atom.
It is preferable to use those having at least two in the molecule. If the amount of SiH is less than 2, the curing reaction becomes poor, which is not preferable. The preferred viscosity is 10 to 10
00 mPa. s. Further, JP-A-11-10
It is also possible to use a SiH-functional organopolysiloxane that increases the peeling force as described in Japanese Patent No. 0551.

The component (d) functions as a catalyst for the reaction between the components (a) and (b). Examples thereof include alcoholic or aldehyde solutions of chloroplatinic acid, chloroplatinic acid and various olefins and vinylsiloxanes. Platinum-based catalysts represented by complex salts of the above are generally used. The above-mentioned viscosity of the release agent composition obtained by mixing (a) to (d) is preferably from 100 to
5000 mPa · s, more preferably 100 to 100
0 mPa · s.

In addition to the components (a), (b), (c) and (d), an adhesion improver such as a silane coupling agent for improving the adhesion to a substrate, or a reaction retarder ( (A reaction inhibitor), or a chain hydrocarbon represented by C _n H _2n such as α-olefin for adjusting viscosity, silicone fine powder for preventing blocking, fine powder silica or the like, alone or in combination. ) To (d) may be added to the release agent to the extent that curability, adhesion to a substrate, release force, etc. are not impaired.

In the present invention, in order to obtain an adhesive tape having a desired non-slip property, the coefficient of kinetic friction between the surfaces of the release agent layers is preferably 0.20 or more. If it is less than 0.20, for example, when the cardboard boxes to which the adhesive tape is stuck are stacked and transported, the collapse of the load easily occurs, which is not preferable. Here, the coefficient of kinetic friction is obtained by measurement based on JIS-P-8147. Incidentally, if the coefficient of dynamic friction is less than 0.20 even if the coefficient of static friction exceeds 0.20, it is not preferable because the collapse of the corrugated cardboard at a certain degree or a force from the side is suddenly caused to collapse the load. More preferably, the coefficient of dynamic friction is equal to or greater than the coefficient of static friction.

The weight ratio of the components (a) to (c) is 60:40 to 99: 1, and the weight ratio of the components (a) and (b) is 60:40 to 99: 1. It is preferable that (c) is 1.0 to 50 parts by weight based on 100 parts by weight in total of (b).

Regarding the weight ratio of (a) and (b), (a)
If the ratio of the components is less than 60, use (a)
Depending on the type of component, the peeling force and the coefficient of friction are also low
The object of the present invention is not preferable because the lamination property and the non-slip property may be poor. On the other hand, if the ratio of the component (a) exceeds 99, the peeling force is too strong (too heavy) when rewinding the pressure-sensitive adhesive tape depending on the type of the component (a) to be used, and it becomes difficult to rewind the tape. Otherwise, it is not preferable because peeling abnormalities may occur in which the function as an adhesive tape cannot be exhibited without rewinding.

The component (c) is a total of 100 of (a) and (b).
It is preferably from 1.0 to 50 parts by weight, more preferably from 1.0 to 10 parts by weight, based on parts by weight. 1.
If it is less than 0, the crosslinking with the alkenyl groups contained in the components (a) and (b) is incomplete, and the curability may be reduced. It is not preferable because it may remain as an unreacted component and adversely affect, for example, the peeling force may become higher than the set value or become unstable with time. It is necessary to change the addition amount of the component (c) depending on the number of alkenyl groups contained in the components (a) and (b). Generally, the alkenyl group and the organohydrogenpolysiloxane (hereinafter simply abbreviated as SiH) are used. In some cases) is SiH /
The alkenyl group is preferably 1 to 10. By the way, if it is less than 1, the curability is lowered, which is not preferable.
If it exceeds 0, the amount of unreacted organohydrogenpolysiloxane changes with time, which is not preferable because the peeling force and the like may become unstable with time.

The amount of the component (d) may be a catalyst amount, and is not particularly limited. However, from the viewpoint of exhibiting the effect and from an economic viewpoint, the total amount of the components (a) and (b) is preferably 100 parts by weight. About 1.0 to 10 parts by weight is preferable.

The solvent-free silicone release agent can of course be applied to a substrate without dilution with an organic solvent, and the coating method is not limited at all. For example, roll coater coating, offset gravure roll coating Coating, gravure coater coating, curtain flow coater coating, air knife coater coating, and the like.

The preferred amount of the solvent-free silicone-based release agent is about 0.05 to 5 g / m ^2. The composition is applied and heated and dried by the above-mentioned coating method to form a cured film. Although it depends on the heat resistance of the substrate to be coated and the drying device, it is preferably about 70 to 150 ° 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, and a tackifier resin, and if necessary, Additives such as a softening agent, an antioxidant, a crosslinking agent, and a pigment are further blended. It is preferable to use a natural rubber-based or synthetic rubber-based pressure-sensitive adhesive as an inexpensive one with a relatively high adhesive strength, and it is preferable to use an acrylic-based pressure-sensitive adhesive as a material excellent in stability over time such as weather resistance. However, it is preferable to use a solventless adhesive, such as a hot melt adhesive, which has no adverse effect on the human body or environmental pollution like the release agent. The amount of the adhesive to be applied should be changed each time according to the application of the adhesive tape, similarly to the type of the adhesive, and is not particularly limited. However, considering the economical efficiency and the adhesive physical properties such as adhesive strength, tackiness, and holding power, 5 About 100 g / m ² , and 10 to 70 g
/ M ² is common.

The method of applying the pressure-sensitive adhesive is not limited at all. For example, comma coating, reverse coating, gravure coating, reverse gravure coating, kiss coating, knife coating, bar coating, etc. A transfer method for transferring a material coated by these methods onto a process paper and a process paper is exemplified.

In the pressure-sensitive adhesive tape of the present invention, by controlling the amount of silicone transferred to the pressure-sensitive adhesive layer to 20 mg / m ² or less, adverse effects on the pressure-sensitive adhesive's inherent adhesive properties can be suppressed. It can be used without inferiority. However, naturally, the above-mentioned silicone transfer amount is 20
mg / m ² or less, in the evaluation of the curability of the solvent-free silicone-based release agent, the drying conditions (at least at least) in which no smear (poor curability) occurs when the coating film is rubbed with the pad of a finger. At 70 ° C. for 20 seconds or more). If the silicone transfer amount exceeds 20 mg / m ² , the inherent adhesive strength of the pressure-sensitive adhesive is undesirably reduced due to the transfer of the release agent layer to the silicone, which has a particularly large effect on tack.

In order to obtain an adhesive tape having the desired laminating property and free from abnormal peeling according to the present invention, it is necessary to use (a)
A release force modifier containing a vinyl-functional silicon resin adjusted to have a viscosity of 50 to 5000 mPa · s at 25 ° C;
(B) The weight ratio of the alkenyl-functional polyorganosiloxane having a viscosity of 50 to 50,000 mPa · s at 25 ° C. can be more preferably adjusted by adjusting the weight ratio to 60:40 to 99: 1. Depending on the type of the solvent silicone or the pressure-sensitive adhesive, the peeling force between the pressure-sensitive adhesive layer and the release agent layer changes, so that the lamination property is deteriorated and the pressure-sensitive adhesive layer may rise from the release agent layer. In this case, if the peeling force according to JIS-Z-0237 between the pressure-sensitive adhesive layer and the release agent layer is 40 to 200 N / m, the desired overlapping can be performed, and the pressure-sensitive adhesive tape is wound (after heat treatment). An adhesive tape having no peeling abnormality upon returning can be obtained.
If it is less than 40 N / m, the adhesive tape attached to the release agent layer may float up, while
/ M is not preferred because peeling abnormality such as difficulty in peeling off the adhesive tape may occur.

[0036]

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" based on solid content or active ingredient, respectively, unless otherwise specified.

Example 1 Melamine clump pack as a base material 73 g / m ² Adhesive as a sealing layer: SBR (L-1571, manufactured by Asahi Kasei Corporation) 50
Parts, pigment: 50 parts kaolin (manufactured by Engelhard, HT clay), defoamer (manufactured by San Nopco, Nopco 1407)
K) 0.5 part, lubricant (San Nopco, Nopcoat C)
104) Applying 0.9 g of a filling layer having a coating amount of 7 g / m
² , which was subjected to a super calender treatment so that the substrate smoothness was 520 seconds. On the other hand, as a release agent (a) containing a vinyl-functional silicon resin as a release agent, a release agent (CRA42, Wacker Chem) containing 65% of a silicon resin containing vinyl groups at both ends is used as a release agent.
available from IE GmbH, viscosity 1400 mP
a.s) In 96 parts, DEHESIVE 636 (Wack) as (b) an alkenyl-functional polyorganosiloxane
er Chemie GmbH, available in a viscosity of 400 mPa · s) and stirred well. Next, with respect to a total of 100 parts of (a) and (b), V06 (Wack) was used as the organohydrogenpolysiloxane (c).
er Chemie GmbH)
2.5 parts, (d) OL (Wacker
Available at Chemie GmbH) 1.5
A part of the mixture was stirred and adjusted to be uniform. 0.5 g / m ^{2 of the} release agent was applied to the surface of the base material on which the sealing layer was provided.
And apply evenly with a roll coater at 120 ° C.
For 20 seconds. Next, a styrene-isoprene block copolymer (trade name: SIS5000, manufactured by Nippon Synthetic Rubber Co., Ltd.) 100 was provided on the surface opposite to the surface on which the release agent was applied.
Parts by weight, aliphatic petroleum resin (trade name:
100 parts by weight of Escolets 1310, manufactured by Exxon Chemical Co., Ltd., 40 parts by weight of a softener (trade name: Diana Process NM280, manufactured by Idemitsu Kosan Co., Ltd.), anti-aging agent (trade name: Nocrack NS-5, manufactured by Ouchi Shinko Chemical Co., Ltd.) 1) parts by weight were mixed to form an adhesive composition, and the adhesive composition was heated and melted,
An adhesive tape was coated with a die coater (trade name: Park Coater C-400, manufactured by Yuri Roll Machine Co., Ltd.) so as to have a coating weight of 50 g / m ² , thereby obtaining an adhesive tape.

Example 2 (a) As a peeling force adjusting agent containing a vinyl-functional silicon resin, a peeling force adjusting agent containing 65% of a silicon resin having vinyl groups at both ends (CRA42, Wacker Chemie G)
(available from mbH, viscosity 1400 mPa · s)
80 parts of DEHESIVE 636 (Wacker C) as (b) alkenyl-functional polyorganosiloxane
available from hemie GmbH, viscosity 400
mPa · s) and stirred well. Next, with respect to 100 parts in total of (a) and (b), V06 (Wacker C) was used as (c) an organohydrogenpolysiloxane.
available at hemie GmbH) 12.0
Part, (d) OL (Wacker Ch) as a platinum-based catalyst
1.5 g / m ² of the base material described in Example 1 was applied to the surface of the base material provided with the plugging layer.
And apply evenly with a roll coater at 120 ° C.
A pressure-sensitive adhesive tape was prepared in the same manner as in Example 1, except that the adhesive tape was dried by heating for 20 seconds.

Example 3 (a) As a peeling force controlling agent containing a vinyl functional silicon resin, a peeling force controlling agent containing 68% of a silicon resin containing vinyl groups at both ends (CRA17, Wacker Chemie G)
available at mbH, viscosity 500 mPa · s) 8
0 parts, as (b) alkenyl-functional polyorganosiloxane as DEHESIVE 924 (Wacker Ch
available from emie GmbH, viscosity 200m
20 Pa.s) and stirred well. Next, with respect to 100 parts in total of (a) and (b), Vc (Wacker C) was used as (c) an organohydrogenpolysiloxane.
available from Hemie GmbH) 5.0 parts,
(D) OL (Wacker Chem) as a platinum-based catalyst
ie, available from IE GmbH), and 1.5 parts of the mixture was stirred to uniformity.
The surface provided with the prospect Me layer substrate according uniformly coated by a roll coater so as to be 0.5g / m ^{2, 2} at 120 ° C.
An adhesive tape was produced in the same manner as in Example 1 except that the adhesive tape was dried by heating for 0 second.

COMPARATIVE EXAMPLE 1 (a) As a peeling force controlling agent containing a vinyl functional silicon resin, a peeling force controlling agent containing 65% of a silicon resin having a vinyl group at both ends (CRA42, Wacker Chemie G)
(available from mbH, viscosity 1400 mPa · s)
50 parts of DEHESIVE 636 (Wacker C) as (b) alkenyl-functional polyorganosiloxane
Available from hemie GmbH, viscosity 400 mP
a.s) 50 parts were added and stirred well. Next, with respect to 100 parts in total of (a) and (b), V06 (Wacker C) was used as (c) an organohydrogenpolysiloxane.
available from Hemie GmbH) 11.5 parts,
(D) OL (Wacker Chem) as a platinum-based catalyst
ie, available from IE GmbH), and 1.5 parts of the release agent was added and stirred to make it uniform, and 0.5 g / m ^{2 of the} release agent was applied to the surface of the base material described in Example 1 on which the sealing layer was provided. An adhesive tape was prepared in the same manner as in Example 1 except that the composition was uniformly applied with a roll coater and dried by heating at 120 ° C. for 20 seconds.

COMPARATIVE EXAMPLE 2 (a) As a peeling force controlling agent containing a vinyl functional silicon resin, a peeling force controlling agent containing 65% of a silicon resin having vinyl groups at both ends (CRA42, Wacker Chemie G)
available at mbH, viscosity 1500 mPa · s)
V06 (Wacker Chemie) as an organohydrogenpolysiloxane (c) was added to 100 parts.
12.5 parts (available from GmbH) and (d) OL (Wacker Chemie GmbH) as a platinum-based catalyst.
1.5 parts of the release agent was added to the surface of the base material described in Example 1 on which the sealing layer was provided, so that the release agent became 0.5 g / m ^2. An adhesive tape was produced in the same manner as in Example 1 except that the composition was uniformly applied with a roll coater and dried by heating at 120 ° C. for 20 seconds.

Comparative Example 3 (a) 55 parts of KS-3800 (available from Shin-Etsu Chemical Co., Ltd., viscosity: 2 mPa · s) as a release force regulator containing a vinyl functional silicon resin, BY24-843 (Dow Corning Toray) Available from Silicone, viscosity 5.5m
Pa.s) 5 parts, (b) alkenyl-functional polyorganosiloxane SD-7220 (available from Dow Corning Toray Silicone Co., Ltd., viscosity 15,000 mP)
a.s, # 40 parts of an organohydrogenpolysiloxane corresponding to (c) was added, and (a) and (b) were dissolved in a toluene solution and stirred well. Next, (a) and (b)
(D) as a platinum-based catalyst, PL-
3 parts of 50T (available from Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was stirred so as to be uniform. ^A pressure-sensitive adhesive tape was prepared in the same manner as in Example 1 except that the composition was uniformly coated with a wire bar so as to obtain No. 2, and dried by heating at 120 ° C. for 20 seconds.

Comparative Example 4 UV-curable silicone X-62-7052 as a release agent
(Available from Shin-Etsu Chemical Co., Ltd., viscosity 30,000 mP
a.s) 100 parts of CAT-7602 as a catalyst
A part of the base material described in Example 1 was coated with the added part using a roll coater, but the viscosity was too high to be applied uniformly. I couldn't.

Comparative Example 5 As a release agent, a long-chain alkyl pendant polymer [Pyroyl 1200, manufactured by YAS & Co., Ltd.] was dissolved in toluene, and the solid content was reduced to 0% on the surface of the base material provided with the filler layer. .
Apply evenly with a wire bar to 1 g / m ^2.
An adhesive tape was produced in the same manner as in Example 1 except that the adhesive tape was dried at 00 ° C. for 20 seconds.

The pressure-sensitive adhesive tapes obtained in the above Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Table 1. <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. Δ: good curability at 140 ° C. × 30 seconds (base temperature 95 ° C.) or less. X: Poor curability even at 140 ° C for 30 seconds (base temperature: 95 ° C).

<Residual Adhesion Ratio> Adhesive tape (polyester tape No. 31 manufactured by Nitto Denko Corporation) was applied to the release agent layer of the adhesive tape.
B) is adhered and adhered with a rubber roll.
After leaving for 20 hours at 70 ° C. while applying a load of g / cm ^2, the adhesive tape was peeled off from the release layer surface,
After leaving it for more than an hour, it is stuck on the polished surface of a stainless steel plate and peeled at 180 m at 0.3 m / min. (A) 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 (%).

<Amount of Transfer to Silicone> An adhesive tape (Nitto 31B) was attached to the surface of the release agent layer of the adhesive tape, adhered with a rubber roll, and then left at 70 ° C. for 20 hours while a load of 25 g / cm ² was applied. Thereafter, the pressure-sensitive adhesive tape was peeled off from the release layer surface, left at room temperature for 1 hour or more, and then the silicone count number (cp) detected on the pressure-sensitive adhesive layer surface by a fluorescent X-ray apparatus (RIX1000 manufactured by Rigaku Denki Kogyo Co., Ltd.)
s) The amount of silicone (mg / mg)
m ² ) was measured.

<Peeling Force> The adhesive-coated surface of the pressure-sensitive adhesive tape prepared in Example 1 according to JIS-Z-0237 was applied to each release agent-coated surface for 30 minutes and then 180 ° peeled at 0.3 m / min. Force was measured in a tensile test.

<Coefficient of Dynamic Friction> The coefficient of dynamic friction in the horizontal direction between the release agent-treated surfaces of each adhesive tape was measured by a friction coefficient test method according to JIS-P-8147.

<Overlapping property> Each adhesive tape was adhered to an exterior cardboard box (K-7 reinforced corrugated cardboard) specified in JIS-P-3902. The time until the applied 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. A: No one sheet is peeled off after one day. ；: Less than 5 sheets peeled off after one day. Δ: 10 sheets or less peeled off after one day. X: All peeled off within 3 hours.

<Rewinding property of pressure-sensitive adhesive tape> The workability in rewinding each of the produced pressure-sensitive adhesive tapes was evaluated. ；: Good workability. Δ: Slightly poor workability (no problem in practical use). ×: Poor workability (practical problem).

<Heat resistance of pressure-sensitive adhesive tape> Regarding heat resistance of the pressure-sensitive adhesive tape, the workability of rewinding the pressure-sensitive adhesive tape by hand after leaving each obtained pressure-sensitive adhesive tape at 80 ° C. for 2 days was evaluated. . ；: Good workability. ×: Rewinding requires a strong force or is difficult to rewind. XX: The substrate was broken, and did not function as an adhesive tape.

<Tack> As a tack on the pressure-sensitive adhesive surface of each prepared pressure-sensitive adhesive tape, a ball is rolled on the pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive tape at an inclination angle of 30 degrees according to JIS-Z-0237, and the ball stops for 5 seconds or more. The size of the ball when it was played was recorded. The measurement was performed three times while changing the sample, and the decimal value of the average value of the three measurements was discarded to obtain a measured value.

[0054]

[Table 1]

As is clear from Table 1, the constitutions of the present invention as in Examples 1 to 3 are excellent in curability, have less silicone transfer to the pressure-sensitive adhesive layer, have laminating property and non-slip property, and Excellent heat resistance. In Comparative Example 1, there is no lamination property and non-slip property, and in Comparative Example 2, the rewinding property of the adhesive tape is poor because the peeling force is too high. The heat-resistant test was not performed on the pressure-sensitive adhesive tape of Comparative Example 2 because the rewinding property was poor before the heat treatment. In Comparative Example 3, the amount of silicone transferred to the pressure-sensitive adhesive layer was large, and the tack reduction rate was high. In Comparative Example 5, zipping (separation with discontinuous sound) occurred during rewinding, and the heat resistance was poor, and the substrate was destroyed after heat treatment, so that it could not be used as an adhesive tape.

[0056]

According to the present invention, since a solventless silicone is used, a large-scale oven is not required for drying and evaporating the solvent, the production cost can be reduced, and the solvent is volatilized and scattered. Can improve the adverse effects on the human body and environmental pollution, such as the adverse effects on the human body and environmental pollution caused by, and have excellent curability, less silicone transfer to the pressure-sensitive adhesive layer, and have the property of laminating and non-slip properties. In addition, it is possible to provide an adhesive tape having excellent heat resistance and greatly contribute to the industry.

Claims (5)

[Claims] 1. An adhesive tape comprising a solvent-free silicone release agent containing a release force adjuster provided on one surface of a substrate and an adhesive layer provided on the other surface, wherein the adhesive tape is provided by a fluorescent X-ray measuring apparatus. Measured silicone transfer to adhesive layer is 20mg
/ M ² or less. 2. The pressure-sensitive adhesive tape according to claim 1, wherein a dynamic friction coefficient according to JIS-P-8147 between the release agent layers is 0.20 or more. 3. JIS-Z-02 of pressure-sensitive adhesive layer and release agent layer
The pressure-sensitive adhesive tape according to claim 1, wherein a peel force according to 37 is 40 to 200 N / m. 4. A solvent-free silicone release agent containing the release force adjusting agent, comprising: (a) 100-5000 mPa at 25 ° C.
A release force modifier comprising a vinyl-functional silicon resin adjusted to a viscosity of s, (b) 50-2000 at 25 ° C.
The pressure-sensitive adhesive tape according to any one of claims 1 to 3, wherein an alkenyl-functional polyorganosiloxane having a viscosity of 0 mPa · s, (c) an organohydrogenpolysiloxane, and (d) a platinum-based catalyst as main components. . 5. The weight ratio of (a) and (b) according to claim 4 is 60:40 to 99: 1, and the total of (a) and (b) is 1
The pressure-sensitive adhesive tape according to any one of claims 1 to 4, wherein (c) is adjusted to be 1.0 to 50 parts by weight with respect to 00 parts by weight.