JPH10121000A - Adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent adhesive tape having good tearability with hands and high adhesive force, capable of being easily be peeled on a peeling operation after an ageing treatment, not leaving on an adherend, having excellent repeelability, not discolored with time and useful for ageing building materials. SOLUTION: This adhesive tape is produced by forming an adhesive layer on one side of a thermoplastic resin substrate, and has good tearability. Therein, the adhesive tape has a tear strength of 0.2-1.0kgf, and the adhesive agent comprises an adhesive composition produced by crosslinking the mixture of 100 pts.wt. (as solid content) of an acrylic copolymer with 3-30 pts.wt. of a petroleum and/or terpene tackifier resin having a softening point of 70-150 deg.C by the use of 0.01-2 pts.wt. of a metal compound. The acrylic copolymer comprises an alkyl (meth)acrylate ester and its copolymerizable vinylic monomer, has a weight-average mol.wt. of 300,000-1,000,000 and a dispersion degree of 6-12.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hand-cut adhesive tape having a pressure-sensitive adhesive layer provided on one side of a thermoplastic resin base material, which is used in such a manner that it is adhered and then peeled off again. For example, it relates to an adhesive tape for use in architectural curing and the like.

[0002]

2. Description of the Related Art Adhesive tapes for curing of building materials, such as paints and interiors, have a sufficiently high initial adhesive strength to various adherends and can be adhered to for a long time depending on the curing period. Hands that can be cut by hand without using tools such as scissors or cutters so that they do not peel off and do not stain adherends with adhesive residue when peeled off, and to perform a series of curing work easily. It is required to have sharpness.

[0003] Conventionally, an adhesive applied to a hand-cut base material made of paper, film, cloth or the like has been widely used. However, it is easy to tear or stretch when pulled out from a roll. When the adhesive is applied for a long period of time, the adhesive strength increases, and when the adhesive is peeled off, the adhesive adheres to the adherend and the adhesive adheres easily to the adherend, which tends to cause contamination.

In order to avoid adhesive residue and tape breakage,
It is sufficient to lower the adhesive strength of the pressure-sensitive adhesive, but there is a problem of insufficient initial adhesive strength. In addition, these pressure-sensitive adhesives tend to have a yellow tint with time, and presently have various problems to be solved, such as a problem that the appearance of the pressure-sensitive adhesive tape is poor and the commercial value is impaired.

[0005]

DISCLOSURE OF THE INVENTION The present invention is excellent in that it has hand-cutting properties and high adhesive strength, can be easily peeled off in a peeling operation after curing, and has no adhesive residue on an adherend. An object of the present invention is to provide an excellent adhesive tape for architectural curing which has removability and does not discolor with time.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a hand-cut adhesive tape having a thermoplastic resin base material provided with an adhesive layer on one surface and having a tear strength of zero. And the pressure-sensitive adhesive has a weight average molecular weight of 300,000 to 1 with an alkyl (meth) acrylate and a vinyl monomer copolymerizable therewith.
100,000, and 100 parts by weight of the acrylic copolymer having a dispersity of 6 to 12, and 3 to 30 parts by weight of a petroleum-based and / or terpene-based tackifier resin having a softening point of 70 to 150 ° C. It is a pressure-sensitive adhesive composition which is crosslinked by adding 0.1 to 2 parts by weight of a metal compound.

In the present invention, as the thermoplastic resin base material, at least one side of a cross layer obtained by weaving a flat yarn formed by chopping and stretching a thermoplastic resin film into at least one side, a laminate layer of the same resin is used. It is preferable to use a cross sheet provided with

[0008] In the cloth sheet, the denier of the flat yarn used for the weft of the cloth is suitably 2.0 to 4.5 times the denier of the warp. Further, it is preferable that the laminate layer is processed at a temperature that is 130 to 220 ° C. higher than the melting point of the thermoplastic resin constituting the cloth.

Further, as the thermoplastic resin base material, an embossed film having a number of parallel grooves provided in the width direction of the thermoplastic resin film may be used.

The acrylic copolymer has a molecular weight distribution divided into three component ranges, and has a weight average molecular weight of 500,000 to 8
It is preferable that the number average molecular weight is 60,000 to 90,000 and the degree of dispersion is 7 to 9.

The metal compound is preferably aluminum acetylacetonate or aluminum ethyl acetoacetate.

As the thermoplastic resin substrate in the present invention, it is preferable to use the above-mentioned cross sheet. The cross sheet is a cross made by weaving flat yarn made by chopping and stretching a thermoplastic resin film in the background,
At least one surface is provided with a laminate layer of a similar resin.

Examples of the thermoplastic resin film used as the material of the flat yarn used for the cloth include a polyolefin-based synthetic resin, a polyvinyl chloride-based synthetic resin comprising a homopolymer or a copolymer of polypropylene, polyethylene and α-olefins. Thermoplastic resins such as polyvinylidene chloride-based synthetic resin and polyethylene terephthalate-based synthetic resin are suitable.

These thermoplastic resin films are shredded and stretched 2 to 10 times to obtain flat yarns. Here, the fineness and yarn width of the flat yarn are not particularly limited, but as the warp of the cloth, the fineness is 60 to 150.
Denier, preferably 80 to 120 denier, and the yarn width is 0.4 to 1.1 mm, preferably 0.6 to 0.9.
mm.

The weft of the cloth has a fineness of 180.
It is suitable that the yarn width is 1.0 to 1.5 mm, preferably 1.1 to 1.3 mm. The warp yarn density is 25
The number is preferably 50 to 50 threads / inch, preferably 30 to 46 threads / inch, and the number of wefts to be driven is 12 to 25 threads / inch, preferably 14 to 20 threads / inch.

From the experimental results so far, the denier of the flat yarn used for the weft of the cloth should be 2.0 to 4.5 of the denier of the warp in order to make it easy to cut by hand in the horizontal direction. Preferably it is doubled.

Next, a laminate layer is formed on one or both sides of the cloth. Here, as the resin forming the laminate layer, a thermoplastic resin of the same system as the flat yarn forming the cloth is used.

The lamination is preferably performed at a processing temperature that is 130 to 220 ° C. higher than the melting point of the thermoplastic resin constituting the cloth. By laminating at a high temperature, the structure of the cloth can be fixed, and the cloth can be moderately thermally degraded, so that the cloth can be hand-cut.

The thermoplastic resin used in the production of the flat yarn of the present invention and the extrusion laminating may include, if necessary, auxiliaries such as pigments, heat stabilizers, light stabilizers, ultraviolet absorbers, inorganic and organic slip agents. And the aforementioned resins can be used in combination in an appropriate combination. Further, the thickness of the cross sheet can be arbitrarily set by changing the thickness of the laminate layer.

Further, as the thermoplastic resin base material in the present invention, an embossed film in which innumerable parallel grooves are provided in the width direction of a thick thermoplastic resin film can be used.

Examples of the thermoplastic resin film constituting the embossed film include a polyolefin-based synthetic resin, a polyvinyl chloride-based synthetic resin, and a polyvinylidene chloride-based synthetic resin comprising a homopolymer or a copolymer of polypropylene, polyethylene, and α-olefins. It is appropriate to use a thermoplastic resin such as a polyethylene terephthalate-based synthetic resin alone or in an appropriate mixture.

The thickness of the thermoplastic resin film is 90 to 2
A thickness of about 00 μm, preferably 100 to 150 μm is appropriate. The width of the groove formed in the thermoplastic resin film is 10 to 80 μm, preferably 20 to 50 μm, the depth of the groove is 15 to 60 μm, and preferably 20 to 40 μm. The thickness is suitably from 1 to 2.0 mm, preferably from 0.2 to 1.0 mm.

The surface of the thermoplastic resin base material to be coated with the pressure-sensitive adhesive according to the present invention is preferably subjected to a surface treatment such as high-pressure corona discharge in order to enhance the anchoring effect of the pressure-sensitive adhesive.

Next, an adhesive is applied to one surface of the thermoplastic resin base material. The adhesive is mainly composed of a copolymer of an alkyl (meth) acrylate and a vinyl monomer copolymerizable therewith. Petroleum and / or terpene based on 100 parts by weight of the copolymer. 3 to 30 parts by weight of a tackifier resin and crosslinked with a metal compound is used.

The alkyl (meth) acrylate in the acrylic copolymer used in the pressure-sensitive adhesive composition of the present invention preferably has an alkyl group having 1 to 18 carbon atoms.
These can be used alone or in combination.

Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate,
N-butyl (meth) acrylate, n- (meth) acrylate
-Octyl, 2-ethylhexyl (meth) acrylate, and the like, and these can be used alone or in combination of two or more.

The vinyl monomers copolymerizable with these (meth) acrylic esters include monomers having a carboxylic acid such as (meth) acrylic acid, maleic anhydride and itaconic acid, and (meth) acrylic acid 2 -A copolymerizable monomer component having a functional group, such as a monomer having a hydroxyl group such as hydroxyethyl and hydroxypropyl (meth) acrylate, and these may be used alone or in combination of two or more. it can.

Also, monomers containing a nitrogen atom such as (meth) acrylamides and vinylpyrrolidone;
Styrene, α-methylstyrene, vinyl acetate, (meth)
Copolymerizable components such as glycidyl acrylate can also be copolymerized with the alkyl (meth) acrylate.

An alkyl (meth) acrylate,
When this is copolymerized with a copolymerizable vinyl-based monomer component, the ratio is such that the alkyl (meth) acrylate is at least 70% by weight and the vinyl-based monomer component is 1 to 30% by weight. Is preferred.

The weight average molecular weight of the acrylic copolymer obtained by copolymerizing the alkyl acrylate and the vinyl monomer component is suitably from 300,000 to 1,000,000. When the weight average molecular weight is 300,000 or less, the cohesive strength of the copolymer is reduced, and adhesive residue is left on the adherend after curing. When the weight-average molecular weight is 1,000,000 or more, the adhesiveness may be reduced, and peeling from the adherend may occur during curing.

The degree of dispersion is suitably from 6 to 12. The dispersity is the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). When the dispersity is less than 6, the initial adhesive strength is insufficient, and when the dispersity is 12 or more, Adhesive residue may be left on the adherend after curing due to a decrease in cohesive force.

Preferably, the molecular weight distribution of the acrylic copolymer is divided into three component ranges, and the weight average molecular weight is 500,000 to 8
Those having a molecular weight of 10,000, a number average molecular weight of 60,000 to 90,000 and a dispersity of about 7 to 9 are preferred.

That is, according to the calibration curve of standard polystyrene by gel permeation chromatography, the weight average molecular weight is in the high molecular weight region of 1,000,000 or more, in the medium molecular weight region of 50,000 to 1,000,000, and in the low molecular weight region of 50,000 or less. , Each having a peak, and generally having a high molecular weight range of 10 to 2
It is preferable that the particles are dispersed so that 5% by weight, the medium molecular weight range is 55 to 85% by weight, and the low molecular weight range is 5 to 20% by weight.

Since the degree of dispersion is 7 to 9 and the molecular weight distribution is divided into three component regions (high, medium and low molecular weight peaks), the high molecular weight region contributes to removability due to an increase in cohesive strength, and the low molecular weight region Contributes to tackiness and high adhesive strength.

The petroleum-based tackifier resin used in the present invention includes an aliphatic hydrocarbon copolymer resin having a weight average molecular weight of 500 to 3000 and a softening point of 70 to 150 ° C.
Aromatic hydrocarbon copolymer resins, aliphatic / aromatic hydrocarbon copolymer resins, hydrogenated petroleum resins, and the like are suitable, and preferably have a weight average molecular weight of 1,000 to 1,700 and a softening point of nine.
0-120 ° C.

The weight average molecular weight is 500 or less, and the softening point is 7
When the temperature is 0 ° C or lower, the cohesive strength of the obtained pressure-sensitive adhesive composition is poor, and when the weight average molecular weight is 3000 or more and the softening point exceeds 150 ° C, the initial adhesive force and tack of the obtained pressure-sensitive adhesive composition are poor.

As the terpene-based tackifier resin used in the present invention, α- having a softening point of 70 to 150 ° C.
Pinene-based, β-pinene-based, limonene-based terpene resins, hydrocarbon-modified terpene resins, hydrogenated terpene resins, terpene phenolic resins and the like are suitable, and the softening point thereof is preferably 100 to 130 ° C. Appropriate.

If the softening point is 70 ° C. or lower, the cohesive strength of the obtained pressure-sensitive adhesive composition is inferior, and there is a risk of adhesive residue. If the softening point exceeds 150 ° C., the initial pressure-sensitive adhesive strength and tack Is inferior.

The above petroleum-based tackifier resin and terpene-based tackifier resin can be used alone or in combination of two or more kinds. 3 to 30 parts by weight with respect to
Preferably, 5 to 15 parts by weight is appropriate.

The pressure-sensitive adhesive composition of the present invention is obtained by crosslinking the above-mentioned mixture of acrylic copolymer and tackifier resin with a metal compound. Examples of the metal compound used include aluminum acetylacetonate,
Aluminum ethyl acetoacetate and the like can be mentioned.

The amount of the metal compound to be added is 0.1 to 2 parts by weight, preferably 0.2 to 0.8 parts by weight, based on 100 parts by weight of the solid content of the acrylic copolymer. When the amount of the metal compound curing agent is 0.1 part by weight or less, the cohesive force is reduced, and the adhesive remains on the adherend after curing. When the amount of the metal compound curing agent is 2 parts by weight or more, the adhesiveness is low. And may be peeled off from the adherend during curing.

The reason why a metal compound is used as a curing agent is that yellowing does not occur over time, the pressure-sensitive adhesive composition on the surface of the pressure-sensitive adhesive tape is not colored with time, and transparency is good. The metal-based compound curing agent may be mixed with the adhesive composition in advance and used in a one-pack type.

Further, the pressure-sensitive adhesive composition of the present invention may optionally
Antioxidants, UV absorbers, to improve weather resistance
A light stabilizer and the like can be added. In addition, a plasticizer can be added to improve coating properties.

The amount of the adhesive applied to the thermoplastic resin base material is suitably from 20 to 60 g / m ² as a solid content.

The pressure-sensitive adhesive tape of the present invention needs to have a tear strength in the width direction of 0.2 to 1.0 kgf, preferably 0.3 to 0.8 kgf. Since the tear strength of the pressure-sensitive adhesive tape depends on the tear strength of the thermoplastic resin base material, the tear strength of the thermoplastic resin base material needs to satisfy the above values.

When the tear strength is less than 0.2 kgf,
The adhesive tape may be inadvertently torn when it is pulled out of the roll, making it impossible to smoothly pull out the adhesive tape over the desired length, or it may be broken when peeling off after curing. If it exceeds 1.0 kgf, it will be difficult to cut it easily by hand.

Although the thickness of the substrate is not limited,
It is desirably 90 to 200 μm, preferably 100 to 150 μm. When the thickness is less than 90 μm, the adhesive tape is hardly turned up in a peeling operation, and when the thickness exceeds 200 μm, the flexibility is deteriorated, and the fitting property to a curved surface or an acute angle portion is significantly reduced, and the adhesive tape is economically disadvantageous. It is just.

[0048]

According to the present invention, the tackifier resin (petroleum-based resin, terpene-based resin) mixed with the pressure-sensitive adhesive composition improves the adhesive force to the thermoplastic resin base material and improves the peeling after curing. No release of the adhesive composition from the substrate,
Good removability and no adhesive residue.

In the case of a rosin-based resin which has been widely used in this type of pressure-sensitive adhesive tape, the cohesive force tends to decrease and the removability tends to deteriorate. There is a rise, and adhesive residue remains on the adherend upon re-peeling. Further, the pressure-sensitive adhesive composition is colored.

According to the present invention, the adhesive strength of the pressure-sensitive adhesive tape to the stainless steel plate is about 800 to 1500 g / 25 mm, the adhesive strength to the polyethylene board is about 300 to 600 g / 25 mm, and the peel strength after sticking to the stainless steel board is 70. 3 at ℃
Even after 30 days at 40 ° C. or day, the adhesive tape for curing has good removability without exceeding twice the initial adhesive strength.

[0051]

The present invention will be described below with reference to examples.

[Manufacture of Base Material] <Crosssheet Manufacturing Example> A high-density polyethylene (MFR) appropriately blended with auxiliaries such as a light stabilizer, a heat stabilizer, and a slip agent.
0.6, melting point: 133 ° C.), extruded from a circular die while melting and kneading in an extruder to form a cylindrical film, slit the film into a narrow width, and then 7.5 times while heating again. , And after annealing, the fineness is 90 denier as the warp, the yarn width is 0.7 mm, and the fineness is 2 as the weft.
Each flat yarn having a denier of 80 and a width of 1.2 mm was obtained.

Next, the warp yarn was woven into a plain weave cloth with a yarn density of 46 yarns / inch and the number of wefts being driven at 16 yarns / inch. A low-density polyethylene resin (MF
R10, melting point: 111 ° C.), the resin temperature and thickness were variously changed as shown in Table 1 to form laminate layers, and the cross sheets of Production Examples 1 to 5 were obtained.

[0054]

[Table 1]

<Example of embossed film production> 100 parts by weight of linear polyethylene (density 0.94, MFR 1.0) was added to low-density polyethylene (density 0.92, MFR 2.
0) On one side of the unstretched film blended with 20 parts by weight,
And the embossed films of Production Examples 6 to 8 were obtained.

[0056]

[Table 2]

Tables 1 and 2 show the physical properties of the substrates (Production Examples 1 to 8) obtained in Production Examples. The physical properties of the substrate were measured by the following methods.

[Physical Properties Test] (1) Tensile Strength and Tensile Elongation of Base Material Measured according to JISL1096. The measurement direction is the winding direction of the tape. (2) Tearing strength of base material According to JIS L1096A-1 method, tearing was performed at a speed of 600 mm / min over a length of 50 mm, and three maximum values and three minimum values were read from the recording paper, and the average value was obtained. Expressed by The measurement direction is a direction perpendicular to the winding direction of the adhesive tape.

[Production of Adhesive Tape] <Example 1> In a reaction vessel equipped with a thermometer, a nitrogen inlet tube, a stirrer, and a cooling tube, 40 parts by weight of toluene and 60 parts by weight of ethyl acetate as a solvent component, Component n-butyl acrylate 49 parts by weight, 2-ethylhexyl acrylate 2
1 part by weight and 4 parts by weight of acrylic acid were charged, and the temperature was increased to 75 ° C. by stirring while blowing nitrogen gas. Then
A separately prepared solution of 21 parts by weight of the polymer component n-butyl acrylate and 9 parts by weight of 2-ethylhexyl acrylate, and 0.1 parts of benzoyl peroxide as a polymerization initiator.
A solution consisting of 2 parts by weight and 10 parts by weight of ethyl acetate was dropped into the system over 3 hours, and a polymerization reaction was carried out at the same temperature for 8 hours. To the mixture was added 17 parts by weight of toluene as a diluting solvent. A coalescence was obtained.

The copolymer was measured by gel permeation chromatography using a calibration curve with standard polystyrene, and peaks appeared at positions where the weight average molecular weight was about 2,000,000, 200,000 and 25,000. The molecular weight distribution was divided into three component ranges, the weight average molecular weight was about 720,000, the number average molecular weight was 96,000, and the dispersity was 7.5.

The solid content weight of this acrylic copolymer solution was 1
The weight average molecular weight was 1300 and the softening point was 10
10 parts by weight of an aromatic hydrocarbon copolymer resin at 0 ° C. is dissolved, and a metal chelate-based curing agent (trade name: aluminum chelate A, manufactured by Kawaken Fine Chemicals Co., Ltd.) is used as a crosslinking agent.
Was added to obtain an adhesive composition (A).

The pressure-sensitive adhesive composition (A) was applied to the substrate obtained in Production Example 1 so that the coating amount after drying was 40 g / m ² , to obtain a pressure-sensitive adhesive tape.

Example 2 An adhesive tape was obtained in the same manner as in Example 1 except that the substrate was changed to Production Example 2.

Example 3 An adhesive tape was obtained in the same manner as in Example 1 except that the substrate was changed to Production Example 3.

Example 4 An adhesive tape was obtained in the same manner as in Example 1 except that the substrate was changed to Production Example-6.

<Example-5> An adhesive tape was obtained in the same manner as in Example-1, except that the substrate was changed to Production Example-7.

<Example-6> An adhesive tape was obtained in the same manner as in Example-1, except that the substrate was changed to Production Example-8.

<Example-7> An adhesive composition (B) was prepared in the same manner as in Example-1 except that the amount of the aromatic hydrocarbon copolymer resin in Example-1 was changed to 15 parts by weight. ) Got.

The pressure-sensitive adhesive composition (B) was applied to the substrate obtained in Production Example 2 so that the coating amount after drying was 40 g / m ² , to obtain a pressure-sensitive adhesive tape.

<Example-8> The procedure of Example-1 was repeated, except that the aromatic hydrocarbon copolymer resin in Example-1 was changed to a terpenephenol copolymer resin having a softening point of 130. An adhesive composition (C) was prepared.

The pressure-sensitive adhesive composition (C) was applied to the substrate obtained in Production Example-2 so that the coating amount after drying was 40 g / m ² , to obtain a pressure-sensitive adhesive tape.

Example 9 In a reaction vessel shown in Example 1, 40 parts by weight of toluene and 60 parts by weight of ethyl acetate as solvent components and n-butyl acrylate 35 as a polymer component were placed.
Parts by weight, 15 parts by weight of 2-ethylhexyl acrylate, and 4 parts by weight of acrylic acid were charged, and the temperature was raised to 75 ° C. while stirring while blowing in nitrogen gas.

Next, a separately prepared solution of 35 parts by weight of n-butyl acrylate and 15 parts by weight of 2-ethylhexyl acrylate, 0.2 parts by weight of benzoyl peroxide and 10 parts by weight of ethyl acetate as polymerization initiators The solution was added dropwise to the system over 6 hours. Further, a polymerization reaction was carried out at the same temperature for 5 hours, and 17 parts by weight of toluene was added as a diluting solvent to obtain an acrylic copolymer.

The molecular weight of this copolymer was measured by a gel permeation chromatography method. As a result, the molecular weight distribution of this copolymer was divided into three component regions, the weight average molecular weight was about 780,000, and the number average molecular weight. Was 88,000, and the degree of dispersion was 8.9.

The solid weight of this acrylic copolymer solution was 10
0 part, weight average molecular weight 1300, softening point 100
10 parts by weight of an aromatic hydrocarbon copolymer resin at 0 ° C. are dissolved, and a metal chelate-based curing agent (aluminum chelate A) is added as a cross-linking agent in a solid weight of 0.35 part to prepare an adhesive composition (D). did.

The pressure-sensitive adhesive composition (D) was applied to the substrate obtained in Production Example 2 so that the coating amount after drying was 40 g / m ² , to obtain a pressure-sensitive adhesive tape.

Example 10 The pressure-sensitive adhesive composition (E) was prepared in the same manner as in Example 9 except that the amount of the aromatic hydrocarbon copolymer resin in Example 9 was changed to 15 parts by weight. Prepared.

The pressure-sensitive adhesive composition (E) was applied to the substrate obtained in Production Example 2 so that the coating amount after drying was 40 g / m ² , to obtain a pressure-sensitive adhesive tape.

<Example 11> The procedure of Example 9 was repeated, except that the aromatic hydrocarbon copolymer resin in Example 9 was changed to a terpene phenol copolymer resin having a softening point of 130. An adhesive composition (F) was prepared.

The above-mentioned pressure-sensitive adhesive composition (F) was applied to the substrate obtained in Production Example 2 such that the coating amount after drying was 40 g / m ² to obtain a pressure-sensitive adhesive tape.

Example 12 An adhesive tape was obtained in the same manner as in Example 9 except that the substrate was changed to Production Example 6.

<Comparative Example-1> The reaction vessel of Example-1 was
40 parts by weight of toluene and 60 parts by weight of ethyl acetate as a solvent, 70 parts by weight of n-butyl acrylate, 30 parts by weight of 2-ethylhexyl acrylate and 4 parts by weight of acrylic acid as a polymer component were stirred and stirred while blowing nitrogen gas. The temperature was raised to 75 ° C.

Next, a solution consisting of 0.3 parts by weight of benzoyl peroxide and 10 parts by weight of ethyl acetate as a polymerization initiator was added dropwise over 3 hours at the same temperature, and a polymerization reaction was carried out at the same temperature for 8 hours. Toluene 1 as diluting solvent
7 parts by weight were added to obtain an acrylic copolymer solution.

The molecular weight of this copolymer was measured by gel permeation chromatography. As a result, the weight average molecular weight was about 530,000, the number average molecular weight was 100,000, and the dispersion ratio was 5.3.

The solid weight of this acrylic copolymer solution was 10
To 0 part, a polyisocyanate compound (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) was added as a crosslinking agent in an amount of 1 part by weight of solid content to obtain an adhesive composition (G).

The pressure-sensitive adhesive composition (G) was applied to the substrate obtained in Production Example 2 so that the coating amount after drying was 40 g / m ² , to obtain a pressure-sensitive adhesive tape.

<Comparative Example 2> An adhesive tape was obtained in the same manner as in Comparative Example 1, except that the substrate was changed to Production Example-6.

Comparative Example 3 A softening point of 9 relative to 100 parts of the solid weight of the acrylic copolymer solution in Comparative Example 1 was obtained.
10 parts by weight of disproportionated rosin glycerin ester at 0 ° C. was dissolved, and 1 part by weight of a polyisocyanate compound (Coronate L) as a crosslinking agent was added to obtain a pressure-sensitive adhesive composition (H).

The pressure-sensitive adhesive composition (H) was applied to the substrate obtained in Production Example 2 so that the coating amount after drying was 40 g / m ² , to obtain a pressure-sensitive adhesive tape.

Comparative Example 4 An adhesive tape was obtained in the same manner as in Comparative Example 3, except that the substrate was changed to Production Example 6.

<Comparative Example-5> The reaction vessel of Example-1 was
40 parts by weight of toluene as a solvent component and 60 parts by weight of ethyl acetate were charged and stirred while blowing in nitrogen gas, and the temperature was raised to 75 ° C.

Next, a previously prepared solution consisting of 70 parts by weight of a polymer component, n-butyl acrylate, 30 parts by weight of 2-ethylhexyl acrylate and 4 parts by weight of acrylic acid, and benzoyl peroxide as a polymerization initiator A solution of 0.1 parts by weight and 10 parts by weight of ethyl acetate was dropped into the system over 6 hours, a polymerization reaction was further performed at the same temperature for 5 hours, and 17 parts by weight of toluene was further added as a diluting solvent. An acrylic copolymer solution was obtained.

The molecular weight of this copolymer was measured by gel permeation chromatography. As a result, the weight average molecular weight was about 740,000, the number average molecular weight was about 60,000, and the degree of dispersion was 12.3.

The acrylic copolymer solution had a solid weight part of 1
To 100 parts of a polyisocyanate compound (Coronate L) as a cross-linking agent, 1 part by weight of solid content was added to obtain a pressure-sensitive adhesive composition (I).

The pressure-sensitive adhesive composition (I) was applied to the substrate obtained in Production Example 2 so that the coating amount after drying was 40 g / m ² to obtain a pressure-sensitive adhesive tape.

Comparative Example 6 A softening point of 90 ° C. was added to 100 parts by solid weight of the acrylic copolymer solution of Comparative Example-5.
Of 10 parts by weight of disproportionated rosin glycerin ester, and 1 part by weight of a polyisocyanate compound (Coronate L) as a cross-linking agent, is added to the pressure-sensitive adhesive composition (J).
I got

The pressure-sensitive adhesive composition (J) was applied to the substrate obtained in Production Example 2 so that the coating amount after drying was 40 g / m ² , to obtain a pressure-sensitive adhesive tape.

<Comparative Example-7> The reaction vessel of Example-1 was
70 parts by weight of ethyl acetate as a solvent, and 70 parts by weight of n-butyl acrylate, 30 parts by weight of 2-ethylhexyl acrylate and 4 parts by weight of acrylic acid as polymer components, and stirred while blowing in nitrogen gas, to 75 ° C. The temperature rose.

Next, a solution of 0.3 parts by weight of benzoyl peroxide as a polymerization initiator and 10 parts by weight of ethyl acetate was added dropwise at the same temperature over 2 hours, and a polymerization reaction was further performed at the same temperature for 8 hours. , Toluene 47 as a diluting solvent
By weight, an acrylic copolymer solution was obtained.

The molecular weight of this copolymer was measured by gel permeation chromatography. As a result, the weight average molecular weight was about 850,000, the number average molecular weight was 200,000, and the degree of dispersion was 4.3.

Solid part by weight 1 of this acrylic copolymer solution
To 100 parts of a polyisocyanate compound (Coronate L) as a crosslinking agent, 2 parts by weight of solid content was added to prepare a pressure-sensitive adhesive composition (K).

The pressure-sensitive adhesive composition (K) was applied to the substrate obtained in Production Example 2 so that the coating amount after drying was 40 g / m ² to obtain a pressure-sensitive adhesive tape.

Comparative Example 8 An adhesive tape was obtained in the same manner as in Example 1 except that the substrate was changed to Production Example 4.

<Comparative Example 9> An adhesive tape was obtained in the same manner as in Example 1, except that the substrate was changed to Production Example-5.

The methods for measuring the adhesive properties and practical physical properties of the adhesive tape are described below. [Adhesive Strength] According to JIS Z 0237, an adhesive tape having a width of 25 mm was adhered to a stainless steel plate (SUS), and allowed to stand for 30 minutes.
The 180 degree peel strength at 0 mm / min was measured. Similarly, the 180-degree peel strength of the polyethylene plate was measured.

[Ball tack] JIS Z 0237
The measurement was carried out in an atmosphere of 20 ° C. and 65% RH at an angle of the inclined plate of 30 ° and the runway of 100 mm in accordance with the above.

[Holding force] According to JIS Z 0237, an adhesive tape was applied to a stainless steel plate (SUS) at 25 × 25.
Then, a 1 kg load was applied at 40 ° C., and the deviation width after 1 hour was measured.

[SUS plate peeling property] An adhesive tape was stuck on a stainless steel plate by the above-mentioned method, and was heated at 70 ° C for 3 days and at 40 ° C.
For 30 days and allowed to cool, and then the 180-degree peel strength was measured according to JISZ0237. At the same time, the stainability of the stainless steel surface was evaluated, and was evaluated as 糊 when there was no contamination (residual adhesive), and as X when there was contamination.

[Practicality evaluation test] Hand tearability: Ten monitors wearing working gloves tore the adhesive tapes of Examples and Comparative Examples by hand in the width direction. Difficult ones or difficult ones were represented by x.

Workability: Adhesive tapes of Examples and Comparative Examples were stuck to the surface of a stainless steel plate subjected to a hairline process, which is widely used as a building material, at 23 ° C. and 65 ° C.
After storing for 50 days in an environment of% RH, the adhesive tape was quickly peeled off from the stainless steel plate.

[0111] The sample was evaluated as ○ when there was no peeling or lifting of the adhesive tape during the 50 days, and the adhesive tape was not cut during peeling, and x when these phenomena occurred.

Stainability: In the above evaluation of workability, the surface of the stainless steel plate after peeling off the adhesive tape was observed.

Table 3 shows the test results.

[Table 3]

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Hiroto Ishiko 671 Mizuhashi, Noguchi-cho, Kakogawa-shi, Hyogo Prefecture Inside Harima Chemicals Co., Ltd. Central Research Laboratory (72) Inventor Hikaru Shibata 671 Mizuhashi, Noguchi-cho, Kakogawa-shi, Hyogo Address 4 Harima Chemicals Central Research Laboratory

Claims (7)

[Claims] An adhesive tape having a hand-cutting property in which an adhesive layer is provided on one side of a thermoplastic resin base material,
The pressure-sensitive adhesive tape has a tear strength of 0.2 to 1.0 kgf, and the pressure-sensitive adhesive has a weight average molecular weight of 300,000 to 1,000,000 with an alkyl (meth) acrylate and a vinyl monomer copolymerizable therewith. Containing 100 parts by weight of an acrylic copolymer having a dispersity of 6 to 12 and 3 to 30 parts by weight of a petroleum-based and / or terpene-based tackifier resin having a softening point of 70 to 150 ° C; Metal compound 0.1
A pressure-sensitive adhesive tape, characterized in that the pressure-sensitive adhesive composition is a cross-linked pressure-sensitive adhesive composition having an addition of 2 to 2 parts by weight. 2. A cloth in which the thermoplastic resin base material is cross-woven with flat yarns obtained by shredding and stretching a thermoplastic resin film, and at least one surface thereof is provided with a laminate layer of a similar resin. The adhesive tape according to claim 1, wherein the adhesive tape is a cross sheet. 3. The denier of the flat yarn used for the weft of the cloth is 2.0 to 4.0 of the denier of the warp.
3. The pressure-sensitive adhesive tape according to claim 2, wherein the pressure-sensitive adhesive tape is five-fold. 4. The method according to claim 2, wherein the laminating layer is formed at a processing temperature higher by 130 to 220 ° C. than a melting point of a thermoplastic resin constituting the cloth.
Or the adhesive tape according to 3. 5. The thermoplastic resin base material is provided with a large number of parallel grooves in a width direction of the thermoplastic resin film.
The adhesive tape according to claim 1, wherein the adhesive tape is an embossed film. 6. The acrylic copolymer has a molecular weight distribution of three components, and a weight average molecular weight of 500,000 to 80.
The pressure-sensitive adhesive tape according to claim 1, wherein the number average molecular weight is from 60,000 to 90,000, and the degree of dispersion is from 7 to 9. 7. The pressure-sensitive adhesive tape according to claim 1, wherein the metal-based compound is aluminum acetylacetonate or aluminum ethyl acetoacetate.