JP2001172586A - Hand-cuttable adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hand-cuttable adhesive tape which has excellent adhesion, re-releasability, hand-cuttable properties, elongation prevention, curl resistance and prevention of lifting at the edges of the tape. SOLUTION: The adhesive tape is obtained by coating (A) a polyester-based resin which has a number average molecular weight of 10,000 or more and a glass transition temperature of 0-80 deg.C on the concave-convex surface of (I) an unoriented polyolefin-based resin base film which has a striped concave- convex surface formed on one side wherein the patterns are 0.03-0.3 mm deep and located at an interval of 0.5-5 mm orthogonal to the longer direction of the adhesive tape and which has a difference between the thickness of the base film and the depth of the pattern of 10-90 μm, and then by coating (B) an acrylic adhesive composition thereon.

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, and more particularly, to a hand-cut adhesive tape excellent in adhesiveness and removability, and further excellent in hand-cutting property, prevention of longitudinal elongation, flexibility and the like. The present invention relates to an adhesive tape.

[0002]

2. Description of the Related Art Conventionally, a removable adhesive tape has been used for architectural curing and paint curing, and such a tape is used so that the tape can be cut easily with bare hands during the attaching operation. A so-called hand-cutting tape with a devised base material is frequently used, and an unstretched polyolefin base material provided with hand-cutting properties by embossing is used as the base material.

However, the hand-cut adhesive tape is easily stretched in the longitudinal direction when the roll-shaped wound tape is developed to a required length or cut with bare hands. Shrinkage causes problems such as, for example, in paint masking applications, the boundary between surfaces to be painted and surfaces not to be painted becomes unclear, or the tape edge floats. Also, in order to suppress elongation,
If the depth of the emboss is reduced or the thickness of the base film is increased, the hand-cutting property deteriorates and the workability is impaired, the flexibility is impaired, and the adhesion to curved or rough surfaces deteriorates. Problem arises.

In order to solve these problems, in recent years, for example, JP-A-10-219203 discloses an adhesive tape containing a specific unstretched polyolefin base material, a reinforcing film layer and an adhesive layer. In the official gazette, the base material layer includes an aluminum foil layer, and a specific unstretched polyolefin resin layer which is bonded to the aluminum foil layer with an adhesive, and an adhesive comprising a pressure-sensitive adhesive layer applied on the base material layer Japanese Patent Application Laid-Open No. Hei 9-137133 proposes an adhesive tape comprising a specific unstretched polyolefin substrate and a composite layer comprising a reinforcing material such as a nonwoven fabric or a split cloth and an adhesive.

[0005]

However, in the technique disclosed in Japanese Patent Application Laid-Open No. H10-219203, a step of bonding a reinforcing film such as a polypropylene film to a base material via an adhesive is required, and workability is complicated. It is not economical at the same time. Furthermore, since the reinforcing film is bonded, prevention of elongation in the longitudinal direction is recognized,
Actually, the hand-cutting property is insufficient, and the two have not been satisfied.

Similarly, Japanese Patent Application Laid-Open Nos. 10-17832 and 9-137133 similarly disclose all aspects such as hand-cutting property, prevention of longitudinal elongation, and flexibility such as adhesive strength to a curved surface. It is not satisfactory, and further improvement is desired. Under these circumstances, the present invention is excellent in adhesiveness and removability, and further excellent in flexibility such as hand cutting property, prevention of elongation in the longitudinal direction, adhesion to a curved surface or a rough surface, and curling resistance. It is an object of the present invention to provide a hand-cut adhesive tape.

[0007]

Means for Solving the Problems However, the inventors of the present invention have conducted intensive studies in view of such circumstances, and as a result, have found that one side has a thickness of 0.03 to 0.3 mm perpendicular to the longitudinal direction of the adhesive tape.
An unstretched polyolefin-based material in which a striped uneven surface having a squeezing depth of 0.5 to 5 mm and a difference between the thickness of the base film and the squeezing depth of 10 to 90 μm is formed. A polyester resin (A) having a number average molecular weight of 10,000 or more and a glass transition temperature of 0 to 80 ° C is applied to the uneven surface of the resin base film (I),
Furthermore, a hand-cut adhesive tape obtained by applying the acrylic adhesive composition (B) thereon was found to meet the above-mentioned object, and the present invention was completed.

In the present invention, it is preferable that a crosslinking agent (C) is further added to the polyester resin (A). Further, the acrylic pressure-sensitive adhesive composition (B) contains 1 to 20% by weight of a carboxyl group- or amino group-containing unsaturated monomer, 0 to 20% by weight of a hydroxyl group-containing unsaturated monomer,
(Meth) acrylic acid alkyl ester 50% by weight or more,
And an acrylic copolymer (D) having a glass transition temperature of less than −20 ° C., which is composed of 0 to 49% by weight of other copolymerizable monomers, and more preferably the acrylic copolymer. It is preferable that (D) contains a tackifier (E) and a crosslinking agent (F).

[0009]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.
As shown in FIG. 1, the polyolefin-based resin base film (I) used in the present invention has, on one surface thereof, a stripe-shaped aperture in the direction perpendicular to the longitudinal direction of the adhesive tape (the aperture has a triangular or rectangular cross-sectional shape). , (Semi-) circular, etc., which is not particularly limited).
0.03 to 0.3 mm (more preferably 0.04 to 0.3 mm).
12 mm), and the depth (a) is
When the thickness is less than 0.03 mm, the tearing property in the longitudinal direction of the adhesive tape is improved, but the tearing property in the width direction is impaired. On the contrary, when it exceeds 0.3 mm, the tearing property in the longitudinal direction of the adhesive tape is impaired, and You cannot achieve your goal.

Also, the distance between the stripe-shaped apertures (b)
Is 0.5 to 5 mm (more preferably 0.6 to 1.4 m
m), and the interval (b) is 0.5
If it is less than 5 mm, the strength of the adhesive tape in the longitudinal direction is insufficient, and if it exceeds 5 mm, the original hand-cutting property becomes insufficient,
Also in this case, the object of the present invention cannot be achieved.

In the present invention, the thickness (c) of the polyolefin resin base film (I) and the depth of drawing (a) are further determined.
Is required to be 10 to 90 μm, and if the difference is less than 10 μm, the tearability in the longitudinal direction is impaired, and at the same time, the base film of the polyester resin (A) and the acrylic pressure-sensitive adhesive composition (B) When the thickness exceeds 90 μm, the tearability in the width direction is impaired, and at the same time, the curl of the substrate film becomes too large, so that the object of the present invention cannot be achieved.

Further, the polyolefin-based resin base film (I) needs to be unstretched. In the case of a stretched film, the film is liable to be torn due to scratches or the like in a step of forming a squeezed portion, and is heated after the squeezing process. This causes inconveniences such as shrinkage of the film, which is inappropriate. Further, the surface roughness (Ra) of the polyolefin resin substrate film (I) on the side opposite to the uneven surface is preferably 30 μm or less, more preferably 20 μm or less, and the surface roughness (Ra) ) Exceeds 30 μm, which leads to a decrease in adhesive strength when the roll-shaped tape is peeled off and adhered to an adherend, and at the same time, when the base film is thin, it leads to a decrease in the strength of the base film. Absent.

The production of the polyolefin-based resin substrate film (I) is not particularly limited. For example, the polyolefin-based resin substrate film is coated on one surface of the polyolefin-based resin substrate film by an embossing roll having an uneven surface satisfying the above-mentioned drawn shape. What is necessary is just to produce a stripe-shaped uneven pattern, and it is sufficient to finally cut such a stripe so as to be in a direction orthogonal to the longitudinal direction of the adhesive tape.

Further, the corrugated surface is subjected to corona treatment to reduce the surface tension to 35 to 60 dyne / cm (more preferably 40 dyne / cm).
~ 50 dyne / cm) is also preferable, and by such treatment, the adhesiveness of the polyester resin (A) and the acrylic pressure-sensitive adhesive composition to the uneven surface of the base film is improved, and the removability is improved. .

A polyester resin (A) is applied to the uneven surface of the unstretched polyolefin resin base film (I) thus obtained, and an acrylic pressure-sensitive adhesive composition (B) is further applied thereon. Thus, the hand-cut adhesive tape of the present invention is obtained.

The polyester resin (A) has a number average molecular weight of 10,000 or more and a glass transition temperature of 0.
８０80 ° C. and a number average molecular weight of 10.0
If it is less than 00, the strength of the coating film is low, there is no effect of suppressing the elongation of the pressure-sensitive adhesive tape in the longitudinal direction, and the hand-cutting property is poor.
If the glass transition temperature is lower than 0 ° C., the coating film strength is low, there is no effect of suppressing the elongation of the adhesive tape in the longitudinal direction, and the hand-cutting property is poor. If it exceeds 80 ° C., the polyolefin resin base film (I However, problems such as the inability to suppress longitudinal elongation of the pressure-sensitive adhesive tape, poor adhesion due to poor flexibility and poor adhesion to curved or rough surfaces, etc., occur.

The method for producing the polyester resin (A) is not particularly limited as long as the number average molecular weight and the glass transition temperature satisfy the above requirements, and the aromatic dicarboxylic acid and / or the aliphatic dicarboxylic acid may be used. A method of producing a polybasic acid and a monomer of a polyhydric alcohol by an ordinary dehydration condensation reaction is exemplified. In the dehydration-condensation reaction, it is preferable to use a catalyst such as tetrabutoxytitanate, dibutyltin oxide, antimony trioxide, cobalt acetate, or zinc acetate, if necessary.

Examples of the polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, 3,6-endomethylenetetrahydrophthalic anhydride, tetrahydrophthalic acid, tetrachlorophthalic anhydride, 3,6-endodichloromethylenetetrachlorophthalic acid, Succinic acid, adipic acid, sebacic acid,
One or more unsaturated polybasic acids such as terpene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc., itaconic acid, mesaconic acid, citraconic acid, citraconic anhydride, chlorinated maleic acid, etc. Two or more are used.
In addition, trivalent or higher valent acids such as pyromellitic acid, pyromellitic anhydride, and trimellitic acid can also be used.

Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol,
Trimethylene glycol, butylene glycol (1,
3), butylene glycol (2,3), tetramethylene glycol, bisphenol dioxyethyl ether,
Bihydric alcohols such as bisphenoldioxypropyl ether, neopentyl glycol and butenediol (1,4); trivalent such as glycerin, trimethylolpropane, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, sorbitol One or more of the above alcohols are used.

In the production of the polyester resin (A), the number average molecular weight and the glass content of the polybasic acid and the polyhydric alcohol are changed by changing the charge ratio of the polybasic acid and the polyhydric alcohol and the molecular weight of the polybasic acid and the polyhydric alcohol monomer. The transition temperature can be adjusted to the above range.

In the present invention, it is preferable to further blend a crosslinking agent (C) with the polyester resin (A) from the viewpoint of improving the adhesion to the base film. The amount is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the system resin (A). When the amount is less than 0.1 part by weight, the strength of the coating film is low and the hand-cutting property is insufficient. On the other hand, when the amount exceeds 20 parts by weight, the adhesion to the substrate film is deteriorated.

The crosslinking agent (C) is not particularly limited, but may be epoxy, metal salt, metal alkoxide, aldehyde compound, non-amino resin amino compound, urea, isocyanate, metal chelate, melamine, aziridine. And the like. Among these, particularly preferred are isocyanate compounds, more preferably polyfunctional isocyanates, for example, trimethylolpropane adduct of tolylene diisocyanate, ethylene diisocyanate, 1,4-butane diisocyanate, dicyclohexyl. Methane diisocyanate, cyclohexane diisocyanate, 2,6-tolylene diisocyanate, 4,
4'-diphenylmethane diisocyanate, isophorone diisocyanate and the like.

In applying the polyester resin (A) to the polyolefin resin base film (I), the polyester resin (A) is diluted with a solvent, and the resin content is 5 to 50% by weight, preferably 10 to 50% by weight. ４０40% by weight is preferably applied.
It is preferably 20 g / cm ² , more preferably 0.2 to 10 g / cm ² . The application amount is 0.1 g /
cm longitudinal elongation-preventing effect of the adhesive tape is less than ² hardly obtained, 20 g / cm ² to greater than the adhesive tape hand cutting property is poor undesirably.

Examples of the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, methyl cellosolve and the like. Further, the application method is not particularly limited,
Known methods such as a gravure coater, a reverse roll coater, and a kiss coater can be employed.

In the present invention, the acrylic pressure-sensitive adhesive composition (B) is further applied thereon. As the acrylic pressure-sensitive adhesive composition (B), a carboxyl group- or amino group-containing unsaturated monomer is used. 1-20% by weight of a monomer, 0-20% by weight of a hydroxyl group-containing unsaturated monomer, 50% by weight or more of an alkyl ester of (meth) acrylic acid, and 0-49% by weight of another copolymerizable monomer Acrylic copolymer (D) having a glass transition temperature of less than −20 ° C. is preferable, and in particular, the acrylic copolymer (D) further comprises a tackifier (E) and a crosslinking agent (D). It is preferable that the pressure-sensitive adhesive composition contains F).

1 to 20% by weight of the unsaturated monomer having a carboxyl group or an amino group, 0 to 20% by weight of an unsaturated monomer having a hydroxyl group, 50% by weight or more of an alkyl ester of (meth) acrylic acid, and others. Having a glass transition temperature of -20 ° C comprising 0 to 49% by weight of a copolymerizable monomer of
The acrylic copolymer (D) is a carboxyl group- or amino group-containing unsaturated monomer (d1), a hydroxyl group-containing unsaturated monomer (d2), an alkyl ester of (meth) acrylic acid (d3 ) And other copolymerizable monomers (d4).

Examples of the unsaturated monomer (d1) containing a carboxyl group or an amino group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, maleic acid, fumaric acid, citraconic acid, glutaconic acid and itaconic acid. Examples include carboxyl group-containing monomers such as polycarboxylic acids and anhydrides thereof, and amino group-containing monomers such as (meth) acrylamide, N, N'-dimethylaminomethacrylate, and N-methylol (meth) acrylamide. Preferably, (meth) acrylamide is used.

Hydroxyl group-containing unsaturated monomer (d2)
Are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Chloro-2-hydroxypropyl (meth) acrylate and the like, and preferably, 2-hydroxyethyl (meth) acrylate is used.

Examples of the alkyl ester (d3) of (meth) acrylic acid include ethyl acrylate and n-acrylic acid.
Butyl, iso-butyl acrylate, methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl acrylate, lauryl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-ethylhexyl methacrylate, methacrylic acid Examples thereof include lauryl, benzyl methacrylate, cyclohexyl methacrylate, stearyl acrylate, stearyl methacrylate, and the like. N-butyl acrylate and 2-ethylhexyl acrylate are preferably used. Still other copolymerizable monomers (d4) include vinyl acetate, acrylonitrile, methacrylonitrile, styrene, vinyl propionate and the like.

In the above acrylic copolymer (D), (d)
The copolymerization ratio of 1) to (d4) is as follows: (d1) is 1 to 20% by weight (further 1 to 10% by weight), (d2) is 0 to 20% by weight (further 0 to 10% by weight), (D3) is 50% by weight
Above (further 70-98% by weight), (d4) is 0-49
If the content of (d1) is less than 1% by weight, poor adhesion to metal and re-peelability become poor, and conversely, 20% by weight.
If it exceeds, the adhesion to the polyolefin resin becomes poor, which is not preferable. If (d2) exceeds 20% by weight, poor adhesion to metal and plastic occurs, and (d3) is 5%.
If the content is less than 0% by weight or (d4) exceeds 49% by weight, the adhesive strength becomes insufficient, which is not preferable.

The acrylic copolymer (D) preferably has the copolymerization ratio as described above, but more preferably has a glass transition temperature of less than -20 ° C, and has a glass transition temperature of -20 ° C or more. In this case, the adhesive strength becomes insufficient, which is not preferable. The adjustment of the glass transition temperature is performed by the above (d3)
And (d4) can be controlled by adjusting the type and the copolymerization ratio.

In preparing the acrylic copolymer (D), the acrylic copolymer (D) is easily produced by a method well known to those skilled in the art, such as radical copolymerization of (d1) to (d4) in an organic solvent. Examples of the organic solvent used include aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, aliphatic alcohols such as n-propyl alcohol and iso-propyl alcohol, methyl ethyl ketone, and methyl isobutyl ketone. ,
Ketones such as cyclohexanone, and the like, and the polymerization catalyst to be used include azobisisobutyronitrile, benzoyl peroxide, which is a usual radical polymerization catalyst,
Specific examples include di-t-butyl peroxide and cumene hydroperoxide.

Examples of the tackifier (E) include rosin resins (rosin or disproportionated rosin, esters of water-added rosin), tempel resins, xylene resins (addition reaction product of xylene and formaldehyde), Phenolic resins, silicone resins, cumarone resins, petroleum resins and the like are mentioned, and preferably one or more of rosin resins, terpene resins and xylene resins are used. The content of the tackifier (E) is preferably 2 to 30 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the acrylic copolymer (D). When the content is less than 2 parts by weight, the adhesive strength does not increase, and
Adhesion to the base film and the polyester-based resin decreases, and if it exceeds 30 parts by weight, removability deteriorates.

Further, as the crosslinking agent (F), epoxy type, metal salt, metal alkoxide, aldehyde type compound,
Non-amino resin-based amino compounds, urea-based, isocyanate-based, metal chelate-based, melamine-based, aziridine-based, and the like, include cross-linking agents used in ordinary pressure-sensitive adhesives, and among these, particularly preferred are isocyanate-based compounds, More preferably, a polyfunctional isocyanate, for example, a trimethylolpropane adduct of tolylene diisocyanate, ethylene diisocyanate, 1,4-butane diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate And isophorone diisocyanate.

The content of the crosslinking agent (F) is not particularly limited, but is preferably 0.2 to 10.0 parts by weight based on 100 parts by weight of the acrylic copolymer (D).
More preferably, it is 0.5 to 5.0 parts by weight. If the content is less than 0.2 parts by weight, the crosslinking reactivity is poor and the removability is poor. On the other hand, if it exceeds 10.0 parts by weight, the crosslinking reaction becomes excessive and the adhesion becomes poor, which is not preferable.

It is also possible to use an acid catalyst such as paratoluenesulfonic acid, phosphoric acid, hydrochloric acid, ammonium chloride or the like in combination to promote the crosslinking. 0.01 to (F)
About 0.1% by weight is appropriate. The acrylic pressure-sensitive adhesive composition (B) is (D) as described above, preferably (D) to (D).
(F), in the present invention, the gelation fraction of the acrylic pressure-sensitive adhesive composition (B) is from 20 to
It is also important to control the amount to 80% by weight, preferably 40 to 75% by weight, particularly preferably 50 to 75% by weight. In such control, the polymerization method and the adjustment of the amount of (d1) and (d2) introduced above are controlled. It can be realized by a method such as adjusting the amount of the crosslinking agent added.

The acrylic pressure-sensitive adhesive composition (B) includes:
Conventionally known pressure-sensitive adhesive additives can be added to the pressure-sensitive adhesive composition as needed without departing from the object of the present invention. Examples of such known additives include pigments, plasticizers, and stabilizers. , Fillers and the like.

In applying the acrylic pressure-sensitive adhesive composition (B) on the coated surface of the polyester resin (A),
The acrylic pressure-sensitive adhesive composition (B) has a resin solid content of 40
About 50% by weight (solvent: ethyl acetate, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.)
After drying at 80-100 ° C, polyester resin (A)
A method of forming a pressure-sensitive adhesive layer on the coated surface of the above, and a method in which the opposite surface is wound into a roll instead of release paper, etc., and the thickness of the pressure-sensitive adhesive after drying is about 5 to 100 μm. It is preferred to adjust to.

In this way, the hand-cut adhesive tape of the present invention can be obtained. Such an adhesive tape is excellent in adhesiveness and removability, and further excellent in hand-cutting property and prevention of elongation in the longitudinal direction. First, it is highly useful as a curing tape for painting and the like.

[0040]

The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.

[Production of Polyester Resin (A)] [Polyester Resin (A-1)] 0.3 mol of terephthalic acid was placed in a reactor equipped with a nitrogen inlet tube, a thermometer, a stirrer and a rectification column. 0.5 mole of isophthalic acid, 0. sebacic acid.
2 mol, 0.9 mol of ethylene glycol and 0.7 mol of neopentyl glycol were charged and reacted at 200 ° C. until the distillate disappeared, and then polycondensation was performed at 250 ° C. under reduced pressure (0.1 torr). After the reaction, a polyester resin (A-1) (number average molecular weight 16,000, glass transition temperature 65 ° C, hydroxyl value 6 mgKOH / g) was dissolved in toluene, and a polyester resin having a solid content of 30% was obtained. (A-1) A solution was obtained.

[Polyester Resin (A-2)] In a reactor equipped with a nitrogen inlet tube, a thermometer, a stirrer and a rectification column, 0.8 mole of isophthalic acid, 0.2 mole of sebacic acid, and 0 9.9 mol and 0.5 mol of neopentyl glycol were reacted at 200 ° C. until no distillate was discharged, and then reduced at 250 ° C. under reduced pressure (0.1 torr).
r) to carry out a polycondensation reaction to obtain a polyester resin (A
-2) (number average molecular weight 14,000, glass transition temperature 4)
After obtaining a hydroxyl value of 7 mgKOH / g at 0 ° C., it was dissolved in toluene and a polyester resin having a solid content of 30% (A-
2) A solution was obtained.

[Polyester Resin (A-3)] A reactor equipped with a nitrogen inlet tube, a thermometer, a stirrer and a rectification column was charged with 0.5 mol of isophthalic acid, 0.5 mol of adipic acid, and 0 mol of ethylene glycol. 8.8 mol and 0.5 mol of 1,4-butanediol were reacted at 200 ° C. until no distillate was discharged, and then reduced pressure (0.1 torr) at 250 ° C.
r) to carry out a polycondensation reaction to obtain a polyester resin (A
-3) (number average molecular weight 15,000, glass transition temperature 2)
After obtaining a hydroxyl value of 5 mgKOH / g at 0 ° C., it was dissolved in toluene and a polyester resin (A-A) having a solid content of 30% was obtained.
3) A solution was obtained.

[Production of acrylic pressure-sensitive adhesive composition (B)] [Acrylic pressure-sensitive adhesive composition (B-1)]
In a flask equipped with a stirrer and a thermometer, add acrylic acid (d
1) 3 parts, hydroxyethyl methacrylate (d2) 1
Parts, 2-ethylhexyl acrylate (d3) 45 parts,
45 parts of n-butyl acrylate (d3), 6 parts of vinyl acetate (d4), azobisisobutyronitrile (AIB)
N) 0.1 part and 100 parts of ethyl acetate were charged, and 80 ° C
And polymerized by heating to 10 parts of toluene during the polymerization.
Polymerization was carried out for 7 hours while successively adding a polymerization catalyst solution in which 0.1 part of BN was dissolved, and then diluted with toluene to obtain an acrylic copolymer (D-1) having a glass transition temperature of -55 ° C.
% Solution was obtained.

The acrylic copolymer (D-1) 10
0 parts, rosin-based tackifier ("Pentalin CJ" manufactured by Rika Hercules) (E) 8 parts, isocyanate-based crosslinking agent (Nippon Polyurethane Industry Co., Ltd., "Coronate L-55")
E ") 1.0 part of (F) was mixed and stirred, and the acrylic pressure-sensitive adhesive composition (B-1) (solution having a solid content of about 45%) (the gelation fraction of the coating film of the pressure-sensitive adhesive composition was 70%) Aging 20 ° C x 1
0 days after insoluble matter in toluene of the adhesive composition -75
% by weight of non-filtered filter).

[Acrylic pressure-sensitive adhesive composition (B-2)] In a flask equipped with a condenser, a stirrer and a thermometer, 2.0 parts of acrylic acid (d1), 0.5 parts of hydroxyethyl methacrylate (d2), 55 parts of ethylhexyl acrylate (d3), n-butyl acrylate (d3) 3
5 parts of vinyl acetate (d4), 5 parts of azobisisobutyronitrile (AIBN) and 100 parts of ethyl acetate were charged, heated to 80 ° C. and polymerized. After polymerization was performed for 7 hours while successively adding a polymerization catalyst solution in which 1 part was dissolved, the mixture was diluted with toluene, and a 40% solution of an acrylic copolymer (D-2) having a glass transition temperature of −53 ° C. was added. Obtained.

The acrylic copolymer (D-2) 10
0 parts, terpene-based tackifier (manufactured by Yasuhara Chemical Co., Ltd.
8 parts of “YS Polystar T-100”) (E) and 1.0 part of isocyanate-based cross-linking agent (“Coronate L-55E” manufactured by Nippon Polyurethane Industry Co., Ltd.) (F) are mixed and stirred to form an acrylic pressure-sensitive adhesive. Composition (B-2) (solution having a solid content of about 45%) (gelation fraction of a coating film of the pressure-sensitive adhesive composition of 65%; insoluble matter in toluene of the pressure-sensitive adhesive composition after aging at 20 ° C. × 10 days -75 μm) % By weight of the filter not passed).

[Acrylic pressure-sensitive adhesive composition (B-3)] A flask equipped with a condenser, a stirrer and a thermometer was charged with 3 parts of acrylic acid (d1), 46 parts of 2-ethylhexyl acrylate (d3), and methyl methacrylate (d3). ) 16
, 35 parts of n-butyl acrylate (d3), 0.1 part of azobisisobutyronitrile (AIBN) and 100 parts of ethyl acetate are charged, and the mixture is heated to 80 ° C. and polymerized. After polymerizing for 7 hours while sequentially adding a polymerization catalyst solution in which 0.1 part of AIBN was dissolved, the mixture was diluted with toluene and a 40% solution of an acrylic copolymer (D-3) having a glass transition temperature of -32 ° C. I got

The acrylic copolymer (D-3) 10
0 parts, rosin-based tackifier (Arakawa Chemical Co., "Superester A-100") (8 parts), isocyanate-based crosslinking agent (Nippon Polyurethane Industry Co., Ltd., "Coronate L-
55E ") (F) 1.0 part was mixed and stirred, and the acrylic pressure-sensitive adhesive composition (B-3) (solution having a solid content of about 45%) (the gelation fraction of the coating film of the pressure-sensitive adhesive composition was 50%) Aging 20 ° C
× Insoluble matter in toluene of the adhesive composition after 10 days-
(% By weight of 75 μm filter non-passing).

[Production of Polyolefin Resin Base Film (I)] [Polyolefin Resin Base Film (I-1)] Polyethylene resin containing 20% by weight of calcium carbonate (density: 0.96 g / cm ³ ) After performing a melt extrusion process at 160 to 190 ° C. to obtain a molten sheet, the sheet is pressed with a smooth rubber roll and an uneven embossing roll,
After cooling, the squeezing depth of 0.12 mm and 1.2 m
A base film having a stripe interval of m is obtained, and the stripe is cut so as to be orthogonal to the longitudinal direction of the tape to obtain a tape-like polyolefin resin base film (I-1). Was. The thickness of the film was 130 μm, the squeezing depth was 0.12 mm (the difference between the thickness and the squeezing depth was 10 μm), and the surface roughness (Ra) opposite to the uneven surface of the film was 1 μm or less. Was.

[Polyolefin resin base film (I
-2)] 160 to 1 polyethylene resin containing 10% by weight of calcium carbonate (density: 0.96 g / cm ³ )
After performing melt extrusion at 90 ° C to obtain a molten sheet,
The sheet is pressed with a smooth rubber roll and a concavo-convex embossing roll, and then cooled to obtain a base film having a 0.04 mm squeezing depth and a 1.2 mm squeezing interval in a stripe shape. This stripe was cut so as to be orthogonal to the longitudinal direction of the tape to obtain a tape-like polyolefin-based resin base film (I-2). In addition, the thickness of such a film is 130 μm and the depth of drawing is 0.04 mm.
(The difference between the thickness and the squeezing depth was 90 μm), and the surface roughness (Ra) opposite to the uneven surface of the film was 10 μm.

Example 1 An isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd., based on 100 parts of solid content of the polyester-based resin (A-1))
"Coronate L-55E") 2 parts of the resin solution was applied to the uneven surface of the polyolefin resin substrate film (I-1) by a roll coater and dried at 80 to 100 ° C (application amount 5 g / m ² ) After that, the above-mentioned acrylic pressure-sensitive adhesive composition (B-1) solution was further applied with a roll coater and dried at 80 to 100 ° C. to form a pressure-sensitive adhesive layer having a thickness of 40 μm. A cut adhesive tape was obtained. The following evaluation was performed using the obtained hand-cut adhesive tape.

(Adhesive strength) Test plate (width 25 mm, length 20
SUS304 (No. 280 polished product) and polyethylene resin (PE) are used as JIS Z
The measurement was carried out according to the method for measuring adhesive strength of No. 0237.

(Rough Surface Adhesion) A rough veneer was used as a test plate (width 25 mm, length 200 mm) as a test plate, and the adhesion was measured in the same manner as the measurement conditions.

(Removability) A hand-cut adhesive tape was pressed onto each surface of a vinyl chloride flooring material, a wooden flooring material, and a SUS304 plate, left at 40 ° C. for 10 days, and the tape was peeled off by hand. Then, the adhesive remaining state of the adhesive at that time was observed and evaluated according to the following criteria. ○ −−− No adhesive residue is observed at all △ −−− Adhesive residue is observed, but the area is less than 50% of the sticking area × −−− The area of the adhesive residue is 50% or more of the sticking area

(Hand-cutting property) The hand-cutting tape was actually cut by hand in the width direction and evaluated according to the following criteria. ◎ −−− Easy to cut straight without resistance ○ −−− Although there is some resistance, it can be cut linearly △ −−− There is some resistance and some cannot be cut linearly × −−− High resistance makes it difficult to cut straight

(Elongation Elongation Prevention Effect) The longitudinal elongation prevention effect was evaluated by breaking strength and elongation as described below. A strip-shaped test piece having a width of 15 mm and a length of 100 mm was prepared in the longitudinal direction of the hand-cut adhesive tape.
In a 5% RH atmosphere, the distance between chucks is 25 mm,
Perform a tensile test under the conditions of a tensile speed of 10 mm / min,
The breaking strength (kg / cm ² ) and the breaking elongation (%) were measured. The breaking strength is 150 to 200 kg / cm ² ,
When the elongation at break is 60% or less, the tape has good hand-cutting properties and good floating prevention. Breaking strength is 200kg /
If it exceeds cm ² , the hand-cutting property of the tape is poor, and if the elongation at break exceeds 60%, floating due to elongation occurs.

(Curl Resistance) A curable sheet of PE is wound around the curved surface of a 25 mmφ iron cylinder, and a hand-cut adhesive tape (25 mm in width and 40 mm in length) is attached to the surface thereof.
After standing at 40 ° C. for 10 days, the floating condition of the tape was observed, and evaluated according to the following criteria. In this evaluation method, since the inside of the substrate of the hand-cut adhesive tape (the surface to which the adhesive was applied) was squeezed with irregularities, the substrate curled outward (the outside of the adhesive tape). This is a method for confirming resistance to such curling. ○ −−− No peeling was observed at all △ −−− Peeling was observed, but an average of 10 from the edge
Less than 10 mm × ---- Average peeling of 10 mm or more from the end

(Floating of Tape Edge) A hand-cut adhesive tape (25 mm in width and 100 mm in length) was attached to a wooden flooring material, and the tape was left standing at 40 ° C. for 10 days. Was evaluated according to the following criteria. In addition, this evaluation method is an evaluation method for floating caused by elongation of the hand-cut adhesive tape at the time of sticking. ○ --- No lifting is recognized at all. △ --- Lifting of less than 3 mm is observed from the end. × --- Lifting of 3 mm or more is observed from the end.

Example 2 In Example 1, the acrylic pressure-sensitive adhesive composition (B-1) was used.
A hand-cut adhesive tape was obtained in the same manner except that the solution was changed to the acrylic adhesive composition (B-2) solution, and the evaluation was performed in the same manner.

Example 3 In Example 1, the acrylic pressure-sensitive adhesive composition (B-1) was used.
The solution was changed to an acrylic pressure-sensitive adhesive composition (B-3) solution,
Further, except that the polyolefin-based resin base film (I-1) was changed to the polyolefin-based resin base film (I-2), a hand-cut adhesive tape was obtained and evaluated in the same manner. .

Example 4 In Example 1, except that the polyester resin (A-1) solution was changed to the polyester resin (A-2) solution.
The same procedure was performed to obtain a hand-cut adhesive tape, which was similarly evaluated.

Example 5 In Example 1, the polyester resin (A-1) solution was changed to the polyester resin (A-2) solution, and the acrylic adhesive composition (B-1) solution was replaced with the acrylic adhesive. A hand-cut adhesive tape was prepared in the same manner except that the composition (B-2) was changed to a solution and the polyolefin-based resin base film (I-1) was changed to a polyolefin-based resin base film (I-2). And evaluated similarly.

Example 6 Example 1 was repeated except that the polyester resin (A-1) solution was changed to the polyester resin (A-3) solution.
The same procedure was performed to obtain a hand-cut adhesive tape, which was similarly evaluated.

Example 7 In Example 1, the polyester resin (A-1) solution was changed to the polyester resin (A-3) solution, and the acrylic adhesive composition (B-1) solution was replaced with the acrylic adhesive. Hand-cut adhesive tape was prepared in the same manner except that the composition (B-3) was changed to a solution and the polyolefin-based resin base film (I-1) was changed to a polyolefin-based resin base film (I-2). And evaluated similarly.

Comparative Example 1 In the above [Production of Polyolefin Resin Base Film (I)], a polyolefin resin base film having a drawing depth of 0.01 mm was produced using an embossed roll having a small degree of irregularity. A hand-cut adhesive tape was obtained in the same manner as in Example 1, and the evaluation was performed in the same manner.

Comparative Example 2 In the above [Production of Polyolefin Resin Base Film (I)], a polyolefin resin base film having a squeezed depth of 0.5 mm was produced using an embossed roll having a large degree of irregularity. A hand-cut adhesive tape was obtained in the same manner as in Example 1, and the evaluation was performed in the same manner.

Comparative Example 3 In the above [Production of Polyolefin Resin Base Film (I)], the degree of unevenness of the embossing roll was adjusted, and the (nip) pressure of the embossing roll was adjusted to obtain a film thickness. Then, a polyolefin-based resin base film having a difference of 5 μm between the squeezing depth and the squeezing depth was manufactured, and a hand-cut adhesive tape was obtained in the same manner as in Example 1 and evaluated in the same manner.

Comparative Example 4 In the above [Production of Polyolefin Resin Base Film (I)], the degree of unevenness of the embossing roll was adjusted, and the (nip) pressure of the embossing roll was adjusted to obtain a film thickness. And a polyolefin-based resin base film having a difference of 100 μm in the squeezing depth was obtained, and a hand-cut adhesive tape was obtained in the same manner as in Example 1 and evaluated in the same manner.

Comparative Example 5 A hand-cut adhesive tape was obtained in the same manner as in Example 1, except that the polyester resin (A-1) solution was changed to the polyester resin (A-4) solution having the following formulation. And evaluated similarly.

Polyester resin (A-4) 0.3 mol of terephthalic acid, 0.5 mol of isophthalic acid, 0.2 mol of sebacic acid were placed in a reactor equipped with a nitrogen inlet tube, a thermometer, a stirrer and a rectification column. Mol, ethylene glycol 0.9
Mol and 0.7 mol of neopentyl glycol,
The reaction was carried out at 200 ° C. until the distillate disappeared, and then the polyester resin (A-
4) (number average molecular weight 5,000, glass transition temperature 60)
° C, a hydroxyl value of 20 mgKOH / g), and dissolved in toluene to obtain a polyester resin (A-A) having a solid content of 30%.
4) A solution was obtained.

Comparative Example 6 A hand-cut adhesive tape was obtained in the same manner as in Example 1, except that the polyester resin (A-1) solution was changed to a polyester resin (A-5) solution having the following formulation. And evaluated similarly.

Polyester resin (A-5) In a reactor equipped with a nitrogen inlet tube, a thermometer, a stirrer and a rectification column, 0.2 mol of isophthalic acid, 0.8 mol of adipic acid,
Ethylene glycol (0.2 mol) and triethylene glycol (1.5 mol) were charged and reacted at 200 ° C. until no distillate was discharged.
After performing a polycondensation reaction under torr) to obtain a polyester resin (A-5) (number average molecular weight 14,000, glass transition temperature -15 ° C, hydroxyl value 5 mgKOH / g),
It was dissolved in toluene to obtain a polyester resin (A-5) solution having a solid content of 30%.

Comparative Example 7 A hand-cut adhesive tape was obtained in the same manner as in Example 1, except that the polyester resin (A-1) solution was changed to the polyester resin (A-6) solution having the following formulation. And evaluated similarly.

Polyester resin (A-6) 0.8 mol of terephthalic acid, 0.2 mol of isophthalic acid, 0.4 g of ethylene glycol were placed in a reactor equipped with a nitrogen inlet tube, a thermometer, a stirrer and a rectification column. Mol and 1.2 mol of neopentyl glycol, and reacted at 200 ° C. until no distillate was discharged.
After performing a polycondensation reaction under torr) to obtain a polyester resin (A-6) (number average molecular weight 16,500, glass transition temperature 95 ° C, hydroxyl value 4 mgKOH / g), dissolving in toluene, solid A 30% polyester-based resin (A-6) solution was obtained. Tables 1 and 2 show the evaluation results of the examples and comparative examples.

[0076] Table 1 adhesion (g / 25 mm) rough surface adhesiveness force (g / 25 mm) removability SUS PE veneer PVC wood SUS Example 1 850 450 200 ○ ○ ○ 〃 2 900 500 250 ○ ○ ○ 〃 3 950 550 300 ○ ○ ○ ○ 4 860 440 210 ○ ○ ○ ○ 5 890 510 240 ○ ○ ○ ○ 6 840 460 210 ○ ○ ○ ○ 7 960 540 300 ○ ○ ○ Comparative example 1 860 440 210 ○ ○ ○ ○ 2700 300 150 ○ ○ ○ ３ 3 650 250 110 ○ ○ ○ ４ 4 840 430 190 ○ ○ ○ 〃 5 860 460 210 △ △ △ 〃 6 840 430 220 × × × ７ 7 860 450 230 × △ ×

[Table 2] Hand-cutting property Elongation prevention effect in the longitudinal direction Curling resistance Tape edge Breaking strength Elongation elongation (kg / cm ² ) (%) Example 1 ◎ 170 50 ○ ○ 〃 2 ◎ 165 45 ○ ○ 〃 3 ○ 180 30 ○ ○ 〃 4 ◎ 172 53 ○ ○ ５ 5 ○ 183 32 ○ ○ ６ 6 ◎ 168 55 ○ ○ 〃 7 ○ 172 40 ○ ○ Comparative Example 1 × 250 23 ○ △ 〃 2 ◎ 110 130 × × 〃 3 ○ 120 150 × × ４ 4 × 260 20 ○ △ 〃 5 △ 130 80 △ △ ６ 6 × 105 100 △ × ７ 7 × 230 18 × △

[0078]

The hand-cut adhesive tape of the present invention is obtained by applying a specific polyester resin to a specific polyolefin resin base film and further applying an acrylic adhesive composition thereon. Excellent in adhesiveness and removability, and also excellent in hand-cutting property, prevention of longitudinal elongation, curling resistance, prevention of tape edge floating, etc., useful as various adhesive tapes, especially curing tape for construction, painting, etc. And very useful.

[Brief description of the drawings]

FIG. 1 is a conceptual view of a longitudinal section of a hand-cut adhesive tape of the present invention.

[Explanation of symbols]

 (B) Drawing depth (b) Drawing interval (c) Thickness of base film

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Ken Ishikawa 3-4-1-17 Shimotakaido, Suginami-ku, Tokyo Inside Koyo Chemical Co., Ltd. (72) Inventor Masayoshi Ishikawa 3-chome Shimotakaido, Suginami-ku, Tokyo No. 17 Koyo Chemical Co., Ltd. F term (reference) 4J004 AA10 AB01 CA04 CC04 CC06 CD06 FA10 4J040 BA202 DF041 DF051 DN072 EB082 GA05 GA07 GA14 JA09 KA16 KA26 LA08 NA12 PA23

Claims (8)

[Claims] 1. A striped irregular surface having a squeezing depth of 0.03 to 0.3 mm and a squeezing interval of 0.5 to 5 mm orthogonal to the longitudinal direction of the adhesive tape is formed on one surface. The difference between the thickness of the material film and the depth of drawing is 10-90μ
m, a polyester resin (A) having a number average molecular weight of 10,000 or more and a glass transition temperature of 0 to 80 ° C. is applied to the uneven surface of the unstretched polyolefin resin base film (I). And an acrylic pressure-sensitive adhesive composition (B) further coated thereon. 2. The hand-cut adhesive tape according to claim 1, wherein a crosslinking agent (C) is further blended with the polyester resin (A). 3. The coating amount of the polyester resin (A) is 0.1 to 20 g / m ^2.
Or the hand-cut adhesive tape according to 2. 4. An acrylic pressure-sensitive adhesive composition (B) comprising 1 to 20% by weight of a carboxyl group- or amino group-containing unsaturated monomer, 0 to 20% by weight of a hydroxyl group-containing unsaturated monomer,
(Meth) acrylic acid alkyl ester 50% by weight or more,
4. An acrylic copolymer (D) having a glass transition temperature of less than -20 [deg.] C., comprising 0 to 49% by weight of another copolymerizable monomer. Hand-cut adhesive tape. 5. The hand-cut adhesive tape according to claim 4, further comprising a tackifier (E) and a crosslinking agent (F). 6. The tackifier (E) comprises at least one of a rosin-based resin, a terpene-based resin, and a xylene-based resin.
6. The hand-cut adhesive tape according to claim 5, wherein the adhesive tape is at least one kind. 7. The surface roughness (Ra) of the unstretched polyolefin resin substrate film (I) on the opposite side of the uneven surface is 3
The hand-cut adhesive tape according to any one of claims 1 to 6, wherein the thickness is 0 µm or less. 8. The hand-cut adhesive tape according to claim 1, which is used for curing.