TWI431058B - Film substrate and adhesive tape - Google Patents

Description

Film substrate and adhesive tape

The present invention relates to a film substrate and an adhesive tape using the same.

Various adhesive tapes used for insulating tapes of various electrical equipments such as automobiles, railways, airplanes, ships, houses, factories, etc., have moderate flexibility and extensibility, flame retardancy, mechanical strength, heat deformation resistance, electricity A film which is excellent in insulating properties and moldability, and which is relatively inexpensive, is a resin composition containing a halogenated vinyl resin such as polyvinyl chloride.

However, the halogenated vinyl resin film has recently produced a toxic gas during the burn-off process, and recently, a polyolefin resin containing a large amount of a metal hydroxide (for example, magnesium hydroxide, aluminum hydroxide, etc.) having a small environmental burden has been used. The non-halogen resin composition of the flame retardant composed of the inorganic metal compound is a film of the raw material.

In the adhesive tape using the non-halogen resin composition as a raw material, it is known that a composition containing an olefin polymer and an inorganic flame retardant is a film substrate (for example, Patent Document 1), and formation of an olefin film. A material and a styrene block polymer such as styrene/ethylene/butene copolymer/styrene are used as a film substrate (for example, Patent Document 2), and further contain a vinyl aromatic elastomer component and a styrene polymer component. The olefin resin composition is used as a film substrate (for example, Patent Document 3).

Patent Document 1: JP-A-2001-192629

Patent Document 2: JP-A-2000-038550

Patent Document 3: JP-A-2002-105217

However, the adhesive tape of a film using a conventional non-halogen resin composition as a raw material, for example, in a case where a complicated electric wire or a cable tape is used in an engine space of an automobile, cannot satisfy flexibility, hand cutability, heat resistance. And any of the characteristics such as abrasion resistance.

The present invention is intended to provide a film substrate and a pressure-sensitive adhesive tape using the same, which have properties such as flexibility, hand cutability (easiness of cutting the tape), heat resistance, and abrasion resistance.

That is, the present invention has the following gist.

(1) A film base material comprising an aromatic vinyl-based elastomer; and 10 to 60 parts by mass of the styrene resin and 1 to 50 in 100 parts by mass of the aromatic vinyl-based elastomer A styrenic copolymer having a Vicat softening point of 100 to 130 ° C in parts by mass.

(2) The film substrate according to (1), wherein the aromatic vinyl-based elastic system is selected from the group consisting of styrene-butadiene random copolymer, styrene-butadiene block copolymer, and styrene-butyl At least one of a hydride of a olefin random copolymer and a hydride of a styrene-butadiene block copolymer.

(3) The film substrate according to (1) or (2), wherein styrene The resin is a polystyrene resin (GPPS) and/or a rubber-reinforced polystyrene resin (HIPS).

(4) The film substrate according to any one of (1) to (3) wherein the styrene copolymer having a Vicat softening point of from 100 to 130 ° C is from 80 to 99% by mass. The aromatic vinyl monomer and 1 to 20% by mass of the ethylenically unsaturated carboxylic acid monomer are polymerized.

(5) The film substrate according to (4), wherein the aromatic vinyl monomer is styrene, and the ethylenically unsaturated carboxylic acid monomer is methacrylic acid.

(6) The film base material according to any one of (1) to (5), wherein the aromatic vinyl-based elastomer contains 1 to 300 parts by mass of an inorganic filler in 100 parts by mass.

(7) The film substrate according to (6), wherein the inorganic filler has an average particle diameter of 20 μm or less.

(8) The film substrate according to any one of (1) to (7) which is crosslinked by electron beam irradiation.

(9) An adhesive tape comprising the adhesive layer formed on one surface of the film substrate according to any one of (1) to (8).

(10) An adhesive tape for binding, which is characterized in that the adhesive tape as described in (9) is used.

By using the film substrate of the present invention, it is possible to obtain an adhesive tape which has properties such as flexibility, hand cutability, heat resistance, and abrasion resistance in a balanced manner.

The aromatic vinyl-based elastomer which can be used in the film substrate of the present invention is composed of a polymer agglomerate of an aromatic vinyl hydrocarbon and an elastomeric polymer agglomerate, and a polymer of the aromatic vinyl hydrocarbon It is preferred that the agglomerates are hard segments and the elastomeric polymer agglomerates are soft segments.

An aromatic vinyl-based elastomer, typically a polymer agglomerate of an aromatic vinyl hydrocarbon-elastomeric polymer agglomerate, or a polymer agglomerate of an aromatic vinyl hydrocarbon-elastomeric polymer agglomerate It is preferred that the polymer agglomerates of the aromatic vinyl hydrocarbons represent a copolymerization structure. The above-mentioned elastomeric polymer agglomerates, which have a partially or fully hydrogenated block copolymer with a double bond, or a random copolymer, are generally known as styrene-based elastomers.

An aromatic vinyl hydrocarbon constituting a polymer agglomerate of an aromatic vinyl hydrocarbon such as styrene, α -methylstyrene, o-, m-, and p-methylstyrene, 1,3-dimethyl Styrene, vinyl naphthalene, vinyl anthracene, etc., of which styrene is preferred.

As the elastomeric polymer agglomerate, a conjugated diene or a conjugated diene may be used as long as the elastomeric property is found, and a conjugated diene is generally preferred. In this case, as the conjugated diene, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene or the like.

As the aromatic vinyl-based elastomer, for example, ethylene-ethylene ‧ styrene copolymer - styrene (SEBS), styrene - ethylene ‧ propylene copolymer - styrene (SEPS) or styrene - butadiene - styrene ( SBS), ABA type block copolymer or random copolymer of styrene-isoprene-styrene (SIS), or ABA type block copolymer of these, a hydride of a copolymer; such as a styrene-butadiene copolymer, an AB-type block copolymer or a random copolymer of a styrene-isoprene copolymer, or an AB-type block copolymer of these, A hydride of a random copolymer.

An aromatic vinyl-based elastomer in which a styrene-butadiene random copolymer, a styrene-butadiene block copolymer, a styrene-butadiene random copolymer hydride or styrene-butyl A hydride of a diene block copolymer is preferred. In particular, a complete hydride of a styrene-butadiene random copolymer is preferred because of low elongation at break.

A styrene resin which can be used for the substrate film of the present invention, a styrene single polymer, a copolymer of styrene and a copolymer copolymerizable with the monomer or a rubbery polymer, or a copolymer which can be copolymerized therewith. One or more (co)polymerizers of the body are preferred.

As a monomer copolymerizable with styrene, for example, α-substituted styrene such as α-methyl styrene; aromatic ring-substituted styrene such as vinyl toluene or butyl styrene; acrylonitrile, A a chlorinated vinyl monomer such as acrylonitrile; an acrylate such as methyl acrylate or ethyl acrylate; a methacrylate such as methyl methacrylate or ethyl methacrylate; or ethylene such as acrylic acid or methacrylic acid. Alkyl carboxylic acid; unsaturated decylamine such as acrylamide or methacrylamide; maleimide, N-phenyl maleimide, N-cyclohexylbutylene An unsaturated phthalamide derivative such as an amine; an unsaturated carboxylic anhydride such as maleic acid, methylene succinic acid or methyl maleic acid. But not limited to these.

The styrene-based resin is not particularly limited, and a conventionally known resin can be used. Specifically, the so-called GPPS polystyrene resin and/or It is a rubber-reinforced polystyrene resin of HIPS. Among them, a styrene resin which can easily adjust the strength of the film by controlling the molecular weight, or a mixture of a styrene resin and a rubber-reinforced polystyrene resin is preferable.

In the film base material of the present invention, the blending amount of the styrene resin is from 10 to 60 parts by mass, preferably from 10 to 40 parts by mass, per 100 parts by mass of the aromatic vinyl-based elastomer. When the styrene resin is less than 10 parts by mass, the strength of the film substrate is low and it is easy to extend. On the other hand, when the styrene resin exceeds 60 parts by mass, the processability of the film substrate is lost, and the film substrate becomes stiff and the pinhole resistance is lowered.

The film substrate of the present invention contains a styrene copolymer having a Vicat softening point of 100 to 130 °C. The styrene copolymer having a softening point of less than 100 ° C in this system has a heat shrinkage of the film substrate and deteriorates heat resistance. A styrene-based copolymer having a softening point of more than 130 ° C causes a fish eye caused by poor kneading, and pinholes are generated to cause a poor appearance of the film substrate. In particular, a styrene copolymer having a softening point of 110 to 120 ° C is preferred.

The blending amount of the styrene-based copolymer having a softening point of 100 to 130 ° C is 1 to 50 parts by mass, preferably 10 to 35 parts by mass, per 100 parts by mass of the aromatic vinyl-based elastomer. When the styrene copolymer having a softening point of 100 to 130 ° C is less than 1 part by mass, the heat shrinkage of the film substrate is deteriorated. On the other hand, when the styrene copolymer having a softening point of 100 to 130 ° C exceeds 50 parts by mass, the film processability is deteriorated.

a styrenic copolymer having a softening point of 100 to 130 ° C, preferably 80 to 99% by mass of an aromatic vinyl monomer and 1 to 20 mass The composition of % ethylenically unsaturated carboxylic acid monomer is polymerized. More preferably, it is 85 to 98% by mass of an aromatic vinyl monomer, 2 to 15% by mass of an ethylenically unsaturated carboxylic acid monomer, and 0.1 to 10% by mass of a polymerizable copolymerizable with these vinyl monomers. .

When the aromatic vinyl monomer is less than 80% by mass or the ethylenically unsaturated carboxylic acid monomer is more than 20% by mass, the heat resistance is too high, the fluidity of the resin is low, and the melt viscosity of the aromatic vinyl-based elastomer is changed. If the melt mixing property is deteriorated, the formability of the film substrate may be lowered. In addition, when the amount of the aromatic vinyl monomer is more than 99% by mass or the amount of the ethylenically unsaturated carboxylic acid monomer is less than 1% by mass, the effect of imparting heat resistance to the film substrate may be deteriorated.

An aromatic vinyl monomer as a styrene copolymer having a softening point of 100 to 130 ° C, such as styrene, α -methylstyrene, vinyltoluene, ethylstyrene, or 3 butylstyrene And other styrenes and their substitutes. It is preferred to control the styrene of the increased molecular weight depending on the reaction.

An ethylenically unsaturated carboxylic acid monomer having a styrene copolymer having a softening point of 100 to 130 ° C, such as acrylic acid or its ester, methacrylic acid or its ester, fumaric acid, and maleic acid An α ,β-unsaturated carboxylic acid such as diacid or methylene succinic acid or a monoester, diester, anhydrate or quinone imide thereof, acrylonitrile, or an acrylic acid adjacent in the molecule A six-membered ring anhydrate derived from the intramolecular dehydration (or dealcoholation) reaction of a monomer unit such as methacrylic acid or an ester such as these, or a quinone imide thereof. Among them, methacrylic acid, maleic acid, and quinone imide are preferred.

a vinyl monomer reactive with an aromatic vinyl monomer and an ethylenically unsaturated carboxylic acid monomer, such as methyl methacrylate or methyl group, as a styrene copolymer having a softening point of 100 to 130 ° C (Meth) acrylate monomer such as n-butyl acrylate; chlorinated vinyl monomer such as acrylonitrile or methacrylonitrile; maleic anhydride, maleic acid, methylene succinic acid An unsaturated carboxylic acid monomer other than methacrylic acid such as methylene succinic anhydride; maleimide, N-methylbutyleneimine, N-phenylbutylene A maleimide monomer such as an imide or the like. These can be used individually or in combination of 2 or more types.

The method for producing the styrene-based copolymer having a softening point of 100 to 130 ° C in the present invention is not particularly limited, and a bulk polymerization method, a suspension polymerization method, a solution polymerization method, or an emulsion polymerization method can be suitably used.

The softening point of the domain of the present invention is determined by the following method.

Device name: domain softening point test machine (for example, manufactured by Toyo Seiki Co., Ltd., trade name: VSP tester)

Test piece: a plate-shaped test piece having a length of 30 mm, a width of 19 mm, and a thickness of 3.2 mm. After injection molding, the film was placed in a constant temperature and humidity chamber at a temperature of 23 ° C and a relative humidity of 50% for 24 hours to adjust the state.

Test method: The temperature was raised using a load of 5 kg and a temperature increase rate of 50 ° C / hour, and the temperature when the pressure was introduced into the test piece of 1 mm was measured. Three tests were performed, and the average value was taken as the softening point of the domain.

The film substrate of the present invention preferably contains an inorganic filler. The reason for blending the inorganic filler is to improve the hand cutting property of the film substrate, and to form The heat conduction during processing becomes large, and the cooling effect of the film substrate is improved, and the distortion of the film substrate can be suppressed. The average particle diameter of the inorganic filler is, for example, 20 μm or less, and preferably 10 μm or less. When the average particle diameter exceeds 20 μm, the tensile strength and elongation at break of the film substrate are low, and the flexibility is also lowered to cause pinholes.

The average particle diameter is a value measured based on the particle distribution of the laser diffraction method. The particle distribution measuring machine is, for example, a product name "LS-230 type" manufactured by Beckman Coulter. Further, in the case where the inorganic filler is blended into a non-halogen flame retardant, formation of charcoal (carbonized layer) is desired, and the flame retardancy of the film substrate can be improved.

As inorganic fillers, for example, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, triphenylphosphite, ammonium polyphosphate, polyphosphonium, zirconium oxide, magnesium oxide , zinc oxide, titanium oxide, molybdenum oxide, barium phosphate, hydrotalcite, snake stone ), zinc borate, anhydrous zinc borate, zinc metaborate, barium metaborate, barium oxide, antimony trioxide, antimony pentoxide, red phosphorus, talc, alumina, cerium oxide, boehmite, bentonite (bentonite) And sodium citrate, calcium citrate, calcium sulfate, calcium carbonate, and magnesium carbonate, and one or two or more of these compounds can be used. In particular, at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, hydrotalcite, and magnesium carbonate is excellent in flame retardancy imparting effect and economically advantageous.

The blending amount of the inorganic filler is preferably from 1 to 300 parts by mass, particularly preferably from 5 to 100 parts by mass, per 100 parts by mass of the aromatic vinyl-based elastomer. If the inorganic filler exceeds 300 parts by mass, the film substrate The formability and mechanical properties such as strength are deteriorated.

Further, in the film substrate, a stabilizer such as a coloring agent, an antioxidant, an ultraviolet absorber, a lubricant, a light stabilizer, or the like may be blended as needed insofar as the effects of the present invention are not impaired.

The light stabilizer is preferably a low base or neutral high molecular weight type which can reduce the production of a product which reacts with an acid base of an ethylenically unsaturated carboxylic acid (acid).

As the lubricant, a conventional lubricant which is generally used can be used, and a fatty guanamine such as mesaconamine, ceramide or stearylamine which suppresses the clogging phenomenon of the substrate can be used.

The molding means of the film substrate is not particularly limited, and various mixing devices such as a 1-axis or 2-axis extruder, a drum, a Bambari mixer, various kneading machines, and the like are used, such as conventional melt kneading. The above components are uniformly dispersed by mixing, and the resulting mixture is formed into a film by a conventional molding method (for example, T-die method, inflation method, calendering method). In the molding machine, a calendering machine is preferred. For the roller arrangement of the calendering, for example, a conventional method such as an L type, an inverted L type, or a Z type can be employed, and the temperature of the roller is usually set to 150 to 200 ° C, preferably 160 to 190 ° C. The formed film is cut to the desired tape width.

The thickness of the film substrate is not particularly limited and is, for example, 40 to 500 μm, more preferably 60 to 300 μm, still more preferably 80 to 160 μm. Furthermore, the film substrate may be in the form of a single layer or a plurality of layers. For the adhesive tape, for example, in order to cope with the work of winding various wires, the thickness of the film substrate becomes thick, and the winding workability is lowered.

By crosslinking the film substrate with an electron beam, it is possible to prevent the film substrate from being deformed or shrunk at a high temperature, and the temperature dependency can be reduced. At this time, the irradiation amount of the electron beam is preferably 10 to 150 Mrad, and particularly 15 to 25 Mrad. If the irradiation amount is less than 10 Mrad, the temperature dependency cannot be improved. On the other hand, when the irradiation amount exceeds 150 Mrad, the film substrate is deteriorated by the electron beam, which causes a problem of workability in subsequent processing.

A crosslinking agent that promotes electron beam crosslinking can also be added. Specifically, the crosslinking agent may be a low molecular weight compound or oligomer having at least two carbon-carbon double bonds in the molecule, such as an acrylate compound or an urethane acrylate oligomer. Epoxy acrylate oligomer.

An adhesive layer can also be formed on one side of the film substrate. As the adhesive for forming the adhesive layer, a commonly used adhesive such as a rubber-based adhesive or an acrylate-based adhesive can be suitably used. Further, in order to achieve a desired function of these adhesives, a tackifier, an aging preventive, and a further hardener for the adhesive may be blended.

As a matrix polymer for rubber-based adhesives, natural rubber, recycled rubber, anthrone rubber, isoprene rubber, styrene butadiene rubber (SBR), acrylate rubber, polyisoprene, nitrile dibutyl Ethylene rubber (NBR), styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer.

For the rubber-based adhesive, a crosslinking agent, a softener, a filler, a flame retardant, or the like may be added as needed. Specific examples include, for example, an isochlorite-based crosslinking agent as a crosslinking agent, a liquid rubber as a softening agent, calcium carbonate as a filler, and an inorganic flame retardant such as magnesium hydroxide or red phosphorus as a flame retardant.

As the acrylate-based adhesive, for example, a single polymer of (meth) acrylate or a copolymer with a copolymerizable monomer. As a (meth) acrylate or a copolymerizable monomer, for example, an alkyl (meth) acrylate (for example, methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, octyl ester, etc.), (meth)acrylic acid Glycidyl ester, (meth)acrylic acid, methylene succinic acid, maleic anhydride, (meth) acrylamide, N-hydroxy decyl (meth) acrylate, alkyl (meth) acrylate Alkyl esters (for example, dimethylaminoethyl methacrylate, butylaminoethyl methacrylate), vinyl acetate, styrene, acrylonitrile, and the like. Among these, as the main monomer, an alkyl acrylate having a glass transition temperature of -50 ° C or less is usually preferable for the individual polymer.

The adhesiveness-imparting resin used as the adhesion-imparting agent is selected in consideration of the softening point, the compatibility with each component, and the like. For example, terpene resin, rosin resin, hydrogenated rosin resin, coumarone-indene resin, styrene resin, aliphatic and alicyclic petroleum resin, terpene-phenol Resin, xylene-based resin, other aliphatic hydrocarbon resin, or aromatic hydrocarbon resin. The adhesion imparts a softening point to the resin, preferably 65 to 170 ° C, particularly preferably 80 to 150 ° C.

Further, an alicyclic saturated hydrocarbon resin of a petroleum resin having a softening point of 65 to 130 ° C, a polydecene resin having a softening point of 80 to 130 ° C, a glycerin of a hydrogenated rosin having a softening point of 80 to 130 ° C, and the like are more preferable. These can be used individually or in combination.

The aging preventive agent is characterized in that the unsaturated double bond in the rubber molecule of the rubber-based adhesive is easily deteriorated in the presence of oxygen or light, and is improved in order to improve the problem. use.

The aging preventive agent is, for example, a phenol-based aging preventive agent, an amine-based aging preventive agent, a benzimidazole-based aging preventive agent, a dithiocarbamate-based aging preventive agent, or a phosphorus-based aging preventive agent.

The curing agent for the adhesive is used as an acrylate-based adhesive, for example, an isochlorite type, an epoxy type, an amine type, an oxazoline type, an aziridine type, etc., not only these individual It can also be a mixture of these.

As the isocyanate-based hardener, specifically, a polyvalent isocyanate compound such as 2,4-cresyl diisochlorate, 2,6-cresyl diisochlorate, and 1,3-xylene dihydrochloride Ester, 1,4-dyl ester of diisochloric acid, diphenylmethane-4,4'-diisochlorite, diphenylmethane-2,4'-diisochlorite, 3-methyl Diphenylmethane diisochlorate, hexamethylene diisochlorate, isophorone diisochlorate, dicyclohexylmethane-4,4'-diisochlorite, dicyclohexylmethane- 2,4'-diisochlorite, isocyanuric acid isocyanate, and the like.

The method of applying the adhesive to the film substrate such as the adhesive, the adhesion-imparting agent, and the aging preventive agent of the adhesive layer of the adhesive tape is not particularly limited, and examples thereof include an adhesive composed of an adhesive, an adhesive-imparting agent, and an anti-aging agent. The solution is applied to one side of the film substrate by a transfer method to dry it. The thickness of the adhesive layer after drying is, for example, 5 to 100 μm, preferably 10 to 50 μm. If it is thinner than 5μm, the adhesion and rewinding force are low. On the other hand, if it is thicker than 100 μm, the coating function is deteriorated.

Example

Hereinafter, the present invention will be described in more detail based on examples. However, the invention is not limited to those explained in the examples.

(Example 1)

Incorporation of the film substrate of the present embodiment, 100 parts by mass of a complete hydride of a styrene-butadiene random copolymer (SOESS 9000 manufactured by Asahi Kasei Chemicals Co., Ltd.), as an aromatic vinyl elastomer, polystyrene (Toyo styrene company, GPPS G-14L) 30 parts by mass of styrene-based resin, T-080 manufactured by Toyo Styrene Co., Ltd. (domain softening point: 115 ° C: 92% by mass of aromatic vinyl monomer and 8 30 parts by mass of the ethyl alcohol unsaturated carboxylic acid), a styrene copolymer having a softening point of 100 to 130 ° C, and magnesium hydroxide having an average particle diameter of 5.0 μm (manufactured by Shendao Chemical Industry Co., Ltd., MAGSEEDS N) -1) 30 parts by mass, 0.1 parts by mass of a hindered phenol-based antioxidant (AO-60, manufactured by ADECA Co., Ltd.), 0.5 parts by mass of a phosphate ester-based lubricant (H-933D-3, manufactured by Seiko Chemical Co., Ltd.), and a black coloring agent ( F-30940MM, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) 3 parts by mass.

These materials were uniformly dispersedly mixed using a Banbury mixer, and a thickness of about 0.1 mm (100 μm) was formed by a calender at a roller temperature of 160 ° C to obtain a film substrate.

Then, a rubber-based adhesive composed of a mixture of natural rubber and SBR is applied to the film substrate by a doctor blade, and a drying step is performed to form an adhesive layer having a thickness of 20 μm on one side of the film substrate, and the width is cut into widths. 25mm tape, get adhesive tape. The adhesive tape had a back adhesion of 3.0 N/10 mm.

(Example 2)

The aromatic vinyl-based elastomer is 100 parts by mass of a completely hydrogenated product of a styrene-butadiene block copolymer (manufactured by KURARAY Co., Ltd., SEPUTON 8007), and the styrene resin is (HIPS E640N manufactured by Toyo Styrene Co., Ltd.) 30 An adhesive tape was obtained in the same manner as in Example 1 except for the mass portion.

(Example 3)

30 parts by mass of the styrene resin (GPPS G-14L) of Example 1 is 15 parts by mass, and 30 parts by mass of the styrene-based copolymer (T-080) having a softening point of 100 to 130 ° C is 5 parts by mass. An adhesive tape was obtained in the same manner as in Example 1.

(Example 4)

The aromatic vinyl-based elastomer is 100 parts by mass of a styrene-butadiene random copolymer (manufactured by Electric Chemical Industry Co., Ltd., STR1250), and the styrene resin is (GPPS G-14L) 15 parts by mass and (HIPS E640N). 15 parts by mass of a styrenic copolymer having a softening point of 100 to 130 ° C (T-040, manufactured by Toyo Styrene Co., Ltd., and a softening point of 107 ° C: 96% by mass of an aromatic vinyl monomer) In the same manner as in Example 1, except that the body and the 4% by mass of the ethylenically unsaturated carboxylic acid monomer were 5 parts by mass. Adhesive tape.

(Example 5)

The aromatic vinyl elastomer is 100 parts by mass of a styrene-butadiene block copolymer (manufactured by Electric Chemical Industry Co., Ltd., STR1602), and the styrene resin is 60 parts by mass of (HIPS E640N), and the softening point is The styrene-based copolymer of 100 to 130 ° C is (AX-053, manufactured by Denki Kagaku Kogyo Co., Ltd., a softening point of 127 ° C: 82.5% by mass of an aromatic vinyl monomer and 17.5% by mass of an acrylonitrile copolymer, and 50 parts by mass of a 50% by mass of an aromatic vinyl monomer, a melt-kneaded product of a copolymer of 1% by mass of an ethylenically unsaturated carboxylic acid monomer and a 35% by mass of a maleimide monomer) In Example 1, an adhesive tape was obtained in the same manner.

(Comparative Example 1)

An adhesive tape was obtained in the same manner as in Example 1 except that the blending amount of the styrene resin of Example 1 was changed to 5 parts by mass.

(Comparative Example 2)

An adhesive tape was obtained in the same manner as in Example 1 except that the blending amount of the styrene resin of Example 1 was changed to 100 parts by mass.

(Comparative Example 3)

In the same manner as in Example 1, except that the blending amount of the styrene-based copolymer having a softening point of 100 to 130 ° C in Example 1 was changed to 0.5 part by mass. Adhesive tape.

(Comparative Example 4)

An adhesive tape was obtained in the same manner as in Example 1 except that the blending amount of the styrene-based copolymer having a softening point of 100 to 130 ° C in Example 1 was changed to 100 parts by mass.

(Comparative Example 5)

An adhesive tape was obtained in the same manner as in Example 1 except that the styrene resin of Example 1 was not blended.

(Comparative Example 6)

An adhesive tape was obtained in the same manner as in Example 1 except that the styrene-based copolymer of Example 1 having a softening point of 100 to 130 ° C was not blended.

(Comparative Example 7)

30 parts by mass of the styrene copolymer having a softening point of 100 to 130 ° C in Example 1 was changed to a styrene copolymer having a softening point of 95 ° C (GR-AT-R, manufactured by Electric Chemical Industry Co., Ltd., An adhesive tape was obtained in the same manner as in Example 1 except that 30 parts by mass of 69% by mass of an aromatic vinyl monomer and 31% by mass of acrylonitrile.

(Comparative Example 8)

In addition to the styrene system of Example 1 having a softening point of 100 to 130 ° C 30 parts by mass of the copolymer was changed to a styrene copolymer having a softening point of 145 ° C (MS-25NF manufactured by Denki Kagaku Kogyo Co., Ltd., a softening point of 145 ° C, 64% by mass of an aromatic vinyl monomer, 1 An adhesive tape was obtained in the same manner as in Example 1 except that 30 parts by mass of the mass% of the ethylenically unsaturated carboxylic acid monomer and the 35% by mass of the maleimide monomer were used.

(Comparative Example 9)

The film substrate of Example 1 was blended in an amount of 100 parts by mass of LDPE (manufactured by TOSOH Co., Ltd., PETROSEN 226), and an adhesive tape was obtained in the same manner as in Example 1 except that a polyolefin substrate was used.

The evaluation results of the film substrate and the adhesive tape obtained in the above Examples and Comparative Examples are shown in Table 1.

In Table 1, "softness" is a tensile strength of 25% modulus measured according to JIS C2107. The test was conducted in an evaluation test chamber in which the set temperature was 23 ± 2 ° C and the humidity was 50 ± 5% RH, and the adhesive tape showed an average value of the measured values of n = 3 or more, and was evaluated by the following evaluation criteria.

Good: The tensile strength of the modulus is 5.0~15.0N/mm ² .

Poor: The tensile strength of the modulus is less than 5.0 N/mm ² or exceeds 15.0 N/mm ² .

In Table 1, "extension" is the elongation of tensile fracture measured according to JIS C2107. The test was conducted in an evaluation test chamber in which the set temperature was 23 ± 2 ° C and the humidity was 50 ± 5% RH, and the adhesive tape showed an average value of the measured values of n = 3 or more, and was evaluated by the following evaluation criteria.

Good: Tensile elongation at break is 100~400%.

Poor: The elongation at break of tensile fracture is less than 100% or exceeds 400%.

In the case of the adhesive tape of the length of 100 mm, it is cut by a human hand in the horizontal direction, and the state of the notch of the cut surface of the adhesive tape is visually determined, and it is evaluated by the following evaluation criteria. .

Excellent: The cut of the cut surface of the adhesive tape is a beautiful cut.

Good: Although the slit of the cut surface of the adhesive tape is slightly extended, it is beautifully cut.

Poor: The slit of the cut surface of the adhesive tape extends and flows toward the adhesive tape.

In Table 1, the "heat shrinkage rate" is a film having a length of 100 mm square and allowed to stand in a 100 ° C environment for 10 minutes, at a set temperature of 23±2°C, humidity: 50±5% RH. In the test chamber, the shrinkage rate in the transport direction (MD) and width direction (TD) after standing for 20 minutes. The average value of the measured values of n=3 or more was shown, and it evaluated by the following evaluation criteria.

Good: The shrinkage rate is less than 10%.

Bad: The contraction rate is 10% or more.

In Table 1, the "wear resistance" is made of canequim No. 3 cotton cloth as a wear material, placed on a film substrate having a length of 100 mm and a width of 50 mm, and loaded with a weight of 500 g per minute. At a speed of 80 times, the film substrate was rubbed with the abrasion material for 60 minutes, and the damage state of the film substrate was visually determined, and then evaluated by the following evaluation criteria.

Good: The film substrate is not damaged.

Poor: The film substrate is damaged.

In Table 1, the "workability" is a usability in the case where an adhesive tape is wound around a wire cable having a diameter of 1 mm, and then evaluated by the following evaluation criteria.

Good: In the winding, the adhesive tape is not extended or cut.

Bad: In the entanglement, the adhesive tape extends or cuts off.

In Table 1, the "pinhole resistance" is formed by forming an adhesive tape having a length of 100 mm and extending it at a tensile speed of 300 mm/min to a length of 200 mm, and visually determining whether or not the adhesive tape has pinholes, and then using the following evaluation criteria. Conduct an evaluation.

Good: no pinholes in the adhesive tape.

Poor: There are more than one pinhole in the adhesive tape.

In Table 1, the "obstruction resistance" is based on a film substrate of 50 cm ² in an environment of 50 ° C, and a load of 15 kg is applied. After standing for 24 hours, the load of 15 kg is removed, and the set temperature is 23 ± In the evaluation test chamber at 2° C. and humidity of 50±5% RH, after standing for 20 minutes or more, the superposed film substrate was peeled off by hand, and the peeled state was evaluated by the following evaluation criteria.

Good: The film substrate is peeled off.

Poor: The film substrate cannot be peeled off.

Although not shown in Table 1, the heating deformation rate of Example 1 was -43%. The heat deformation rate is a deformation rate of the length of the adhesive tape which is left at a temperature of 140 ° C for 5 minutes and then placed at 23 ° C for 30 minutes or more and the length of the adhesive tape before the treatment, and the temperature dependence of the adhesive tape can be exhibited. In another embodiment, when the film substrate of the first embodiment is irradiated with an electron beam of 20 Mrad to crosslink, the heat deformation rate becomes -6%, and the temperature dependency is small. Further, Examples 1 and 2 have the same tensile strength, elongation at break, electrical insulation (volume characteristic resistance value of 1 × 10 ¹² Ω ‧ cm or more), electric resistance, and breakdown voltage as those of the conventional polyvinyl chloride tape. .

As shown in Table 1, according to the present invention, it is possible to easily obtain a film substrate and a use of properties which are balanced in flexibility, hand cuttability, heat resistance, abrasion resistance, pinhole resistance, and blocking resistance. Its adhesive tape.

Industrial utilization possibility

The adhesive tape of the film substrate of the present invention can be suitably used, for example, as a binding tape for a bundled wire or a cable for use in a wire harness of an automobile.

In addition, the specification of the present invention is incorporated by reference to the specification of the Japanese Patent Application No. 2005-313824, the entire disclosure of which is incorporated herein by reference.

Claims (9)

A film base material comprising an aromatic vinyl-based elastomer; and 10 to 60 parts by mass of a styrene-based resin per 100 parts by mass of the aromatic vinyl-based elastomer; and 1 to 50 parts by mass The Vicat softening point is a styrene-based copolymer of 100 to 130 ° C, and the styrene resin is a polystyrene resin (GPPS) and/or a rubber-reinforced polystyrene resin (HIPS). The film substrate of claim 1, wherein the aromatic vinyl-based elastic system is selected from the group consisting of styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butyl At least one of a hydride of a diene random copolymer and a hydride of a styrene-butadiene block copolymer. For example, in the film substrate of claim 1 or 2, the styrene-based copolymer having a Vicat softening point of 100 to 130 ° C is composed of 80 to 99% by mass of an aromatic vinyl group. The monomer and 1 to 20% by mass of the ethylenically unsaturated carboxylic acid monomer are polymerized. The film substrate of claim 3, wherein the aromatic vinyl monomer is styrene, and the ethylenically unsaturated carboxylic acid monomer is methacrylic acid. The film substrate of claim 1 or 2, wherein the aromatic vinyl-based elastomer contains 1 to 300 parts by mass. Parts by mass of inorganic filler. The film substrate of claim 5, wherein the inorganic filler has an average particle diameter of 20 μm or less. The film substrate of claim 1 or 2, which is crosslinked by electron beam irradiation. An adhesive tape characterized by forming an adhesive layer on one side of a film substrate according to any one of claims 1 to 7. An adhesive tape for binding, which is characterized in that an adhesive tape as in item 8 of the patent application is used.