JP2003013022A - Pressure-sensitive adhesive tape and pressure-sensitive adhesive tape substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive tape having excellent heat distortion resistance and flame retardance (more excellent extensibility) without emitting toxic gases by combustion during an incineration treatment, and a pressure-sensitive adhesive tape substrate used for the pressure-sensitive adhesive tape. SOLUTION: This pressure-sensitive adhesive tape comprises a substrate containing an olefinic polymer and an inorganic flame-retardant without substantially containing a halogen atom. A pressure-sensitive adhesive layer is formed on at least one surface of the substrate and the pressure-sensitive adhesive tape exhibits <=65% heat distortion ratio at 100 deg.C and >=150% breaking elongation at 300 mm/min speed of testing rate of stressing.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive tape having flame retardancy and a pressure-sensitive adhesive tape base material used for the pressure-sensitive adhesive tape.

[0002]

2. Description of the Related Art Conventionally, a tape base material made of polyvinyl chloride (hereinafter referred to as PVC) (hereinafter also simply referred to as base material)
Adhesive tape using is excellent in mechanical properties (especially flexibility and extensibility), flame retardancy, heat distortion resistance, electrical insulation, etc. Furthermore, it is relatively inexpensive, so it can be used for automobiles, trains, buses. It has been used as an insulating tape for electric devices in various fields such as aircraft, ships, houses, factories, etc. In particular, a wire harness used for electric wiring of automobiles, a coil of electric home appliances, and an adhesive tape around which electric wires are bundled and wound have high flame retardancy (oxygen index concentration of 25% or more) and heat deformation resistance. Needed, PVC-based adhesive tapes have been commonly used to meet these needs.

However, due to the suspicion of the generation of harmful gases such as dioxin and chlorine gas when incinerated, PVC is restricted in use due to the increasing environmental awareness in recent years.
There is a movement to switch to materials with less environmental impact. Therefore,
As an alternative to PVC, it has been considered to use a polyolefin resin as a base material, which is less likely to generate dioxin even when incinerated, and which does not generate harmful gas such as chlorine gas. Since a system resin has a drawback that it burns more easily than PVC, it is necessary to add a flame retardant. For example, Japanese Patent Publication Sho 57-
Japanese Patent No. 10898 proposes to add an inorganic flame retardant such as magnesium hydroxide or aluminum hydroxide, which has a low environmental load.

However, considering the flexibility and extensibility required for the adhesive tape, polypropylene or high density polyethylene having a relatively high melting point is not suitable as the polyolefin resin, and low density polyethylene or linear low density polyethylene is not suitable. A low melting point polyolefin resin such as polyethylene, ultra low density polyethylene, medium density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer must be used. It is flexible and easy to stretch, but has the drawback of being easily deformed by heat.

As a method for improving the heat distortion resistance of a resin film, for example, a method of irradiating the film with ionizing radiation, or a crosslinking agent such as an organic peroxide such as dicumyl peroxide is added to the resin in advance. A method is known in which a formed film is subjected to steam heating or the like to form a crosslinked structure in the film. However, since these methods increase the number of production steps and increase the manufacturing cost,
It is difficult to put to practical use. As another method, polypropylene, ethylene-propylene copolymer, high-density polyethylene, etc., which have a relatively high melting point, and an elastomer composed of an ethylene-based copolymer (for example, EPM (ethylene-propylene copolymer rubber), EBR). (Ethylene-butene rubber),
EPDM (ethylene-propylene-diene copolymer rubber)
Etc.) has been investigated, but when an inorganic flame retardant is added to the polymer mixture, the molded product is extremely hard and lacks flexibility in an atmosphere at room temperature. As a result, the extensibility is remarkably reduced, and the heat distortion resistance cannot be sufficiently improved.

[0006]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention is an adhesive tape which does not generate toxic gas due to combustion during incineration and has excellent heat distortion resistance and flame retardancy, and the adhesive. An object is to provide an adhesive tape base material used for a tape. Furthermore, it is an object of the present invention to provide an adhesive tape having excellent heat distortion resistance and flame retardancy, and also excellent extensibility suitable for a tape winding operation, and an adhesive tape base material used for the adhesive tape.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, as an olefin polymer, a thermoplastic resin having a carbonylic oxygen atom in the molecular skeleton, and an ethylene component. And a polymer alloy containing a propylene component are used in combination, and an inorganic flame retardant is mixed with these to form a tape base material. They have found that an excellent adhesive tape substrate can be obtained, and have completed the present invention. That is, the present invention has the following features.

(1) A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on at least one side of a base material, wherein the base material contains an olefin polymer and an inorganic flame retardant and does not substantially contain a halogen atom. Yes, 10 of the adhesive tape
A pressure-sensitive adhesive tape having a heat deformation rate of 65% or less at 0 ° C. (2) The adhesive tape according to (1) above, wherein the adhesive tape has a breaking elongation at a tensile speed of 300 mm / min of 150% or more. (3) The olefin-based polymer constituting the base material has the following A
The above (1) or (2) containing a component and a B component
Adhesive tape as described. Component A: thermoplastic resin having a carbonylic oxygen atom in the molecular skeleton Component B: polymer alloy containing ethylene component and propylene component (4) The blending weight ratio (A: B) of component A and component B is 1: 9.
The adhesive tape according to (3) above, wherein the adhesive tape is from 8: 2. (5) The pressure-sensitive adhesive tape according to any one of (1) to (4), wherein the base material contains 20 to 200 parts by weight of an inorganic flame retardant per 100 parts by weight of an olefin polymer. (6) The adhesive tape according to any one of (1) to (5) above, wherein the inorganic flame retardant constituting the substrate is a metal hydroxide. (7) The dynamic storage elastic modulus (E ′) at 80 ° C. of the adhesive tape is 25 MPa or more, and the dynamic storage elastic modulus (E ′) at 120 ° C. is 10 MPa or more (1) to (). The adhesive tape according to any one of 6). (8) The above (1) to (7), wherein the base material is not subjected to a crosslinking treatment in the molding process and / or after the molding.
The adhesive tape according to any one of 1. (9) An adhesive tape base material containing an olefin polymer and an inorganic flame retardant and containing substantially no halogen atom, wherein the olefin polymer contains the following components A and B: Adhesive tape base material. Component A: thermoplastic resin having a carbonylic oxygen atom in the molecular skeleton Component B: polymer alloy containing ethylene component and propylene component (10) The blending weight ratio (A: B) of component A and component B is 1:
The adhesive tape substrate according to (9) above, which is 9 to 8: 2. (11) The adhesive tape substrate according to the above (9) or (10), which contains 20 to 200 parts by weight of an inorganic flame retardant per 100 parts by weight of an olefin polymer. (12) The above (9), wherein the inorganic flame retardant is a metal hydroxide.
The adhesive tape base material according to any one of to (11). (13) Dynamic storage elastic modulus (E ′) at 80 ° C. is 25
(9) to (1) above which the dynamic storage elastic modulus (E ′) at 120 ° C. is 10 MPa or more.
The pressure-sensitive adhesive tape substrate according to any one of 2). (14) The pressure-sensitive adhesive tape substrate according to any one of (9) to (13), wherein the substrate is not subjected to a crosslinking treatment in the molding process and / or after the molding.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The pressure-sensitive adhesive tape of the present invention comprises an olefin-based polymer and an inorganic flame-retardant and has a pressure-sensitive adhesive layer provided on at least one surface of a tape base material substantially free of halogen atoms. The heat deformation rate of the adhesive tape at 100 ° C. is 65% or less (preferably 40% or less, particularly preferably 0%), and the heat deformation rate is 65% or less, and the tensile speed is 300 mm /
The breaking elongation of the adhesive tape in minutes is 150% or more (preferably 170 to 500%).

Here, "the tape substrate is substantially free of halogen atoms" means that a substance containing halogen atoms in its molecule is not used as a constituent material of the substrate, For example, when the composition of the tape base material is analyzed by instrumental analysis means, a halogen atom detected at a trace level (for example, a halogen atom due to a halogen-containing substance used as a catalyst when synthesizing a compound (constituent material) is a compound ( As a result of being mixed into the constituent material), the inclusion of an extremely small amount of halogen atoms, etc. detected from the base material) is allowed.
Further, the heat deformation rate at 100 ° C. of the adhesive tape and the elongation at break (%) at a pulling speed of 300 mm / min are used as an index of the heat deformation resistance and the elongation of the adhesive tape, respectively. Heat deformation rate is 6
Those exhibiting 5% or less show sufficient heat distortion resistance in an actual use state (adhesion to an object), and the breaking elongation of the adhesive tape at the pulling speed of 300 mm / min is 15
Those showing 0% or more can be easily stretched in an actual use state (at the time of sticking (wrapping) around an object), and the sticking (wrapping) work can be performed with good workability. The heat deformation rate and elongation at break of such an adhesive tape are values measured by the following methods.

[Heat Distortion Rate Measuring Method] It is carried out according to UL-510. As shown in FIG. 1A, a test body 10 is prepared by winding an adhesive tape T around the outer peripheral surface of a round bar 1 having a diameter (d) of 2 mm and a length of 30 mm made of a conductor. The outer diameter (D ₀ ) of the test body 10 at room temperature is determined according to JIS B7503.
The dial gauge specified in 1), the caliper specified in JIS B7507, or a measuring instrument having a measurement accuracy similar to these is used. Next, the test body 10 is set to a specified temperature (1
The test piece was placed in a tester heated to 00 ° C. ± 1.0 ° C.) and heated for 60 minutes. Then, as shown in FIG. 1B, a cylindrical convex portion 2a having a diameter of 9.5 ± 0.2 mm was used. It is installed between the pressure plate 2 and the parallel plate 3 each having a pressure, and pressure (4.9 N) is applied from the direction perpendicular to the plate plane, and further the specified temperature (100 ° C ± 100 ° C).
After being left for 60 minutes at 1.0 ° C.), the outer diameter (D ₁ ) of the test piece was measured as it was, and the thickness of the tape before heating (t ₀ ) and the thickness of the tape after heating (t) were measured. ₁ ) is expressed by the following formula (I
I) and further by the following formula (III),
The reduction rate (heating deformation rate) (X) of the thickness of the tape after heating from the thickness of the tape before heating is calculated.

T = (D-d) / 2 (II) (In the formula, D is the outer diameter of the test body, d is the diameter of the round bar)

X (%) = {(t ₀ −t ₁ ) / t ₀ } × 100 (III) (where, t ₀ is the thickness before heating (mm), and t ₁ is the thickness after heating ( mm))

[Method of measuring elongation at break] Test piece (width 19 mm, length 100 mm) taken from an adhesive tape (a tape base material having a thickness of 0.2 mm provided with an adhesive layer having a thickness of 30 μm on one surface) Under an atmosphere of 23 ° C. and 60% RH, both ends in the length direction of the test piece (here, the length direction is applied to the molding flow direction (MD direction) of the tape base material). Then, with a universal tensile compression tester, pulling speed: 300
pulling the test piece in the length direction at mm / min,
Elongation at break (%) is measured.

In the present invention, the olefin-based polymer constituting the tape substrate is a mixture of an olefin-based polymer and an inorganic flame-retardant in an amount capable of obtaining sufficient flame-retardant property, and the adhesive tape is excellent in heat resistance and deformation resistance. And those which can impart extensibility can be used without particular limitation.
Those mainly composed of the component and the component B are preferable. Component A: thermoplastic resin having a carbonylic oxygen atom in the molecular skeleton Component B: polymer alloy containing ethylene and propylene components

The thermoplastic resin having a carbonylic oxygen atom (oxygen atom belonging to the carbonyl group) in the molecular skeleton of the component A mainly activates the flame retardancy-imparting action of the inorganic flame retardant and at the same time the tape group Material (adhesive tape)
Is a component that imparts appropriate flexibility and good extensibility, and a soft polyolefin resin having a carbonyl oxygen atom in the molecular skeleton is particularly preferable. As the soft polyolefin resin having a carbonylic oxygen atom in the molecular skeleton, an ethylene copolymer using a vinyl ester compound and / or an α, β-unsaturated carboxylic acid or a derivative thereof as a monomer or a comonomer. Or a metal salt (ionomer) thereof, etc., and generally has a melting point of 120 ° C. or lower, preferably 40 to 1
It is 00 ° C. Here, the melting point is a differential scanning calorimeter (DSC).
Is the measured value.

Examples of the vinyl ester compound in the above ethylene copolymer or its metal salt (ionomer) include vinyl alcohol lower alkyl esters such as vinyl acetate. Examples of the α, β-unsaturated carboxylic acid or its derivative include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride, or their anhydrides; acrylic. Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate , Stearyl acrylate, stearyl methacrylate, lauryl acrylate, lauryl methacrylate, maleic acid monomethyl ester,
Maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, glycidyl acrylate, unsaturated carboxylic acid esters such as glycidyl methacrylate, and the like, among them, (meth) acrylic acid alkyl ester is preferable, Particularly preferred is ethyl acrylate.

Preferable specific examples of the ethylene copolymer or its metal salt (ionomer) include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene- Acrylic acid-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-ethyl acrylate copolymer Examples thereof include coalesce and metal salts (ionomers) thereof, and these may be used alone or in combination of two or more.

The effect of activating the flame-retardant imparting action of the inorganic flame retardant by the thermoplastic resin having a carbonylic oxygen atom in the molecular skeleton of the component A is that the carbonylic oxygen atom is also present in the molecular skeleton. It cannot be obtained with a thermoplastic resin that does not stand.

The polymer alloy containing the ethylene component and the propylene component as the component B is a component mainly for suppressing the thermal deformation of the tape base material (adhesive tape), and by alloying two or more kinds of polymers, In particular, it is a polymer alloy showing viscoelasticity suitable for suppressing thermal deformation of the tape base material (adhesive tape).

The constitution (form) of the polymer alloy is not particularly limited, and for example, a polymer blend (physical mixture) in which two or more polymers are physically mixed, and two or more polymers are covalently bonded. IPN (Interpenetrati) in which block copolymers or graft copolymers that have been bonded are entangled with each other without being covalently bonded to each other.
ng Polymer Network) Various structures (forms) such as structures
Things are acceptable. In addition, the polymer alloy does not necessarily have to be uniform in composition (may have a distribution), and a polymer in which two or more polymers are compatible (compatible polymer alloy) or two or more polymers May be incompatible with each other to form a phase-separated structure (incompatible polymer alloy). Further, it may have thermal characteristics such that it has a plurality of exothermic or endothermic peaks measured by DSC.

Examples of the polymer alloy containing the ethylene component and the propylene component of the B component are, for example, polypropylene (homopolypropylene, random polypropylene).
Mixture of ethylene and polyethylene (including a copolymer of ethylene and a small amount of α-olefin), propylene / ethylene copolymer, terpolymer of propylene and ethylene and other α-olefins (As other α-olefins, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like can be mentioned, with 1-butene being preferred). Can be mentioned. Here, "homopolypropylene" means a polymer substantially consisting of 100% polypropylene, and "random polypropylene" means a polymer in which several% of ethylene components are randomly copolymerized.

When the polymer alloy is a copolymer, it is preferably a copolymer polymerized by multistage polymerization of two or more stages,
Further, a propylene / ethylene copolymer is preferable. The copolymer polymerized by the multi-stage polymerization of two or more stages is
Specifically, as described in JP-A-4-224809, for example, propylene or propylene and an α-olefin other than propylene are first subjected to multistage polymerization in the presence of a titanium compound and an organoaluminum compound catalyst. Prepolymerization in the first stage, and then in the second stage and thereafter, in the presence of the titanium-containing polyolefin produced and the organoaluminum compound, propylene and ethylene are copolymerized (if necessary, other than propylene and ethylene). It is obtained by further adding and copolymerizing α-olefin. Thereby, the polymer generated in the first stage (for example, polypropylene (propylene homopolymer), propylene-α-olefin copolymer, etc.)
And the polymer produced in the second and subsequent stages (for example, propylene-ethylene copolymer, propylene-ethylene-other α-olefin copolymer, etc.), at the molecular level in the polymerization process in the second and subsequent stages. It becomes a copolymer blended with.
As the titanium compound, for example, spherical particles obtained by co-milling titanium trichloride and magnesium chloride and treating with n-butyl orthotitanate, 2-ethyl-hexanol, ethyl p-toluate, silicon tetrachloride, diisobutyl phthalate and the like. A solid catalyst having an average particle diameter of 15 μm is used, and as the organic aluminum compound, for example, alkyl aluminum such as triethyl aluminum is used.
Further, in the polymerized layer, a silicon compound such as diphenyldimethoxysilane may be added as an electron donor,
It is also possible to add an iodine compound such as ethyl iodide.

The polymer alloy containing the ethylene component and the propylene component of the B component shows high elasticity at a high temperature, that is, in consideration of the temperature at the time of using the adhesive tape,
Its dynamic storage elastic modulus (E ') at 80 ° C is 40MP
a or more and less than 180 MPa (preferably 45 to 160 M)
A material having a dynamic storage elastic modulus (E ′) at 120 ° C. of 12 MPa or more and less than 70 MPa (preferably within a range of 15 to 65 MPa) is preferable. By exhibiting such a dynamic storage elastic modulus (E ′), thermal deformation of the tape base material (adhesive tape) is sufficiently suppressed. The dynamic storage elastic modulus (E ′) used here is the dynamic viscoelastic behavior of a test piece made of a polymer alloy (thickness 0.2 mm: width 10 mm, length 20 mm) and the temperature dispersion of the test piece. DMS200 (manufactured by Seiko Instruments, Inc.) is used as a measuring instrument, and the values are measured under the measuring conditions of measuring method: tension mode, temperature rising rate: 2 ° C./min, frequency: 1 Hz.

Specific examples of the polymer alloy exhibiting such a dynamic storage elastic modulus (E ') include, for example, Catalloy K manufactured by Montel SDC Sunrise Co., Ltd.
Examples include S-353P, Catalloy KS-021P, and Catalloy C200F.

In consideration of workability of the pressure-sensitive adhesive tape near room temperature (following property of the pressure-sensitive adhesive tape to an adherend) at room temperature, the polymer alloy of the component B has a dynamic storage elastic modulus (E ') at 23 ° C. Is preferably 200 MPa or more and less than 400 MPa. When the polymer alloy of the component B has such a dynamic storage elastic modulus (E ′), the tape base material has good flexibility and the followability to the adherend is improved. The dynamic storage elastic modulus (E ′) here is a value measured by the above-mentioned method, and specific examples of the polymer alloy exhibiting the dynamic storage elastic modulus (E ′) include, for example, Montel Sd. K-Sunrise Co., Ltd. product names Catalloy KS-353P, Catalloy KS-0
21P, Catalloy C200F and the like.

The blending weight ratio (A: B) of the component A (thermoplastic resin having a carbonylic oxygen atom in the molecular skeleton) and the component B (polymer alloy containing an ethylene component and a propylene component) is usually 1: 9 to. 8: 2, preferably 2: 8-
It is 6: 4. When the content of A component is small (the content of B component is large) out of such a weight ratio, the extensibility and flame retardancy of the tape substrate may decrease, and the content of A component is large (the content of B component is small). May reduce the heat distortion resistance.

In the present invention, as the inorganic flame retardant,
For example, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide and barium hydroxide; metal carbonates such as basic magnesium carbonate, magnesium-calcium carbonate, calcium carbonate, barium carbonate and dolomite. ; Hydrotalcite,
Metal hydrates such as borax (hydrates of metal compounds); barium metaborate, magnesium oxide and the like. These may be used alone or in combination of two or more. Among these, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide and barium hydroxide, and those selected from the group consisting of basic magnesium carbonate and hydrotalcite are flame-retardant. It is excellent in imparting effect and economically advantageous.

The particle size of the inorganic flame retardant varies depending on the kind of the compound, but for example, in metal hydroxides such as aluminum hydroxide and magnesium hydroxide, the average particle size is 0.1 to 50 μm, preferably A particle size of about 0.5 to 20 μm is suitable. The particle size here is the particle size measured by the laser diffraction method.

An appropriate amount of the inorganic flame retardant compounded is usually 20 to 200 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the olefin polymer. If the content of the inorganic flame retardant is out of this range and it is small, it becomes difficult to impart sufficient flame retardancy to the tape substrate (adhesive tape), and if it is large, the tape substrate (adhesive tape) The flexibility and extensibility tend to decrease.

Red phosphorus may be used for the purpose of promoting char (carbonized layer) of the inorganic flame retardant. When using red phosphorus, as a method (stabilization of the surface of red phosphorus) that does not generate toxic phosphine even when heated in the presence of water, red phosphorus is added to aluminum hydroxide, magnesium hydroxide, zinc hydroxide, hydroxide Double-coated by using a metal hydroxide coating selected from titanium, or by coating a thermosetting resin (phenolic resin, etc.) on the metal hydroxide coating. It is preferable to use the treated one. The char forming aid containing such red phosphorus is usually 2 to 100 parts by weight of the olefin polymer.
10 parts by weight, preferably 4 to 8 parts by weight is suitable.

When a char-forming aid containing red phosphorus is used, at least one selected from carbon black, borate and silicone compounds (silicone oil, silicone rubber, silicone resin, etc.) may be further used in combination. Good results can be obtained. In this case, at least one selected from carbon black, borate, and silicone compound is usually used in an amount of 0.5 to 10% by weight, preferably 1 to 5% by weight, based on 100 parts by weight of the olefin polymer.

In the present invention, the tape base material is composed of an olefin polymer and an inorganic flame retardant as essential components, and if necessary, an inorganic filler such as titanium oxide or zinc oxide, an amine type or a quinoline. -Based, hydroquinone-based, phenol-based, phosphorus-based, phosphite-based antioxidants and antioxidants, salicylic acid derivatives, benzophenone-based, benzotriazole-based, hindered amine-based UV absorbers, lubricants, plasticizers, etc. You may mix.

In the present invention, the tape base material is usually obtained by dry blending a polyolefin polymer and an inorganic flame retardant (and a material such as a filler, if necessary), and mixing the mixture with a Banbury mixer, rolls, It is obtained by kneading using an extruder or the like, and molding the kneaded product into a film by a known molding method such as compression molding, calender molding, injection molding or extrusion molding. The thickness of the tape substrate (film) varies depending on the application of the adhesive tape, but is generally 0.01 to 1 mm, preferably 0.0
It is 5 to 0.5 mm.

The tape base material of the present invention is subjected to a crosslinking treatment of irradiating with ionizing radiation such as electron beam, β ray, γ ray after forming the film, or crosslinking of an organic peroxide in the film forming material. It is preferable not to perform the crosslinking treatment in the molding process by adding the agent or the crosslinking aid. That is, it is preferable that the crosslinked structure is not formed on the entire substrate.

The adhesive tape of the present invention comprises an adhesive layer provided on at least one surface of the tape base material. As the pressure-sensitive adhesive, all existing pressure-sensitive adhesives such as rubber type, hot melt type, acrylic type and emulsion type can be applied. Examples of base polymers of rubber-based and hot-melt adhesives include natural rubber, recycled rubber, silicone rubber, isoprene rubber, styrene-butadiene rubber, polyisoprene, NBR, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer. Etc. are preferred.

Examples of tackifiers used for the pressure-sensitive adhesive include rosin-based tackifiers, terpene-based tackifiers, aliphatic petroleum hydrocarbon (C ₅ ) -based tackifiers,
Examples include aliphatic petroleum hydrocarbon (C ₉ ) tackifiers and hydrogenated compounds. Further, additives such as oils, waxes, and antioxidants that are generally added to the adhesive of the adhesive tape may be added. The amount of addition of these is determined according to a conventional method.

Of the above-mentioned pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferable, and examples of the acrylic pressure-sensitive adhesives include homopolymers of (meth) acrylic acid esters or copolymers with copolymerizable monomers. Examples of the (meth) acrylic acid ester or copolymerizable monomer include (meth) acrylic acid alkyl ester (for example, methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, octyl ester, etc.), (meth) acrylic acid glycidyl ester. , (Meth) acrylic acid, itaconic acid, maleic anhydride, (meth) acrylic acid amide, (meth) acrylic acid N-hydroxyamide, (meth) acrylic acid alkylaminoalkyl ester (for example, dimethylaminoethyl methacrylate, t- Butylaminoethylmethacrylate etc.), vinyl acetate, styrene, acrylonitrile and the like. Of these, as the main monomer, an acrylic acid alkyl ester whose homopolymer (homopolymer) has a glass transition temperature of −50 ° C. or lower is usually preferable.

As a method of applying the pressure-sensitive adhesive, a conventionally known method can be used, for example, a casting method, a roll coater method, a reverse coater method, a doctor blade method or the like can be used.

The thickness of the pressure-sensitive adhesive layer (thickness after drying) varies depending on the application of the pressure-sensitive adhesive tape, but is generally 10 to 50 μm.
m, preferably 15-40 μm.

In the present invention, the pressure-sensitive adhesive tape has a dynamic storage elastic modulus (E ′) at 80 ° C. of 25 MPa or more and 120 ° C.
It is preferable that the storage elastic modulus (E ′) is 10 MPa or more. By having such dynamic viscoelasticity, thermal deformation of the tape base material (adhesive tape) is extremely unlikely to occur. The dynamic storage elastic modulus (E ′) at 80 ° C. is 200 in view of appropriate flexibility and extensibility required for the adhesive tape.
It is preferably not more than MPa, and the dynamic storage elastic modulus (E ′) at 120 ° C. is preferably not more than 150 MPa. The dynamic storage elastic modulus (E ′) of the adhesive tape here is a test piece (width 10 mm, length 20 mm) prepared from an adhesive tape having a 0.2 mm-thick tape base material provided with an adhesive layer, and the test Dynamic viscoelastic behavior due to temperature dispersion of a piece is measured using DMS200 (manufactured by Seiko Instruments, Inc., trade name) as a measuring device under measurement conditions: tensile mode, temperature rising rate: 2 ° C / min, frequency: 1 Hz. It is the value.

The dynamic storage elastic modulus (E ') of the pressure-sensitive adhesive tape has almost no effect on its value (that is, it varies depending on whether the pressure-sensitive adhesive layer has the pressure-sensitive adhesive layer or only the tape base material). The value of the dynamic storage elastic modulus (E ') does not change.), Which is substantially the dynamic storage elastic modulus (E') of the tape substrate.

[0043]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[Materials Used] Component A (having a carbonylic oxygen atom in the molecular skeleton )
Thermoplastic resin A1: Ethylene-vinyl acetate copolymer (EVA), melting point 84 ° C [trade name: Evaflex P-1905, manufactured by Mitsui DuPont Polychemical Co., Ltd.] A2: ethylene-ethyl acrylate copolymer ( EE
A), melting point 84 ° C. [Brand name: EVAFLEX A-70
2, manufactured by Mitsui DuPont Polychemical Co., Ltd.]

Component B (ethylene component and propylene component
Including polymer alloy) B1: Catalloy KS-353P (trade name), manufactured by Montel SDC Sunrise Co., Ltd. B2: Catalloy KS-021P (trade name), manufactured by Montel SDC Keith Sunrise Co., Ltd. B3: Catalloy C200F (Trade name), manufactured by Montel SDK Sunrise Co., Ltd.

23 ° C., 80 ° C., 120 of the above B1 to B3
The dynamic storage modulus at ° C is as follows. B1 (23 ° C: 210 MPa, 80 ° C: 52 MPa, 1
20 ° C .: 21 MPa) B2 (23 ° C .: 294 MPa, 80 ° C .: 125 MPa,
120 ° C .: 59 MPa) B3 (23 ° C .: 303 MPa, 80 ° C .: 65 MPa, 1
20 ° C: 20 MPa)

C Component (Inorganic Flame Retardant) C1: Magnesium Hydroxide (Mg (OH) ₂ ) [Brand Name: Magcise N-3 Kamijima Chemical Industry Co., Ltd.] C2-1: Red Phosphorus [Brand Name: Hishigad] CP-A15
Nippon Chemical Industry Co., Ltd.] C2-2: Red phosphorus [Product name: Nova Excel F5 Phosphorous Chemical Industry Co., Ltd.] C3: Carbon black [Product name: Seast 3H Tokai Carbon Co., Ltd.]

[Method for Making Tape Base Material and Adhesive Tape]
The materials of the above-mentioned components A, B and C are dry blended, and then kneaded at 180 ° C. in a 3 L pressure kneader to pelletize. The composition was molded into a film having a thickness of 0.2 mm by a T-die extruder to prepare a tape base material, and one side of the tape base material was subjected to corona discharge treatment and then prepared by the following method. A system adhesive is applied (thickness 30 μm) to produce an adhesive tape.

[Preparation Method of Acrylic Adhesive] Cooling Tube,
2-Ethylhexyl acrylate 100 in a toluene solvent was placed in a reaction vessel equipped with a nitrogen introduction tube, a thermometer and a stirrer.
By weight, 2 parts by weight of acrylic acid and 0.2 parts by weight of benzoyl peroxide as a polymerization initiator were added, and the mixture was reacted at 60 ° C. for 8 hours to obtain a polymer. An acrylic pressure-sensitive adhesive was prepared by adding 3 parts by weight of a polyisocyanate crosslinking agent (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) to 100 parts by weight of the polymer solid content in this polymer solution.

(Examples 1 to 7) Component A, component B and C
A tape base material (adhesive tape) was prepared according to the above-mentioned preparation method, using the ingredients and the compounding amounts shown in Table 1 below.

Comparative Example 1 A component (A1: 100 parts by weight) was used, B component and C component were not used, and the other components were prepared according to the above-mentioned tape substrate (adhesive tape) preparation method. Tape).

(Comparative Example 2) A component (A2: 100 parts by weight) was used, B component and C component were not used, and the other components were prepared according to the above-mentioned tape substrate (adhesive tape) preparation method. Tape).

(Comparative Example 3) Component B (B1: 100 parts by weight) was used, components A and C were not used, and the other components were prepared according to the above tape substrate (adhesive tape) preparation method. Tape).

(Comparative Example 4) 100 parts by weight of polypropylene (PP) [trade name: Novatec FX3 Nippon Polychem Co., Ltd.] was used without using the components A, B and C, and the other components were the above tape bases. A tape base material (adhesive tape) was created according to the method of creating the material (adhesive tape).

(Comparative Example 5) A component (A1: 100 parts by weight) and a component C (C1: 50 parts by weight) were used, the component B was not used, and the other components were the above-mentioned tape base material (adhesive tape). A tape base material (adhesive tape) was prepared according to the method.

(Comparative Example 6) A component (A1: 100 parts by weight) and a component C (C1: 100 parts by weight) were used, the component B was not used, and the other components were the above-mentioned tape base material (adhesive tape). A tape base material (adhesive tape) was prepared according to the method.

(Comparative Example 7) A component (A1: 100 parts by weight) and C component (C1: 105 parts by weight, C2-1: 5 parts by weight) were used, B component was not used, and the others were the above tapes. A tape base material (adhesive tape) was prepared according to the method for preparing the base material (adhesive tape).

(Comparative Example 8) A component (A1: 100 parts by weight), C component (C1: 50 parts by weight, C2-2: 4 parts by weight, C3: 2 parts by weight) were used, and B component was not used. Other than that, the tape base material (adhesive tape) was prepared according to the above-described method for preparing the tape base material (adhesive tape).

(Comparative Example 9) A component (A1: 50 parts by weight), C component (C1: 100 parts by weight, C3: 2 parts by weight), polypropylene (PP) [trade name: Novatec F
X3 Nippon Polychem Co., Ltd.] 15 parts by weight, ethylene-
Propylene rubber (EPR) [Product name: SPO VO-1
41 Sumitomo Chemical Co., Ltd.]
A tape base material (adhesive tape) was prepared according to the above-mentioned tape base material (adhesive tape) preparation method without using any component.

[Evaluation Test] Examples 1 to 7 and Comparative Example 1
The following evaluation tests were performed for each tape base material (adhesive tape) of No. 9 to No. 9. The dynamic storage elastic modulus (E ′) of the adhesive tape at 80 ° C. and 120 ° C. was measured by the method described above.

Evaluation of Flame Retardancy At the stage of forming a sheet having a thickness of 3 mm with a pressing machine at the time of producing the tape base material, a test piece (dimension: length 70 mm, width 6.5 mm) was taken from the sheet. , J
The test piece is burned according to the burning test method of the polymer material by the oxygen index method of IS K7201, and the burning time of the test piece is 3 minutes or more continuously, or the burning length after the burning is 50.
The minimum oxygen flow rate and the nitrogen flow rate at that time required to continue burning for more than 1 mm are measured by a flow meter (device name "candle combustion tester").
It was measured by Toyo Seiki Co., Ltd., and the oxygen index was determined by the following formula (I), and flame retardancy was evaluated by the oxygen index. 25
% Or more was accepted, and less than 25% was rejected.

Oxygen index (OI) = {[O ₂ ] / ([O ₂ ] + [N ₂ ])} × 100 (I)

(In the formula, [O ₂ ] is the flow rate of oxygen (l / mi
n) and [N ₂ ] are nitrogen flow rates (1 / min). )

Evaluation of Heat Deformation and Elongation The heat deformation of the adhesive tape was measured by the above-mentioned method, and the heat deformation of 65% or less was regarded as acceptable. The extensibility was measured by measuring the breaking elongation of the pressure-sensitive adhesive tape by the above-mentioned method, and the breaking elongation of 150% or more was regarded as acceptable.

These evaluation results and the adhesive tape at 80 ° C.
The dynamic storage elastic modulus (E ') at 120 ° C is shown in Table 1 below.

[0066]

[Table 1]

In the table, the amounts of the components A, B and C are parts by weight. Further, * means that the adhesive tape (base material) was melted and the dynamic storage elastic modulus (E ′) could not be measured. A heating deformation rate of 100% means that the adhesive tape melted and flowed down from the round bar, and the tape form could not be retained. Polypropylene (PP) used in Comparative Examples 4 and 9, ethylene-propylene rubber (E
(PR) is described in the column of B component for convenience.

[0068]

As is apparent from the above description, according to the present invention, the adhesive tape base material contains the olefin polymer and the inorganic flame retardant and does not substantially contain a halogen atom. The heat deformation rate of the adhesive tape at 100 ° C is 65% or less, and the pulling speed is 300 mm.
Since the elongation at break (%) in 1 / min is 150% or more, it has appropriate flexibility, excellent extensibility and heat distortion resistance while containing an inorganic flame retardant, It is possible to obtain an adhesive tape that exhibits flame retardancy and that does not generate toxic gases such as dioxins and halogen gases during incineration. The adhesive tape is a substitute for an adhesive tape using a PVC base material that has been used as an insulating tape for electric devices in various fields such as vehicles such as automobiles, trains and buses, aircraft, ships, houses, factories, etc. Since it can be used sufficiently as it is, and it does not generate toxic gas during incineration, it has a low environmental load and its utility value is extremely high.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a method for evaluating a heat deformation rate of an adhesive tape, in which (a) is a side view of a test body and (b) is a side view of a test apparatus.

[Explanation of symbols]

1 round bar 2 pressure plate 2a convex part 3 parallel plates 10 specimens T adhesive tape

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masayoshi Natsume             1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto             Electric Works Co., Ltd. (72) Inventor Shinichi Takada             1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto             Electric Works Co., Ltd. (72) Inventor Takaki Oyama             1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto             Electric Works Co., Ltd. (72) Inventor ▼ Yanagi ▲ Hajime Ta             1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto             Electric Works Co., Ltd. F-term (reference) 4J004 AB01 CA04 CA07                 4J040 JA09 JB09

Claims (14)

[Claims] 1. A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on at least one surface of a base material, wherein the base material contains an olefin polymer and an inorganic flame retardant and does not substantially contain a halogen atom. , 100 ° C of the adhesive tape
An adhesive tape having a heat deformation rate of 65% or less. 2. The pulling speed of the adhesive tape is 300 mm /
The adhesive tape according to claim 1, which has a breaking elongation of 150% or more per minute. 3. The pressure-sensitive adhesive tape according to claim 1, wherein the olefin polymer constituting the base material contains the following A component and B component. Component A: thermoplastic resin having a carbonylic oxygen atom in the molecular skeleton Component B: polymer alloy containing ethylene and propylene components 4. A blending weight ratio of component A and component B (A: B).
Is 1: 9 to 8: 2, The adhesive tape according to claim 3. 5. The adhesive tape according to claim 1, wherein the base material contains 20 to 200 parts by weight of an inorganic flame retardant per 100 parts by weight of an olefin polymer. 6. The pressure-sensitive adhesive tape according to claim 1, wherein the inorganic flame retardant constituting the substrate is a metal hydroxide. 7. The dynamic storage elastic modulus (E ′) at 80 ° C. of the adhesive tape is 25 MPa or more, and 12
The adhesive tape according to claim 1, which has a dynamic storage elastic modulus (E ′) at 0 ° C. of 10 MPa or more. 8. The substrate according to claim 1, wherein the substrate is not subjected to a crosslinking treatment during and / or after the molding process.
7. The adhesive tape according to any one of 7. 9. An adhesive tape substrate containing an olefin polymer and an inorganic flame retardant and containing substantially no halogen atom, wherein the olefin polymer contains the following components A and B. Adhesive tape base material characterized by. Component A: thermoplastic resin having a carbonylic oxygen atom in the molecular skeleton Component B: polymer alloy containing ethylene and propylene components 10. A blending weight ratio of the component A and the component B (A:
The pressure-sensitive adhesive tape substrate according to claim 9, wherein B) is 1: 9 to 8: 2. 11. The pressure-sensitive adhesive tape base material according to claim 9, which contains 20 to 200 parts by weight of an inorganic flame retardant per 100 parts by weight of an olefin polymer. 12. The adhesive tape base material according to claim 9, wherein the inorganic flame retardant is a metal hydroxide. 13. The dynamic storage elastic modulus (E ′) at 80 ° C. is 25 MPa or more, and the dynamic storage elastic modulus (E ′) at 120 ° C. is 10 MPa or more. The adhesive tape substrate according to. 14. The pressure-sensitive adhesive tape substrate according to any one of claims 9 to 13, wherein the substrate is not subjected to a crosslinking treatment in the molding process and / or after the molding.