KR101133001B1 - Film base material and adhesive tape - Google Patents

Abstract

With a relatively small amount of bromine-based flame retardant, there is provided a film base material having a good balance of flexibility, cutting properties, heat resistance, abrasion resistance, flame retardancy, and bleed-out characteristics, and an adhesive tape using the film base material.

10 to 60 parts by mass of the styrene resin, 1 to 50 parts by mass of the styrene copolymer, and 5 to 100 parts by mass of the bromine flame retardant based on the aromatic vinyl elastomer and 100 parts by mass of the aromatic vinyl elastomer. It is a film base material to make. The aromatic vinyl elastomer is at least one member selected from the group consisting of styrene-butadiene random copolymers, styrene-butadiene block copolymers, hydrogenated styrene-butadiene random copolymers, and hydrogenated styrene-butadiene block copolymers. It is preferable.

Description

Film base material and adhesive tape {FILM BASE MATERIAL AND ADHESIVE TAPE}

The present invention relates to a film base material having a high flame retardancy with the addition of relatively little bromine-based flame retardant and an adhesive tape using the same.

Various adhesive tapes, such as insulating tapes used for electric machines in automobiles, railways, aircraft, ships, houses, factories, etc., have moderate flexibility and extensibility, and have flame retardancy, mechanical strength, heat deformation resistance, electrical insulation, and molding processability. Since the point is excellent and relatively inexpensive, the film which uses the resin composition containing vinyl halide resins, such as polyvinyl chloride, as a raw material has been used. However, since a halogenated vinyl resin film produces | generates toxic gas at the time of incineration disposal, the film which uses the non-halogen resin composition which consists of polyolefin resins as a raw material is beginning to be used in recent years. Using the composition which mix | blended the olefin resin and styrene resin as a film base material (for example, refer patent document 1), and using the composition which mix | blended the olefin resin and inorganic flame retardant as a film base material (Example For example, Patent Document 2) is known. However, these tapes were inferior in flexibility, cutability, heat resistance, and abrasion resistance as compared with films using resin compositions containing vinyl halide resins as raw materials.

The adhesive tape which uses a non-halogen-type resin composition as a raw material generally lacks flame retardance. On the other hand, since vinyl chloride contains a large amount of chlorine atoms, it has flame retardancy by itself. For this reason, even if a large amount of plasticizer is added, a vinyl chloride tape can have a flame retardance of the level of self-extinguishing (the extent to which it will naturally extinguish when a fire source is removed from air).

On the other hand, the request of more advanced flame retardance of the film which uses a non-halogen-type resin composition as a raw material, and the adhesive tape using the same is increasing. In the flame retardant method, various studies have been made so far, but in order to obtain an effective flame retardant effect, it is necessary to add a very large amount of flame retardant. In particular, the method of using a bromine flame retardant has a higher flame retardant effect than other flame retardants, and among many industrial standards, there is a standard that does not pass unless a bromine flame retardant is used. However, when bromine-based flame retardants are added in a large amount in order to obtain flame retardancy equivalent to that of vinyl chloride tape, since the film substrate for the adhesive tape is very thin, a bleed-out phenomenon in which the flame retardant floats on the surface of the film substrate occurs, leading to a decrease in mechanical properties. It was sometimes difficult to obtain a flame retardant equivalent to vinyl chloride.

Patent Document 1: Japanese Unexamined Patent Publication No. 2000-38550

Patent Document 2: Japanese Unexamined Patent Publication No. 2001-192629

DISCLOSURE OF INVENTION

Problems to be Solved by the Invention

The present invention provides a film base material having a relatively low amount of bromine-based flame retardant, flexibility, cutability, heat resistance, abrasion resistance, flame retardancy, and bleed-out, and having a good balance of these properties, and an adhesive tape using the film base material. It aims to provide.

Means to solve the problem

This invention achieves the said objective and has the following summary.

(1) 10 to 60 parts by mass of styrene resin, 1 to 50 parts by mass of styrene copolymer, and 5 to 100 parts of brominated flame retardant based on the aromatic vinyl elastomer and 100 parts by mass of the aromatic vinyl elastomer. It contains a mass part, The film base material characterized by the above-mentioned.

(2) The aromatic vinyl elastomer is at least one member selected from the group consisting of styrene-butadiene random copolymers, styrene-butadiene block copolymers, hydrogenated styrene-butadiene random copolymers and hydrogenated styrene-butadiene block copolymers. The film base material as described in said (1).

(3) The film base material as described in said (1) or (2) whose styrene resin is polystyrene resin (GPPS) and / or rubber reinforced polystyrene resin (HIPS).

(4) The styrene-based copolymer is a styrene-based copolymer having a non-cut softening point of 100 to 130 ° C, and is also obtained by polymerizing 80 to 99 mass% of an aromatic vinyl monomer and 1 to 20 mass% of an ethylenically unsaturated carboxylic acid monomer. The film base material in any one of said (1)-(3) whose aromatic vinyl monomer is styrene, and this ethylenic unsaturated carboxylic monomer is methacrylic acid.

(5) The film base material in any one of said (1)-(4) whose bromine flame retardant is a bromine flame retardant whose 5% weight loss temperature is 220-350 degreeC.

(6) The film base material in any one of said (1)-(5) whose bromine content of a brominated flame retardant is 50-99 mass%.

(7) The film base material in any one of said (1)-(6) containing 1-300 mass parts of inorganic fillers with respect to 100 mass parts of aromatic vinyl-type elastomers.

(8) The film base material in any one of said (1)-(7) whose oxygen index of a film base material is 25 or more.

(9) The adhesive tape which provided the adhesive layer in the at least single side | surface of the film base material in any one of said (1)-(8).

(10) The tape for binding using the adhesive tape as described in said (9).

(11) (a) 10-60 mass parts of styrene resins, 1-50 mass parts of styrene copolymers, and a brominated flame retardant with respect to an aromatic vinyl elastomer and 100 mass parts of the aromatic vinyl elastomer Of an adhesive tape having a step of mixing a composition containing 5 to 100 parts by mass, (b) molding the mixed composition on a film substrate, and (c) applying a pressure-sensitive adhesive on at least one surface of the film substrate. It is a manufacturing method.

Effects of the Invention

By using the film base material of this invention, the adhesive tape which has flexibility, cutting property, heat resistance, abrasion resistance, flame retardance, and a bleed-out hardly generate | occur | produce, and which balanced these characteristics can be obtained.

Best Mode for Carrying Out the Invention

The film base material of this invention consists of a styrene resin and a styrene-type copolymer whose resin component uses an aromatic vinyl elastomer as a base resin component. The reason why the aromatic vinyl elastomer is used as the base resin component is that the film base material is not hardened and flexibility can be expressed.

In addition, the unit of "part" which shows the compounding composition of this invention is represented on a mass basis unless there is particular notice.

The aromatic vinyl elastomer that can be used for the film base material of the present invention comprises a polymer block of an aromatic vinyl hydrocarbon and an elastomeric polymer block, wherein the polymer block of the aromatic vinyl hydrocarbon is a hard segment, and the elastomeric polymer block is a soft segment. It is preferable to comprise each.

The aromatic vinyl elastomer typically has a copolymer structure represented by an aromatic vinyl hydrocarbon polymer block-elastomeric polymer block or an aromatic vinyl hydrocarbon polymer block-elastomeric polymer block-aromatic vinyl hydrocarbon polymer block, and a double of an elastomeric polymer block. As a block copolymer or random copolymer which the bond may be partially or completely hydrogenated, it is generally known as a styrene-type elastomer.

As an aromatic vinyl hydrocarbon which comprises an aromatic vinyl hydrocarbon block, styrene, (alpha) -methylstyrene, o-, m-, and p-methylstyrene, 1, 3- dimethyl styrene, vinyl naphthalene, vinyl anthracene etc. are mentioned, for example. Among them, styrene is preferable.

Moreover, as an elastomeric polymer block, if an elastomer property is expressed, it may be a conjugated diene system and may be other than a conjugated diene system, but a conjugated diene system is generally preferable. Examples of the conjugated diene in this case include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like.

Examples of the aromatic vinyl elastomer include styrene-ethylene butylene copolymer-styrene (SEBS), styrene-propylene copolymer-styrene (SEPS), styrene-butadiene-styrene (SBS), and styrene-isoprene-styrene (SIS). ABA type block copolymers or random copolymers, or hydrogenated products of these ABA type block copolymers or random copolymers, or AB type block copolymers such as styrene-butadiene copolymers and styrene-isoprene copolymers or random aerials A copolymer, or the hydrogenated substance of these AB type block copolymers and a random copolymer, etc. are mentioned. Among the aromatic vinyl elastomers, hydrogenated products of styrene-butadiene random copolymers, styrene-butadiene block copolymers, styrene-butadiene random copolymers and hydrogenated products of styrene-butadiene block copolymers are preferable. In particular, the complete hydrogenated substance of the styrene-butadiene random copolymer is more preferable because of its low elongation at break.

The styrene resin which can be used for the film base material of this invention is the monomer 1 which can copolymerize styrene or styrene and styrene in the presence of the homopolymer of styrene, the copolymer of styrene and the monomer copolymerizable with styrene, and a rubbery polymer. (Co) polymerization of species or more is preferable.

As a monomer which can be copolymerized to styrene, (alpha)-substituted styrene, such as (alpha) -methylstyrene; Aromatic ring-substituted styrenes such as vinyltoluene and t-butyl styrene; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; Acrylate esters such as methyl acrylate and ethyl acrylate; Methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; Vinyl carboxylic acids such as acrylic acid and methacrylic acid; Unsaturated carboxylic acid amides such as acrylic acid amide and methacrylic acid amide; Unsaturated dicarboxylic acid imide derivatives such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; And unsaturated dicarboxylic anhydrides such as maleic acid, itaconic acid and citraconic acid. However, it is not limited to these.

It does not specifically limit as styrene resin, Well-known resin generally used can be used. Specifically, a polystyrene resin called GPPS and / or a rubber-reinforced polystyrene resin called HIPS may be mentioned. Especially, the polystyrene resin which is easy to adjust the film strength by molecular weight control, or the mixture of a polystyrene resin and rubber reinforcement polystyrene resin is preferable.

The compounding quantity of styrene resin in the film base material of this invention is 10-60 mass parts with respect to 100 mass parts of aromatic vinyl-type elastomers, Preferably it is the range of 10-50 mass parts. If the styrene-based resin is less than 10 parts by mass, the strength of the film base material is low, so that the film is easily stretched. On the other hand, when styrene resin exceeds 60 mass parts, the workability of a film base material will disappear, and a film base material may be rigid and pinhole resistance may fall.

As for the styrene copolymer which can be used for the film base material of this invention, the styrene copolymer whose beaker softening point is 100-130 degreeC is preferable. If the beaker softening point is less than 100 ° C., the film base material is heat-shrinked and its heat resistance is poor, and appearance defects may occur due to wrinkles caused by film shrinkage during adhesive processing. On the other hand, when a beaker softening point exceeds 130 degreeC, the poor appearance of the film base material by the fish eye and pinhole generation by the kneading | mixing defect of resin may arise. In particular, a styrene copolymer having a beaker softening point of 110 to 120 ° C is preferable.

The compounding quantity of the styrene copolymer whose beaker softening point is 100-130 degreeC is 1-50 mass parts with respect to 100 mass parts of aromatic vinylic elastomers, Preferably it is 10-35 mass parts. When the styrene-based copolymer having a beaker softening point of 100 to 130 ° C is less than 1 part by mass, the heat shrink of the film base material may be deteriorated. On the other hand, when the non-curing softening point exceeds 50 mass parts of the styrene copolymer of 100-130 degreeC, the workability of a film base material may worsen.

The styrene-based copolymer having a beaker softening point of 100 to 130 ° C is preferably formed by polymerizing 80 to 99% by mass of an aromatic vinyl monomer and 1 to 20% by mass of an ethylenically unsaturated carboxylic acid monomer. More preferably, it is a thing formed by superposing | polymerizing 85-98 mass% of aromatic vinyl monomers, 2-15 mass% of ethylenically unsaturated carboxylic monomers, and 0.1-10 mass% of vinyl monomers copolymerizable with these. 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 lowered, and the melt viscosity difference with the aromatic vinyl elastomer is large, resulting in poor melt mixing properties. Since the workability of a film base material may worsen. Moreover, when an aromatic vinyl monomer exceeds 99 mass% or ethylenically unsaturated carboxylic monomer is less than 1 mass%, the heat-resistant provision effect as a film base material may worsen.

As an aromatic vinyl monomer of the styrene-type copolymer whose beaker softening point is 100-130 degreeC, styrene, such as styrene, (alpha) -methylstyrene, vinyltoluene, ethyl styrene, and t-butyl styrene, and its substituent are mentioned. Preferably it is styrene that facilitates control of the molecular weight increased by the reaction.

As an ethylenic unsaturated carboxylic monomer of the styrene copolymer whose beaker softening point is 100-130 degreeC, acrylic acid or its ester acid; Methacrylic acid or esters thereof; Α, β-unsaturated dicarboxylic acids such as fumaric acid, maleic acid and itaconic acid or monoesters, diesters, anhydrides or imides thereof; Acrylonitrile; And 6-membered ring anhydrides or imides secondary derived by intramolecular dehydration (or dealcoholization) reaction of monomer units such as acrylic acid, methacrylic acid or esters thereof adjacent to the molecule. Especially, it is methacrylic acid preferably.

As a vinyl monomer which can be copolymerized with the aromatic vinyl monomer and ethylenic unsaturated carboxylic monomer of the styrene-type copolymer whose beaker softening point is 100-130 degreeC, (meth) acrylic acid, such as methyl methacrylate and n-butyl acrylate Ester monomers; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; Unsaturated carboxylic acid monomers other than methacrylic acid such as maleic anhydride, maleic acid, itaconic acid and itaconic anhydride; Maleimide monomers, such as maleimide, N-methyl maleimide, and N-phenyl maleimide, etc. are mentioned. These may be used independently or may use two or more types together.

Although the beaker softening point of this invention does not have a restriction | limiting in particular in the manufacturing method of the styrene copolymer which is 100-130 degreeC, The bulk polymerization method, suspension polymerization method, solution polymerization method, and emulsion polymerization method can be employ | adopted preferably.

Beaker softening point (degreeC) in this invention is measured by the following method.

Name of device: Vicut Softening Point Tester (manufactured by Toyo Corp., trade name: VSP tester)

Test piece: The plate-shaped test piece of length 30mm x width 19mm x thickness 3.2mm was shape-molded by injection molding, left to stand in the constant temperature and humidity chamber of temperature 23 degreeC, and 50% of a relative humidity for 24 hours.

Test Method: Using a weight of 5 kg, 50 ℃ / hr. The temperature was raised at a temperature rising rate of and the temperature when the indenter entered 1 mm into the test piece was measured. The test was carried out three times and the average value was taken as the non-cut softening point.

The film base material of this invention mix | blends a brominated flame retardant in order to provide desired flame retardance. As a bromine flame retardant, what is already known can be added, What is close to the thermal decomposition temperature of an aromatic vinyl elastomer is preferable, The brominated flame retardant whose 5% weight loss temperature is 220-350 degreeC is preferable.

In the present invention, the desired flame retardancy is, as an index, an oxygen index of 25 or more, preferably 27 or more, which is generally a flame retardant level having self-extinguishing property. This is consistent with the flame retardant level of vinyl chloride tape used for general electrical insulation and binding applications. In addition, the present invention can be adapted even when higher flame retardancy is required.

The compounding quantity of the bromine type flame retardant whose 5% weight loss temperature is 220-350 degreeC is 5-100 mass parts with respect to 100 mass parts of aromatic vinylic elastomers, Preferably it is the range of 10-30 mass parts. When the brominated flame retardant having a 5% weight loss temperature of 220 to 350 ° C. is less than 5 parts by mass, sufficient flame retardant performance may not be exhibited. When the bromine-based flame retardant having a 5% weight loss temperature of 220 to 350 ° C exceeds 100 parts by mass, bleed out may occur and the film substrate may be rigid and pinhole resistance may decrease.

The bromine flame retardant having a 5% weight loss temperature of 220 to 350 ° C preferably has a bromine content of 50 to 99 mass%, preferably 70 to 90 mass%. For example, tris (tribromopentyl) phosphate, tetrabromobisphenol A bis (2,3-dibromopropyl ether), pentabromobenzyl acrylate, poly (pentabromobenzyl acrylate), hexabro Mocyclododecane, tetrabromobisphenol-A, brominated trimethylphenylindane, tris (2,3-dibromopropyl) isocyanate, bis (3,5-dibromo-4 (2,3-dibromorph Lopoxy) phenyl) sulfone, ethane-1,2-bis (pentapropophenyl), poly-4,4'-isopropylidenebis (2,6-dibromophenyl) carbonate, 4,4'-dibro Mobiphenyl, etc., but is not limited to these. These may be used independently or may use two or more types together. Among them, hexabromocyclododecane and ethane-1,2-bis (pentapropophenyl) are more preferable.

The brominated flame retardant having a 5% weight loss temperature of 220 to 350 ° C has a 5% weight loss temperature of 220 to 350 ° C, preferably 230 to 260 ° C. When the 5% weight loss temperature is less than 220 ° C, bleed out may occur or be different from the thermal decomposition temperature of the aromatic vinyl elastomer resin, thereby not exhibiting sufficient flame retardant performance. On the other hand, when 5% weight loss temperature exceeds 350 degreeC, it may differ from the thermal decomposition temperature of aromatic vinyl-type elastomer resin, and may not exhibit sufficient flame-retardant performance.

The 5% weight loss temperature in the present invention is measured by the following method.

Equipment Name: Differential Heat Balance DTA / TG (manufactured by TA Instruments, trade name: Model2950)

Test method: It measures on the conditions of temperature rising rate 10 degree-C / min, and nitrogen atmosphere.

The bromine flame retardant having a 5% weight loss temperature of 220 to 350 ° C has a weight average molecular weight of 500 to 2000. More preferably, it is 550-1000. If the weight average molecular weight of the brominated flame retardant whose 5% weight loss temperature is 220-350 degreeC is less than 500, a bleed out may arise. On the other hand, when a weight average molecular weight exceeds 2000, 5% weight loss temperature may become high and a flame retardant performance may not be exhibited.

It is preferable that the film base material of this invention contains an inorganic filler. The reason why the inorganic filler is blended is to improve the cutting property of the film base material, and to increase the thermal conductivity during the molding process to increase the cooling effect of the film base material and to suppress the deformation generated in the film base material small.

The average particle diameter of an inorganic filler is 20 micrometers or less, for example, Preferably it is the range of 10 micrometers or less. When the average particle diameter exceeds 20 µm, the tensile strength and the elongation at break of the film substrate may be lowered, and the flexibility and the pinhole may be generated. The average particle diameter is a value based on particle distribution measurement by laser diffraction method.

As a particle distribution measuring device, there exists a brand name "model LS-230" by the Beckman Coulter company. Moreover, when mix | blending an inorganic filler as a non-halogen-type flame retardant, the formation of a car (carbonized layer) can be aimed at and the flame retardance of a film base material can also be improved.

As the inorganic filler, for example, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, triphenylphosphite, ammonium polyphosphate, polyphosphamide, zirconium oxide, magnesium oxide, zinc oxide, titanium oxide , Molybdenum oxide, guanidine phosphate, hydrotalcite, smectite, zinc borate, zinc anhydride, zinc metaborate, barium metaborate, antimony oxide, antimony trioxide, antimony pentaoxide, red phosphorus, talc, alumina, silica, boehmite, Bentonite, sodium silicate, calcium silicate, calcium sulfate, calcium carbonate, magnesium carbonate, and one or two or more compounds selected from these are used. In particular, the use of at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, hydrotalcite, and magnesium carbonate is excellent in imparting flame retardancy and advantageously economically.

As for the compounding quantity of an inorganic filler, 1-300 mass parts is preferable with respect to 100 mass parts of aromatic vinyl-type elastomers, Especially 5-100 mass parts is preferable. If an inorganic filler is less than 1 mass part, cutting property may worsen. On the other hand, when the inorganic filler exceeds 300 parts by mass, mechanical properties such as moldability and strength of the film substrate may be inferior.

Moreover, a well-known coloring agent, antioxidant, a ultraviolet absorber, a lubricating agent, a stabilizer, another additive, etc. can be mix | blended with a film base material as needed in the range which does not impair the effect of this invention.

The manufacturing method of the adhesive tape using the film base material of this invention, Preferably it is 10-60 mass parts of styrene resin with respect to 100 mass parts of (a) aromatic vinyl-type elastomers, and its aromatic vinyl-type elastomer, and a styrene type Mixing 1 to 50 parts by mass of the copolymer with a composition containing 5 to 100 parts by mass of the brominated flame retardant; (b) molding the mixed composition to a film substrate; and (c) at least the film substrate. It has the process of apply | coating an adhesive on one surface in order.

Thus, if it has the process of (a)-(c) in order, a film base material which has flexibility, cutting property, heat resistance, abrasion resistance, flame retardancy, and bleed-out hardly generate | occur | produced, and has the balance of these characteristics, and this film base material The adhesive tape using can be manufactured stably.

The means for mixing the composition of the above step (a) is not particularly limited, but conventional melt kneading and various mixing apparatuses (for example, single or twin screw extruders, rolls, Banbury mixers, etc.) Various kneader etc.), and the method of mixing so that each component may be disperse | distributed uniformly is mentioned.

Although the means for shaping | molding to the film base material of the said (b) process is not specifically limited, Especially, a shaping | molding machine is a calender shaping | molding machine among these. The roll arrangement method in calender molding can employ | adopt well-known methods, such as an L type | mold, an inverted L type | mold, and Z type | mold, for example, Moreover, roll temperature is 150-200 degreeC normally, Preferably it is 160- It is set to 190 ° C.

The molded film is cut to the desired tape width.

The means for applying the pressure-sensitive adhesive of the step (c) is not particularly limited, but, for example, a gravure roll coater, reverse roll coater, kiss roll coater, dip roll coater, bar coater, knife coater, spray coater can be used. have.

The thickness of a film base material is not specifically limited, For example, 40-500 micrometers, Preferably it is 70-300 micrometers, More preferably, it is 80-160 micrometers.

In addition, the film base material may have the form of a single | mono layer, and may have the form of a multilayer.

An adhesive tape is for example respond | corresponding to the operation | work which winds around the electric wire which forms various forms, but when the thickness of a film base material becomes thick, winding workability may fall.

By irradiating and crosslinking a film base material with an electron beam, it can prevent that a film base material deforms or shrinks when it puts at high temperature, and can reduce temperature dependency. The irradiation amount of the electron beam at this time becomes like this. Preferably it is 10-150 Mrad, Especially 15-25 Mrad is preferable. If the dose is less than 10 Mrad, the temperature dependency may not be improved. On the other hand, when irradiation amount exceeds 150 Mrad, a film base material may deteriorate by an electron beam, and a problem may arise in the workability in post-processing.

You may add a crosslinking agent for promoting electron beam crosslinking. As a specific crosslinking agent, a low molecular weight compound or an oligomer which has at least 2 or more carbon-carbon double bonds in a molecule | numerator is preferable, For example, an acrylate type compound, a urethane acrylate type oligomer, and an epoxy acrylate type oligomer are mentioned.

You may provide an adhesive layer on the single side | surface of a film base material. As an adhesive for forming an adhesive layer, the adhesive generally used can be used suitably, For example, a rubber adhesive, an acrylic adhesive, etc. can be used. Moreover, in order to make these adhesives into preferable performances, a tackifier, an antiaging agent, the hardening | curing agent of an adhesive, etc. can be mix | blended.

As the base polymer of the rubber-based adhesive, natural rubber, recycled rubber, silicone rubber, isoprene rubber, styrene butadiene rubber, polyisoprene, nitrile butadiene rubber, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer and the like are preferable.

A crosslinking agent, a softener, a filler, a flame retardant, etc. can be added to a rubber adhesive as needed. Specific examples include an isocyanate-based crosslinking agent as a crosslinking agent, liquid rubber as a softener, calcium carbonate as a filler, and inorganic flame retardants such as magnesium hydroxide and red phosphorus as a flame retardant.

As an acrylic adhesive, the copolymer with the homopolymer or copolymerizable monomer of (meth) acrylic acid ester is mentioned. As (meth) acrylic acid ester or a copolymerizable monomer, (meth) acrylic-acid alkylester (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 (e.g., dimethylaminoethyl methacrylate, t -Butylaminoethyl methacrylate etc.), vinyl acetate, styrene, acrylonitrile, etc. are mentioned. Among these, as the main monomer, an acrylic acid alkyl ester in which the glass transition temperature of the homopolymer (monopolymer) is usually -50 ° C or less is preferable.

As tackifying resin agent used for a tackifier, it can select by considering a softening point, compatibility with each component, etc. Examples include terpene resins, rosin resins, hydrogenated rosin resins, coumarone-indene resins, styrene resins, petroleum resins such as aliphatic and alicyclic compounds, terpene-phenol resins, xylene resins, other aliphatic hydrocarbon resins, or Aromatic hydrocarbon resin etc. are mentioned.

As for the softening point of tackifying resin, 65-130 degreeC, especially 80-110 degreeC is preferable. Moreover, alicyclic saturated hydrocarbon resin of petroleum resin of softening point 65-130 degreeC, polyterpene resin of softening point 80-130 degreeC, glycerin ester of hydrogenated rosin of softening point 80-130 degreeC, etc. are more preferable. These can be used also in any form of single and complex.

The anti-aging agent is used to improve the rubber-based pressure-sensitive adhesive because the unsaturated double bond in the rubber molecule is likely to deteriorate in the presence of oxygen or light. As an antioxidant, a single substance or mixture, such as a phenolic antioxidant, an amine antioxidant, a benzimidazole-type antioxidant, a dithiocarbamate-type antioxidant, and a phosphorus antioxidant, is mentioned, for example.

As a hardening | curing agent for acrylic adhesives, hardening | curing agents, such as an isocyanate type, an epoxy type, and an amine type, are mentioned, for example, Not only these individual substances but mixtures may be sufficient.

Specifically as an isocyanate hardening | curing agent, a polyhydric isocyanate compound, for example, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, 1, 3- xylylene diisocyanate, 1, 4- xyl Rendiisocyanate, diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane -4,4'- diisocyanate, dicyclohexyl methane-2,4'- diisocyanate, lysine isocyanate, etc. are mentioned.

Although the thickness after drying of an adhesive layer can be suitably selected in the range which does not impair adhesiveness or handleability, the thickness of an adhesive layer is 5-100 micrometers, for example, Preferably it is 10-50 micrometers. When thinner than 5 micrometers, adhesive force and rewinding force may fall. On the other hand, when it is thicker than 100 micrometers, coating performance may worsen.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail based on an Example, but this invention is not limited by these Examples.

In Tables 1-3, "flexibility" is the tensile strength of 25% modulus measured based on JISC2107. In the evaluation test room set to the temperature of 23 +/- 2 degreeC, and the humidity of 50 +/- 5% RH, the adhesive tape to test is shown the average value of n = 3 or more measured value, and the following evaluation criteria evaluated.

Good: Tensile strength of modulus is from 5.0 to 15.0 N / mm2

Poor: Tensile strength of modulus is less than 5.0N / mm2, 15.0N / mm2 or more

In Tables 1-3, "stretching" is the tensile breaking elongation measured based on JISC2107. In the evaluation laboratory set to a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH, the adhesive tape to be tested was shown the average value of the measured values of n = 3 or more, and the following evaluation criteria were evaluated.

Good: tensile elongation at break of 100 to 400%

Poor: Tensile fracture elongation less than 100%, 400% or more

In Tables 1-3, "cleavability" cut | disconnected the adhesive tape formed in length 100mm with a human hand in the horizontal direction, visually determined the cross-sectional state of the adhesive tape cut surface, and evaluated by the following evaluation criteria.

Superior: Cleanly cut cross section of adhesive tape cutting surface

Good: The cross section of the adhesive tape cut surface is slightly stretched, but cut cleanly

Poor: The cross section of the adhesive tape cut surface is stretched and cut in the flow direction of the adhesive tape

In Tables 1-3, "thermal contraction rate" is 20 minutes or more in the evaluation laboratory set to the temperature 23 +/- 2 degreeC, and the humidity 50 +/- 5% RH after leaving a film base material 100 mm square in 10 minutes in 100 degreeC atmosphere. It is shrinkage rate of MD (tape direction of tape) and TD (width direction of tape) after standing still. The average value of the measured value of n = 3 or more was shown, and the following evaluation criteria evaluated.

Good: Shrinkage is less than 10%

Poor: Shrinkage is 10% or more

In Tables 1-3, "wear resistance" means the Kanekin No. 3 cotton cloth as a wear material on a film substrate having a length of 100 mm and a width of 50 mm. The number of round trips when the base material and the wear material were rubbed and largely punched was evaluated according to the following evaluation criteria.

Good: 3000 round trips or more

Poor: less than 3000 round trip

In Tables 1-3, "workability" evaluated the usefulness when the adhesive tape was wound around the electric wire cable of diameter 1mm by the following evaluation criteria.

Good: No stretching or cutting of the adhesive tape during winding

Poor: during stretching, with stretched or cut adhesive tape

In Tables 1-3, "pinhole resistance" extends | stretches the adhesive tape formed in length 100mm until it becomes 200 mm in length by 300 mm / min of tensile velocity, and visually determines the presence or absence of the pinhole on the surface of an adhesive tape, The following evaluation criteria evaluated.

Good: 0 pinholes on the adhesive tape surface

Poor: One or more pinholes on the surface of the adhesive tape

In Tables 1-3, "blocking resistance" refers to two 50-cm <2> film base materials in 50 degreeC atmosphere, and adds 15 kg of loads, and 15 kg after leaving for 4, 8, 12, 24, and 48 hours. After the load was removed and allowed to stand for 20 minutes or more in the evaluation laboratory set at a temperature of 23 ± 2 ° C. and a humidity of 50 ± 5% RH, the overlapped film substrates were peeled by hand, and the time for peeling off the film substrate was evaluated as follows. Evaluation was made based on the criteria.

Rainfall: 48 hours or more

Good: More than 24 hours

Poor: less than 24 hours

In Tables 1-3, "flame retardance" shows JIS method OI value. This JIS method OI value is an index of flame retardancy, and is combusted according to the combustion test method for polymer materials by the oxygen index method of JIS K 7201, and the combustion length of the test piece is continuously burned for 3 minutes or more, or the combustion length after complex salt is 50. The minimum oxygen flow rate and nitrogen flow rate at that time necessary to continue burning more than mm are measured with a flowmeter (the apparatus name "candle combustion tester" manufactured by Toyo Shogyo Co., Ltd.), an oxygen index is calculated by the following formula (I), and the oxygen index is calculated. The following evaluation criteria evaluated.

Good: OI value above 25

Poor: OI value less than 25

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

(Wherein, [O ₂ ] is the flow rate of oxygen (l / min) and [N ₂ ] is the flow rate of nitrogen (l / min))

In Tables 1-3, a bleed-out is a film base material after leaving a 30 mm x 40 mm film base material in 70 degreeC warm water for 1, 2, 3, 6, 12, 24, 48 hours, and then draining water well. It was visually confirmed whether a flame retardant floated on the surface (whether a bleed-out occurred), and the time was evaluated by the following evaluation criteria.

Rainfall: 48 hours or more

Good: More than 24 hours

Poor: less than 24 hours

(Example 1)

The mixing | blending of the film base material in a present Example is an aromatic vinyl elastomer, 100 mass parts of complete hydrogenated products (SOE SS9000 by Asahi Kasei Chemicals Co., Ltd.) of a styrene-butadiene random copolymer, and polystyrene (Toyo styrene as a styrene resin) GPPS G-14L manufactured by Co., Ltd., a styrene copolymer (Beyo Soften Co., Ltd. T-080: 92 mass% of aromatic vinyl monomers 92 mass%, ethylenically unsaturated carboxylic monomer 8) Mass%) 30 parts by mass, bromine flame retardant (5% weight loss temperature is 247 ° C, FR-1206 (HBCD) manufactured by ICL Industrial, hexabromocyclododecane, weight average molecular weight 641.7: bromine content 73 mass%) 20 2 parts by mass of magnesium hydroxide (Mug's N-1 manufactured by Fukushima Chemical Industries, Ltd.) having an average particle diameter of 5.0 µm, and a small amount of stabilizer (Ca-Zn system, manufactured by Mizu Corporation) , A lubricant (stearic acid, manufactured by Nippon held Company) to which contained 0.2 parts by weight. These materials were mixed so that each component may be uniformly dispersed using Banbury mixer, and it shape | molded to thickness of about 0.1 mm at roll temperature of 160 degreeC with the calender molding machine, and obtained the film base material. Subsequently, a rubber-based adhesive made of a mixture of natural rubber and SBR (styrene-butadiene rubber) is applied to one side of the film base material using a gravure roll coater, followed by a drying process to form a pressure-sensitive adhesive layer having a thickness of 20 μm after drying. It cut to the tape shape of width 25mm, and obtained the adhesive tape. The back adhesive force of the obtained adhesive tape was 3.0 N / 10 mm.

(Example 2)

15 parts by mass of a styrene resin (GPPS G-14L manufactured by Toyo Styrene) as 100 parts by mass of a fully hydrogenated additive (Septon 8007 manufactured by Gureray Co., Ltd.) of the styrene-butadiene block copolymer with an aromatic vinyl elastomer, and a styrene copolymer The same as in Example 1, except that 5 parts by weight of a styrene copolymer (Beyo Styrene Co., Ltd. T-080: aromatic vinyl monomer 92% by mass, ethylenically unsaturated carboxylic acid monomer 8% by mass) at 115 ° C as the Vicat softening point. The adhesive tape was obtained.

(Example 3)

An adhesive tape was obtained in the same manner as in Example 1 except that the brominated flame retardant of Example 1 was 90 parts by mass.

(Example 4)

The aromatic vinyl elastomer is a styrene-butadiene random copolymer (STR1250 manufactured by Denki Chemical Industries, Ltd.), and the styrene resin is 15 parts by mass of GPPS (G-14L manufactured by Toyo Styrene) and 15 parts by mass of HIPS (E640N manufactured by Toyo Styrene) 5 mass parts of styrene copolymers (T-040 by Toyo Styrene: 96 mass% of aromatic vinyl monomers, 4 mass% of ethylenically unsaturated carboxylic monomers) which are made into mixing, and have a beaker softening point of 107 degreeC as a styrene copolymer. Except having done, it carried out similarly to Example 1, and obtained the adhesive tape.

(Example 5)

Aromatic vinyl elastomer is made of styrene-butadiene block copolymer (STR1602 manufactured by Denki Chemical Industries, Ltd.), and styrene resin is 60 parts by mass of HIPS (E640N manufactured by Toyo Styrene Co., Ltd.), and a styrene copolymer is a non-cut softening point of 127 ° C. Copolymer (DX Chemical Co., Ltd. AX-053: Copolymer of 82.5 mass% of aromatic vinyl monomers and 17.5 mass% of acrylonitrile, 64 mass% of aromatic vinyl monomers, 1 mass% of ethylenically unsaturated carboxylic acid monomers, and maleimide A pressure-sensitive adhesive tape was obtained in the same manner as in Example 1, except that 50 parts by mass of the melt kneaded product of the copolymer of 35 mass% of monomers was used.

(Example 6)

Bromine flame retardant, Bromine flame retardant with a 5% weight loss temperature of 344 ° C. (SAYTEX8010 manufactured by ALBEMARLE CORPORATION, ethane-1,2-bis (pentabromophenyl), weight average molecular weight 971.2, 5%, bromine content 82.3 mass Except having changed into%), it carried out similarly to Example 1, and obtained the adhesive tape.

(Comparative Example 1)

The adhesive tape was obtained like Example 1 except having changed the compounding quantity of the styrene resin of Example 1 into 5 mass parts.

(Comparative Example 2)

The adhesive tape was obtained like Example 1 except having changed the compounding quantity of the styrene resin of Example 1 into 100 mass parts.

(Comparative Example 3)

The adhesive tape was obtained like Example 1 except having changed the compounding quantity of the styrene-type copolymer of Example 1 into 0.5 mass part.

(Comparative Example 4)

The adhesive tape was obtained like Example 1 except having changed the compounding quantity of the styrene-type copolymer of Example 1 into 100 mass parts.

(Comparative Example 5)

The adhesive tape was obtained like Example 1 except having changed the compounding quantity of the brominated flame retardant of Example 1 into 1 mass part.

(Comparative Example 6)

The adhesive tape was obtained like Example 1 except having changed the compounding quantity of the brominated flame retardant of Example 1 into 200 mass parts.

(Comparative Example 7)

The bromine flame retardant of Example 1 was a bromine flame retardant (FR-613 (TBP) manufactured by ICL Industrial, FR-613 (TBP), tetrabromophenol, weight average molecular weight 330.8, bromine content 72 mass%) of 5% weight loss temperature. Except having changed, it carried out similarly to Example 1, and obtained the adhesive tape.

(Comparative Example 8)

The brominated flame retardant of Example 1 was a brominated flame retardant having a 5% weight loss temperature of 410 ° C. (SAYTEX BT-93W manufactured by ALBEMARLE CORPORAION, ethylene bistetrabromophthalimide, weight average molecular weight 951.5, and bromine content 67.2 mass% ), And an adhesive tape was obtained in the same manner as in Example 1.

(Comparative Example 9)

Example 1 except having changed into the styrene-based copolymer (GR-AT-R made from Denki Chemical Co., Ltd .: 69 mass% of aromatic vinyl monomer, 31 mass% of acrylonitrile) which has a beaker softening point of 95 degreeC as a styrene copolymer. In the same manner as in the above, an adhesive tape was obtained.

(Comparative Example 10)

Styrene-based copolymer having a non-cut softening point of 145 ° C as a styrene-based copolymer (MS-25NF manufactured by Denki Chemical Industries, Inc .: 64% by mass of aromatic vinyl monomer, 1% by mass of ethylenically unsaturated carboxylic acid monomer, 35% by mass of maleimide monomer) Except having changed into, it carried out similarly to Example 1, and obtained the adhesive tape.

(Comparative Example 11)

A tape was obtained in the same formulation as in Example 1 except that the formulation of the styrene resin of Example 1 was excluded.

(Comparative Example 12)

A tape was obtained in the same formulation as in Example 1 except that the formulation of the styrene copolymer of Example 1 was excluded.

(Comparative Example 13)

An adhesive tape was obtained in the same manner as in Example 1 except that the formulation for the film substrate of Example 1 was 100 parts by mass of LDPE (Tosoh Corporation, Petrocene 226), and a polyolefin substrate was used.

Although not shown in Table 1, the heating strain of Example 1 was -43%. This heat strain is the strain of the length in the longitudinal direction of the adhesive tape left after heat-processing at 140 degreeC for 5 minutes, and left at 23 degreeC for 30 minutes or more, and shows the temperature dependence of the adhesive tape. As another example, when the film base material of Example 1 was irradiated with a 20 Mrad electron beam and crosslinked, the heating strain became -6%, resulting in less temperature dependence. In addition, Examples 1 and 2 have tensile strength, elongation at break, electrical insulation (1 × 10 ¹² Ω · cm or more in volume resistivity), electric resistance and breakdown voltage equivalent to those of conventional polyvinyl chloride tapes. there was.

As is apparent from Table 1, according to the present invention, a film base material having flexibility, cutting property, heat resistance, abrasion resistance, flame retardancy, and bleed-out hardly occur, and having a good balance of these characteristics, and an adhesive tape using the film base material It can be seen that it is easily obtained.

The adhesive tape using the film base material of this invention can be used suitably for the binding tape which binds wire and cable, such as a wire harness of an automobile, for example.

In addition, the JP Patent application 2006-285695, the claim, and all the content of the abstract for which it applied on October 20, 2006 are referred here, and it introduces as an indication of the specification of this invention.

Claims (11)

At least one aromatic vinyl elastomer selected from the group consisting of styrene-butadiene random copolymers, styrene-butadiene block copolymers, hydrogenated products of styrene-butadiene random copolymers and hydrogenated additives of styrene-butadiene block copolymers; 10 to 60 parts by mass of polystyrene resin (GPPS), rubber-reinforced polystyrene resin (HIPS), or styrene resin, which is polystyrene resin (GPPS) and rubber-reinforced polystyrene resin (HIPS), based on 100 parts by mass of the aromatic vinyl elastomer; 1-50 mass parts of the styrene copolymer formed by superposing | polymerizing 80-99 mass% of aromatic vinyl monomers and 1-20 mass% of ethylenically unsaturated carboxylic monomers; And 5-100 mass parts of bromine flame retardants whose bromine content is 50-99 mass%. delete delete The method of claim 1, The styrene-based copolymer is a styrene-based copolymer having a non-cut softening point of 100 to 130 ° C, and is formed by polymerizing 80 to 99% by mass of an aromatic vinyl monomer and 1 to 20% by mass of an ethylenically unsaturated carboxylic acid monomer. The film base material whose aromatic vinyl monomer is styrene and that ethylenic unsaturated carboxylic monomer is methacrylic acid. The method of claim 1, A bromine-based flame retardant is a film-based brominated flame retardant having a 5% weight loss temperature of 220 to 350 ° C. delete The method of claim 1, Furthermore, the film base material containing 1-300 mass parts of inorganic fillers with respect to 100 mass parts of aromatic vinyl-type elastomers. The method of claim 1, The film base material whose oxygen index of a film base material is 25 or more and 100 or less. The adhesive tape which provided the adhesive layer on the at least single side | surface of the film base material of Claim 1. The tape for binding using the adhesive tape of Claim 9. (a) at least one aromatic vinyl elastomer selected from the group consisting of styrene-butadiene random copolymers, styrene-butadiene block copolymers, hydrogenated products of styrene-butadiene random copolymers and hydrogenated products of styrene-butadiene block copolymers ; 10 to 60 parts by mass of polystyrene resin (GPPS), rubber-reinforced polystyrene resin (HIPS), or styrene resin, which is polystyrene resin (GPPS) and rubber-reinforced polystyrene resin (HIPS), based on 100 parts by mass of the aromatic vinyl elastomer; 1-50 mass parts of the styrene copolymer formed by superposing | polymerizing 80-99 mass% of aromatic vinyl monomers and 1-20 mass% of ethylenically unsaturated carboxylic monomers; And a process of mixing a composition containing 5 to 100 parts by mass of a bromine flame retardant having a bromine content of 50 to 99% by mass, (b) forming the mixed composition on a film substrate; (c) The manufacturing method of the adhesive tape which has a process of apply | coating an adhesive to at least one surface of the said film base material in order.