WO2008047915A1 - Matériau de base de film et ruban adhésif - Google Patents

Matériau de base de film et ruban adhésif Download PDF

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Publication number
WO2008047915A1
WO2008047915A1 PCT/JP2007/070468 JP2007070468W WO2008047915A1 WO 2008047915 A1 WO2008047915 A1 WO 2008047915A1 JP 2007070468 W JP2007070468 W JP 2007070468W WO 2008047915 A1 WO2008047915 A1 WO 2008047915A1
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Prior art keywords
mass
styrene
parts
aromatic
copolymer
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PCT/JP2007/070468
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English (en)
Japanese (ja)
Inventor
Shigeo Kawasaki
Seiji Saita
Mizuki Hasumi
Original Assignee
Denki Kagaku Kogyo Kabushiki Kaisha
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Application filed by Denki Kagaku Kogyo Kabushiki Kaisha filed Critical Denki Kagaku Kogyo Kabushiki Kaisha
Priority to KR1020097007298A priority Critical patent/KR101133001B1/ko
Priority to CN2007800389094A priority patent/CN101528842B/zh
Priority to JP2008539889A priority patent/JP5268647B2/ja
Publication of WO2008047915A1 publication Critical patent/WO2008047915A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2425/00—Presence of styrenic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer

Definitions

  • the present invention relates to a film base material having high flame retardancy with the addition of relatively little brominated flame retardant, and an adhesive tape using the same.
  • Various adhesive tapes such as insulating tapes used for electrical equipment in automobiles, railways, aircraft, ships, houses, factories, etc. have moderate flexibility and extensibility, flame resistance, mechanical properties
  • a film made from a resin composition containing halogenated bur resin such as polychlorinated bur is used because of its excellent strength, heat distortion resistance, electrical insulation and moldability, and relatively low cost. It has been.
  • halogenated bur resin films generate toxic gases when incinerated, and recently, films using non-halogen resin compositions made of polyolefin resins as raw materials have begun to be used.
  • a film substrate comprising a composition containing an olefin resin and a styrene resin (see, for example, Patent Document 1), or a composition containing an olefin resin and an inorganic flame retardant. (For example, see Patent Document 2).
  • Patent Document 1 A film substrate comprising a composition containing an olefin resin and a styrene resin
  • Patent Document 2 A film substrate comprising a composition containing an olefin resin and a styrene resin
  • Patent Document 2 a composition containing an olefin resin and an inorganic flame retardant.
  • these tapes are sometimes inferior in flexibility, hand cutting properties, heat resistance and wear resistance as compared with films made from a resin composition containing a halogenated bur resin.
  • An adhesive tape made from a non-halogen resin composition is generally poor in flame retardancy.
  • butyl chloride contains a large amount of chlorine atoms and thus has flame retardancy by itself. Therefore, even if a large amount of plasticizer is added, the chlorinated bule tape can have a flame retardancy of self-extinguishing level (a level that will naturally extinguish when the fire source is removed in the air).
  • Patent Document 2 JP 2001-192629 Noriyuki
  • the present invention has a relatively small amount of! /, The amount of addition of brominated flame retardant, flexibility, hand cutting, heat resistance, wear resistance, flame resistance, and bleed-out hardly occur It is an object of the present invention to provide a film base material having a good balance of the above characteristics and an adhesive tape using the film base material.
  • the present invention achieves the above object and has the following gist.
  • Aromatic Bulle Elastomer One Group Styrene-butadiene random copolymer, styrene-butadiene block copolymer, hydrogenated product of styrene-butadiene random copolymer, hydrogenated product of styrene-butadiene block copolymer.
  • the film substrate according to (1) or (2) above which is styrene resin strength S, polystyrene resin (GPPS) and / or rubber-reinforced polystyrene resin (HIPS).
  • the styrenic copolymer is a styrenic copolymer having a Vicat softening point of 100 to 130 ° C, an aromatic bulle monomer of 80 to 99% by mass and an ethylenically unsaturated carboxylic acid monomer.
  • the aromatic bulle monomer is styrene
  • the ethylenically unsaturated carboxylic acid monomer is methacrylic acid. Description Film substrate.
  • brominated flame retardant is a brominated flame retardant having a 5% weight loss temperature of 220 to 350 ° C.
  • a pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer is formed on at least one side of the film substrate according to any one of the above (1) to (8).
  • the film substrate of the present invention comprises a styrene resin and a styrene copolymer, the resin component of which is an aromatic bull elastomer as a base resin component.
  • the reason why the aromatic bullet elastomer is used as the base resin component is that the film base material is not rigid and can exhibit flexibility.
  • An aromatic bur-based elastomer that can be used for the film substrate of the present invention comprises an aromatic bulu hydrocarbon polymer block and an elastomeric polymer block, and the aromatic bulu hydrocarbon.
  • the polymer block is a hard segment
  • the elastomeric polymer block is a soft segment.
  • Aromatic Bulle Elastomer is typically an Aromatic Bulle Hydrocarbon Polymer Block Elastomeric Polymer Block or Aromatic Bulle Hydrocarbon Polymer Block Elastomer Uniform Polymer Block One Aromatic Bulle Hydrocarbon It is a block copolymer having a copolymer structure represented by a polymer block, and the double bond of the elastomeric polymer block may be partially or completely hydrogenated, or a random copolymer. This is generally known as a styrene elastomer.
  • aromatic bur hydrocarbon constituting the aromatic bur hydrocarbon block examples include styrene, ⁇ -methyl styrene, o-, m-, and p-methyl styrene, 1,3-dimethylolene styrene, burnaphthalene, bur. Anthracene and the like can be mentioned, among which styrene is preferred.
  • the elastomeric polymer block may be a conjugated gen series or other than a conjugated gen series as long as elastomeric properties are expressed, but a conjugated gen series is generally preferred.
  • conjugated gen examples include butadiene, isoprene, 1,3 pentagen, 2,3-dimethyl-1,3-butadiene and the like.
  • aromatic bur elastomers examples include styrene-ethylene / butylene copolymer / styrene (SEBS), styrene-ethylene / propylene copolymer styrene (SEPS), styrene-butadiene styrene (SBS), styrene isoprene styrene.
  • SEBS styrene-ethylene / butylene copolymer / styrene
  • SEPS styrene-ethylene / propylene copolymer styrene
  • SBS styrene-butadiene styrene
  • styrene isoprene styrene examples include styrene-ethylene / butylene copolymer / styrene (SEBS), styrene-ethylene / propylene copolymer styrene
  • SIS SIS
  • examples thereof include A-B type block copolymers or random copolymers such as styrene isoprene copolymers, and hydrogen additives of these A-B type block copolymers and random copolymers. it can.
  • Aromatic Bulle elastomers include styrene butadiene random copolymer, styrene butadiene block copolymer, hydrogenated styrene butadiene random copolymer, styrene butadiene block copolymer, among others.
  • a combined hydrogenated product is preferred.
  • a completely hydrogenated styrene-butadiene random copolymer is preferable because it has a low elongation at break!
  • the styrene-based resin that can be used for the film substrate of the present invention includes a styrene homopolymer, a copolymer of styrene and a monomer copolymerizable with styrene, and a rubbery polymer. Preference is given to those obtained by (co) polymerizing styrene or one or more monomers copolymerizable with styrene and styrene.
  • Monomers copolymerizable with styrene include ⁇ -substituted styrene such as ⁇ -methylstyrene; aromatic ring-substituted styrene such as butyltoluene and t-butylstyrene; cyanide butyl monomers such as acrylonitrile and methacrylonitrile.
  • Acrylic acid esters such as methyl acrylate and ethyl acrylate; Methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; Bull carboxylic acids such as acrylic acid and methacrylic acid; Unsaturated carboxylic acids such as acrylic amide and methacrylic acid amide Amides; Unsaturated dicarboxylic acid imide derivatives such as maleimide, N-phenylmaleimide, N-cyclohexenolemaleimide; Unsaturated dicarboxylic acid anhydrides such as maleic acid, itaconic acid, and citraconic acid. However, it is not limited to these.
  • the styrene resin is not particularly limited, and a commonly used known resin can be used. Specific examples include polystyrene resin called GPPS and / or rubber-reinforced polystyrene resin called HIPS. Among these, a polystyrene resin or a mixture of a polystyrene resin and a rubber-reinforced polystyrene resin that can easily adjust the film strength by controlling the molecular weight is preferable.
  • the blending amount of the styrenic resin in the film substrate of the present invention is in the range of 10 to 60 parts by mass, preferably 10 to 50 parts by mass with respect to 100 parts by mass of the aromatic bull elastomer.
  • the styrene-based resin is less than 10 parts by mass, the strength of the film base material is low and the film is easily stretched.
  • the styrene-based resin exceeds 60 parts by mass, the workability of the film base material is lost, and the film base material becomes rigid and pinhole resistance may be lowered.
  • the styrenic copolymer that can be used for the film substrate of the present invention is preferably a styrenic copolymer having a Vicat softening point of ⁇ 130 ° C. This is because when the Vicat softening point is less than 100 ° C, the film base shrinks and the heat resistance is poor. Appearance defects may occur due to the occurrence of wrinkles. On the other hand, if the Vicat softening point exceeds 130 ° C, the appearance of the film substrate may be poor due to the occurrence of fishery and pinholes due to poor resin kneading. In particular, a styrene copolymer having a Vicat softening point of 110 to 120 ° C is preferable.
  • Vicat softening point is 100 to; the blending amount of the styrene copolymer at 130 ° C is 1 to 50 parts by mass, preferably 10 to 35 parts by mass with respect to 100 parts by mass of the aromatic bur elastomer. Part. If the styrene copolymer having a Vicat softening point of 100 to 130 ° C is less than 1 part by mass, the thermal shrinkage of the film substrate may be deteriorated. On the other hand, when the styrene copolymer having a Vicat softening point of 100 to 130 ° C exceeds 50 parts by mass, the workability of the film substrate may be deteriorated.
  • the styrenic copolymer having a Vicat softening point of 100 to 130 ° C is preferably 80 to 99% by mass of an aromatic vinyl monomer and an ethylenically unsaturated carboxylic acid monomer; % Overlap. More preferably, the aromatic Bulle monomer 85 to 98 weight 0/0, E Ji Ren unsaturated carboxylic acid monomer 2; 15 mass 0/0, and copolymerizable with these Bulle single-mer 0 ;! ⁇ 10% by mass polymerized.
  • the aromatic bulle monomer When the aromatic bulle 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 Since the melt viscosity difference is increased and the melt mixing property is deteriorated, the workability of the film substrate may be deteriorated. Further, if the aromatic bulle monomer exceeds 99% by mass or the ethylenically unsaturated carboxylic acid monomer is less than 1% by mass, the heat imparting effect as a film substrate may be deteriorated. is there.
  • the aromatic butyl monomer of the styrene copolymer having a Vicat softening point of 100 to 130 ° C includes styrenes such as styrene, ⁇ -methylstyrene, butyltoluene, ethyl styrene, and t-butylstyrene, and their substitution.
  • the body is mentioned.
  • it is styrene which can easily control the molecular weight which increases by reaction.
  • Vicat softening point of 100-; ethylenically unsaturated carboxylic acid monomer of styrene copolymer at 130 ° C includes acrylic acid or esters thereof; methacrylic acid or esters thereof; fumaric acid , Maleic acid, itaconic acid, etc. 2 by an intramolecular dehydration (or dealcoholization) reaction of monomer units such as acrylic acid, methacrylic acid or esters thereof adjacent in the molecule; acrylonitrile; Examples thereof include 6-membered cyclic anhydrides or imides that are subsequently derived. Of these, methacrylic acid is preferred.
  • the method for producing a styrene copolymer having a Vicat softening point of 100 to 130 ° C of the present invention is not particularly limited, but a bulk polymerization method, a suspension polymerization method, a solution polymerization method, and an emulsion polymerization method are preferably used. Can be adopted.
  • the Vicat softening point (° C) in the present invention is measured by the following method.
  • Specimen Length 30mm X Width 19mm X Thickness 3. After molding a 2mm plate specimen by injection molding, leave it in a constant temperature and humidity chamber with a temperature of 23 ° C and a relative humidity of 50% for 24 hours. did. Test method: Using a 5 kg weight, the temperature was increased at a heating rate of 50 ° C / hr., And the temperature when the indenter entered lmm into the test piece was measured. Three tests were conducted, and the average value was defined as the Vicat softening point.
  • the film base material of the present invention contains a brominated flame retardant in order to impart desired flame retardancy.
  • a brominated flame retardant the ability to add known ones should be close to the thermal decomposition temperature of aromatic bur elastomers. Brominated flame retardants with a 5% weight loss temperature of 220-350 ° C are recommended. preferable.
  • the desired flame retardancy in the present invention uses an oxygen index of 25 or more, preferably 27 or more, which is generally regarded as a flame retardant level having self-digestibility. This is because of the flame retardant level of the chlorinated bull tape used in general electrical insulation and bundling applications. Also match.
  • the present invention can also be applied to cases where higher flame retardancy is required.
  • the amount of the brominated flame retardant having a 5% weight loss temperature of 220 to 350 ° C is 5 to 100 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the aromatic bulur elastomer. The range of. If the brominated flame retardant with a 5% weight loss temperature of 220 to 350 ° C is less than 5 parts by mass, sufficient flame retardancy may not be achieved. 5% weight loss temperature power When the flame retardant of ⁇ 20-350 ° C exceeds 100 parts by mass, bleeding out occurs, the film base becomes rigid, and pinhole resistance may decrease.
  • brominated flame retardant 5% weight loss temperature is two hundred and twenty to three hundred and fifty ° C is bromine content is 50 to 99 mass 0/0, preferably those 70-90 mass 0/0.
  • a 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. If the 5% weight loss temperature is less than 220 ° C, bleed out may occur or it may deviate from the thermal decomposition temperature of the aromatic bull elastomer resin, resulting in insufficient flame retardancy. On the other hand, if the 5% weight loss temperature exceeds 350 ° C, it may deviate from the thermal decomposition temperature of the aromatic bull elastomer resin and may not exhibit sufficient flame retardancy.
  • the 5% weight loss temperature in the present invention is measured by the following method.
  • a brominated flame retardant having a 5% weight loss temperature of 220 to 350 ° C has a weight average molecular weight of 500 to The range is 2000. More preferably, it is 550-000. If the weight average molecular weight of a brominated flame retardant with a 5% weight loss temperature power of 20 to 350 ° C is less than 500, bleed out may occur. On the other hand, if the weight average molecular weight exceeds 2000, the 5% weight loss temperature may increase and flame retardancy may not be achieved.
  • the film substrate of the present invention preferably contains an inorganic filler.
  • the reason for adding an inorganic filler is to improve the film substrate's hand cutting property, while increasing the heat conduction during the molding process to increase the cooling effect of the film substrate and to reduce the distortion generated in the film substrate. This is to suppress.
  • the average particle diameter of the inorganic filler is, for example, not more than 20,1 m, preferably not more than 10 m. If the average particle size exceeds 20 inches, the tensile strength and elongation at break of the film base material may be lowered, and the flexibility and pinholes may be reduced.
  • the average particle diameter is a value based on particle distribution measurement by a laser diffraction method.
  • Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, triphenyl phosphate, ammonium polyphosphate, polyphosphate amide, and zirconium oxide.
  • One or more compounds selected from these are used.
  • the use of at least one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, hydrated talcite, and magnesium carbonate is excellent in flame retardancy and is economically advantageous.
  • the blending amount of the inorganic filler is preferably 1 to 300 parts by weight, particularly preferably 5 to 100 parts by weight, with respect to 100 parts by weight of the aromatic bur elastomer. 1 part by weight of inorganic filler If it is full, hand cutting may be worse. 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.
  • the film base material is blended with known colorants, antioxidants, ultraviolet absorbers, lubricants, stabilizers, other additives and the like as long as they do not impair the effects of the present invention.
  • the power S
  • the method for producing an adhesive tape using the film base material of the present invention preferably comprises (a) an aromatic bulle elastomer and 100 parts by mass of the styrene aromatic styrene elastomer. Mixing a composition containing 10 to 60 parts by weight of a resin; styrene copolymer;! To 50 parts by weight and 5 to 100 parts by weight of a brominated flame retardant, (b) A step of forming the mixed composition into a film base material, and a step (c) applying an adhesive to at least one surface of the film base material are sequentially provided.
  • Means for mixing the composition of the step (a) is not particularly limited! /, However, the above-mentioned various materials are mixed with conventional melt-kneading or various mixing devices (for example, uniaxial or 2). And a method of mixing so that the respective components are uniformly dispersed using a screw extruder, a roll, a Banbury mixer, various kneaders, etc.).
  • the means for forming the film substrate in the step (b) is not particularly limited, but the molding machine is preferably a calendering machine.
  • the roll arrangement method in calendering known methods such as L-type, reverse L-type and Z-type can be adopted, and the roll temperature is usually 150 to 200.
  • C preferably ⁇ 160 ⁇ ; 190. Set to C.
  • the formed film is cut to a desired tape width.
  • the means for applying the pressure-sensitive adhesive in the step (c) is not particularly limited.
  • a gravure rho-recoater-reno-kuno lano coater, xylo-no-recoater, diplo-no-recoater, bar coater, knife A coater or spray coater can be used.
  • the thickness of the film substrate is not particularly limited, and is, for example, 40 to 500 m, preferably 70 to 3. OO ⁇ m, more preferably 80-;
  • the film substrate may have a single layer form or may have a multi-layer form.
  • the winding workability may be reduced when the thickness of the film base is increased.
  • the film base material By irradiating the film base material with an electron beam and crosslinking, the film base material can be prevented from being deformed or shrunk when placed at a high temperature, and temperature dependency can be reduced.
  • the irradiation amount of the electron beam is preferably 10 to 150 Mrad, particularly preferably 15 to 25 Mrad. If the irradiation dose is less than lOMrad, the temperature dependence may not be improved. On the other hand, if the irradiation amount exceeds 150 Mrad, the film base material deteriorates due to the electron beam, which may cause a problem in workability in post-processing.
  • a crosslinking agent for promoting electron beam crosslinking may be added.
  • the cross-linking agent include low molecular weight compounds and oligomers having at least two carbon-carbon double bonds in the molecule. Examples thereof include acrylate compounds, urethane acrylate oligomers, and epoxy acrylate oligomers. It is done.
  • An adhesive layer may be formed on one side of the film substrate.
  • a commonly used pressure-sensitive adhesive can be appropriately used.
  • a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, or the like can be used.
  • a tackifier, an anti-aging agent, and a curing agent for the pressure-sensitive adhesive it is necessary to add a tackifier, an anti-aging agent, and a curing agent for the pressure-sensitive adhesive.
  • Base polymers of rubber adhesives include natural rubber, recycled rubber, silicone rubber, isoprene rubber, styrene butadiene rubber, polyisoprene, nitrile butadiene rubber, styrene-isoprene copolymer, styrene-isoprene-butadiene copolymer. Polymers are preferred.
  • the rubber-based pressure-sensitive adhesive can be added with a crosslinking agent, a softening agent, a filler, a flame retardant, and the like.
  • a crosslinking agent e.g., a crosslinking agent, a softening agent, a filler, a flame retardant, and the like.
  • Specific examples include isocyanate crosslinking agents as crosslinking agents, liquid rubber as softening agents, calcium carbonate as fillers, and inorganic flame retardants such as magnesium hydroxide and red phosphorus as flame retardants.
  • examples of the acrylic pressure-sensitive adhesive include a homopolymer of (meth) acrylic acid ester or a copolymer with a copolymerizable monomer.
  • (meth) acrylic acid esters or copolymerizable monomers examples include (meth) acrylic acid alkyl esters (for example, methyl ester, ethyl ester, butyl ester, 2-ethylhexyl ester, octyl ester), (meth) Glycidyl acrylate, (meth) acrylic acid, itaconic acid, maleic anhydride, (meth) acrylic acid amide, (meth) acrylic acid N hydroxyamide, (meth) acrylic acid alkylaminoalkyl ester (for example, dimethylaminoethyl meta Talylate, t-butylaminoethyl methacrylate, etc.), butyl acetate, styrene, acrylonitrile and the like.
  • an alkyl acrylate ester whose homopolymer (homopolymer) usually has a glass transition temperature of ⁇ 50 ° C. or lower is prefer
  • the tackifier resin agent used for the tackifier can be selected in consideration of the softening point, compatibility with each component, and the like.
  • examples include terpene resins, rosin resins, hydrogenated rosin resins, coumarone-indene resins, styrene resins, aliphatic and alicyclic petroleum resins, terpene phenol resins, xylene resins, and other aliphatic hydrocarbons.
  • examples thereof include resins and aromatic hydrocarbon resins.
  • the softening point of the tackifying resin is preferably 65 to 130 ° C, particularly 80 to 110 ° C.
  • petroleum resin alicyclic saturated hydrocarbon resin with a softening point of 65 to 130 ° C polyterpene resin with a softening point of 80 to 130 ° C, glycerin ester of hydrogenated rosin with a softening point of 80 to 130 ° C, etc. preferable. These can be used either alone or in combination.
  • the anti-aging agent is used to improve the rubber-based pressure-sensitive adhesive because the unsaturated double bond in the rubber molecule tends to deteriorate in the presence of oxygen or light.
  • the anti-aging agent include, for example, phenol-based anti-aging agents, amine-based anti-aging agents, benzimidazole-based anti-aging agents, dithiocarbamate-based anti-aging agents, phosphorous anti-aging agents, etc. Lifting things with power S
  • curing agent for the acrylic pressure-sensitive adhesive examples include, for example, isocyanate-based, epoxy-based, and amine-based curing agents, and these may be used alone or as a mixture thereof.
  • a polyvalent isocyanate compound for example, Isocyanate, 1,4-xylene diisocyanate, diphenylmethane-1,4'-diisocyanate, diphenylmethane-1,2,4'-diisocyanate, 3 methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate And dicyclohexylmethane 4,4'-diisocyanate, dicyclohexylmethane 2,4'-diisocyanate, lysine isocyanate and the like.
  • a polyvalent isocyanate compound for example, Isocyanate, 1,4-xylene diisocyanate, diphenylmethane-1,4'-diisocyanate, diphenylmethane-1,2,4'-diisocyanate, 3 methyldiphenylmethane diisocyanate, hexamethylene diis
  • the thickness of the pressure-sensitive adhesive layer after drying can be appropriately selected within a range that does not impair the adhesiveness and handleability.
  • the thickness of the pressure-sensitive adhesive layer is, for example, 5 to 100 m, preferably 10 to 50 111. is there. If it is thinner than 5 inches, the adhesive strength and unwinding force may be reduced. On the other hand, if it is thicker than 100 m, coating performance may deteriorate.
  • “Abrasion resistance” means “Kanakin No. 3 cotton cloth as a wear material on a 100 mm long and 50 mm wide film base material, and a weight of 500 g is placed on it. The film substrate and the wear material were rubbed at a speed of 110 reciprocations per minute, and the reciprocation number when a large hole was opened was evaluated according to the following evaluation criteria.
  • blocking resistance means that two 50 cm 2 film substrates are stacked in an atmosphere of 50 ° C., 15 kg of load is applied, 4, 8, 12, 24, 48 After standing for 15 hours, remove the 15 kg load and leave it in the evaluation test chamber set at a temperature of 23 ⁇ 2 ° C and humidity of 50 ⁇ 5% RH for 20 minutes or more. The time for removing the substrate was evaluated according to the following evaluation criteria.
  • flame retardancy refers to the JIS method OI value.
  • This JIS method OI value is an indicator of flame retardancy. Whether the specimen burns continuously for 3 minutes or longer according to the combustion test method for polymer materials by the oxygen index method of JIS K 7201. Or, measure the minimum oxygen flow rate and the nitrogen flow rate required to continue burning for 50 mm or more after the flame is reached with a flow meter (device name “Candle Combustion Tester” manufactured by Toyo Seiki Co., Ltd.). The oxygen index was obtained from formula (I), and the oxygen index was evaluated according to the following evaluation criteria.
  • Oxygen index (OI) ⁇ [O] / ([O] + [N]) ⁇ X 100 (I)
  • bleed out means 30 mm ⁇ 40 mm film substrate in 70 ° C warm water for 1, 2, 3, 6, 12, 24, 48 hours and then drain well. After removing the film, it was visually checked whether the flame retardant floated on the surface of the film base (bleed out occurred! /), And the time was evaluated according to the following evaluation criteria.
  • the film base was blended as an aromatic bur elastomer, 100 parts by mass of a completely hydrogenated styrene butadiene random copolymer (SOE SS9000, manufactured by Asahi Kasei Chemicals), and polystyrene ( Toyo styrene Co., Ltd. GPPS G-14U 30 parts by weight, a styrene copolymer Vicat softening point 115 ° C as the styrene copolymer (manufactured by Toyo styrene Co.
  • SOE SS9000 completely hydrogenated styrene butadiene random copolymer
  • polystyrene Toyo styrene Co., Ltd. GPPS G-14U 30 parts by weight
  • a styrene copolymer Vicat softening point 115 ° C as the styrene copolymer
  • T 080 aromatic Bulle monomer 92 mass 0/0, Ethylenically unsaturated carboxylic acid monomer (8% by mass) 30 parts by mass, brominated flame retardant (5% weight loss temperature 247 ° C, ICL Industrial FR-1206 (HBCD) (Average molecular weight 641.7.7: bromine content: 73% by mass) 20 parts by mass and magnesium hydroxide with an average particle size of 5.0 am (Madashies N—1 manufactured by Kamishima Chemical Co., Ltd.) 5 parts by mass Agent (Ca-Zn, Mizusawa Chemical) 2 parts by weight, lubricant (stearic acid, manufactured by Nippon Oil & Fats Co., Ltd.) 0.2 parts by weight.These ingredients are uniformly dispersed using a Banbury mixer.
  • Example 3 An adhesive tape was obtained in the same manner as in Example 1 except that 90 parts by mass of the brominated flame retardant in Example 1 was used.
  • Styrene butadiene random copolymer (STR1250 made by Denki Kagaku Kogyo Co., Ltd.) is used as the aromatic bullet elastomer and 15 parts by mass of GPPS (G-14L made by Toyo Styrene Co.) and HIPS (E640N made by Toyo Styrene Co., Ltd.) 15 Styrene copolymer with Vicat softening point ⁇ 07 ° C (made by Toyo Styrene Co., Ltd.)
  • T040 Aromatic bulle monomer 96% by mass, ethylenically unsaturated carboxylic acid monomer 4% by mass
  • An adhesive tape was obtained in the same manner as in Example 1 except that 5 parts by mass was used.
  • Viral softening point as styrene-based copolymer with styrene-butadiene block copolymer (STR1602 manufactured by Electrochemical Co., Ltd.), 60 parts by mass of HIPS (E640N manufactured by Toyo Styrene Co., Ltd.) Styrenic copolymer at 127 ° C (AX-053 manufactured by Denki Kagaku Kogyo Co., Ltd.: Copolymer of aromatic bull monomer 82.5% by mass and attarilonitriletriol 17.5% by mass, and aromatic A melt kneaded product of 64% by weight of a bull monomer, 1% by weight of an ethylenically unsaturated carboxylic acid monomer and 35% by weight of a maleimide monomer) An adhesive tape was obtained in the same manner as in 1.
  • Brominated flame retardant, brominated flame retardant with 5% weight loss temperature of 344 ° C (SAYTEX8010 manufactured by ALBEMARLE CORPORATION, ethane-1,2 bis (pentabromophenyl), weight average molecular weight 971.2, 5%
  • a pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the bromine content was changed to 82.3% by mass.
  • An adhesive tape was obtained in the same manner as in Example 1 except that the blending amount of the styrene resin in Example 1 was changed to 5 parts by mass.
  • a pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that the blending amount of the styrene copolymer of Example 1 was changed to 0.5 parts by mass.
  • An adhesive tape was obtained in the same manner as in Example 1 except that the blending amount of the styrene copolymer of Example 1 was changed to 100 parts by mass.
  • An adhesive tape was obtained in the same manner as in Example 1 except that the amount of the brominated flame retardant in Example 1 was changed to 1 part by mass.
  • An adhesive tape was obtained in the same manner as in Example 1 except that the amount of the brominated flame retardant in Example 1 was changed to 200 parts by mass.
  • the brominated flame retardant of Example 1 is a brominated flame retardant having a 5% weight loss temperature of 120 ° C (FR-613 (TBP) manufactured by ICL Industrial, tetrabromophenol, weight average molecular weight 330.8, bromine content.
  • An adhesive tape was obtained in the same manner as in Example 1 except that the content was changed to 72% by mass.
  • the brominated flame retardant of Example 1 is a brominated flame retardant having a 5% weight loss temperature of 410 ° C.
  • An adhesive tape was obtained in the same manner as in Example 1 except that the content was changed to 2% by mass).
  • Vicat softening point as styrene copolymer S145 ° C styrene copolymer (Electrification MS-25NF manufactured by Gaku Kogyo Co., Ltd .: Example 1 except that it was changed to 64% by weight of aromatic bule monomer, 1% by weight of ethylenically unsaturated carboxylic acid monomer, and 35% by weight of maleimide monomer).
  • An adhesive tape was obtained in the same manner.
  • a tape was obtained with the same composition as in Example 1 except that the composition of the styrenic resin in Example 1 was omitted.
  • a tape was obtained with the same composition as in Example 1 except that the composition of the styrenic copolymer in Example 1 was omitted.
  • a pressure-sensitive adhesive tape was obtained in the same manner as in Example 1 except that 100 parts by mass of LDPE (manufactured by Tosohichi Co., Ltd., Petrocene 226) was used for the film base of Example 1, and a polyolefin base was used.
  • LDPE manufactured by Tosohichi Co., Ltd., Petrocene 2266
  • Example 1 Forces not shown in Table 1
  • the heat deformation rate of Example 1 was 43%. This heat deformation rate is the deformation rate of the length in the longitudinal direction of the adhesive tape that was heat-treated at 140 ° C for 5 minutes and then left at 23 ° C for 30 minutes or more and the adhesive tape before treatment. It shows temperature dependence.
  • the heating deformation ratio became 6%, and the temperature dependency was reduced.
  • tensile strength, breaking elongation, electrical insulation (volume resistivity value of 1 X 10 12 ⁇ or more), electrical resistance and breakdown voltage are the same as those of conventional polychlorinated bure-based tapes. It was equipped with.
  • the pressure-sensitive adhesive tape using the film base material of the present invention can be suitably used, for example, as a binding tape for binding electric wires and cables such as automobile wire harnesses. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2006-285695 filed on October 20, 2006 are cited herein as the disclosure of the specification of the present invention. It is something that is incorporated.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un matériau de base de film qui présente un bon équilibre entre souplesse, maniabilité lors de la découpe du film, résistance à la chaleur, résistance à l'abrasion, propriétés ignifuges, et une propriété consistant à causer à peine une exsudation lorsqu'une quantité relativement faible d'un agent ignifugeant organique à base de brome lui est ajouté. L'invention concerne également un ruban adhésif produit par l'utilisation du matériau de base de film. Le matériau de base de film comporte 100 parties en masse d'un élastomère vinylique aromatique, entre 10 et 60 parties en masse d'une résine styrénique, entre 1 et 50 parties en masse d'un copolymère de styrène et entre 5 et 100 parties en masse d'un agent ignifugeant contenant du brome. L'élastomère vinylique aromatique est de préférence au moins un élément choisi parmi le groupe constitué d'un copolymère statistique styrène butadiène, un copolymère bloc styrène butadiène, un produit hydrogéné d'un copolymère statistique styrène butadiène et un produit hydrogéné d'un copolymère bloc styrène butadiène.
PCT/JP2007/070468 2006-10-20 2007-10-19 Matériau de base de film et ruban adhésif WO2008047915A1 (fr)

Priority Applications (3)

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KR1020097007298A KR101133001B1 (ko) 2006-10-20 2007-10-19 필름 기재 및 점착 테이프
CN2007800389094A CN101528842B (zh) 2006-10-20 2007-10-19 膜基材及胶粘带
JP2008539889A JP5268647B2 (ja) 2006-10-20 2007-10-19 フイルム基材及び粘着テープ

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JP2006-285695 2006-10-20
JP2006285695 2006-10-20

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KR (1) KR101133001B1 (fr)
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010001959A1 (fr) * 2008-07-03 2010-01-07 電気化学工業株式会社 Film adhésif sensible à la pression, stratifié utilisant le film adhésif sensible à la pression et procédé de protection d'un article moulé
CN102618182A (zh) * 2011-01-25 2012-08-01 麦克赛尔狮力昂科技股份有限公司 防水用两面粘着带
EP3181630A4 (fr) * 2014-09-08 2018-05-23 Sumitomo Rubber Industries, Ltd. Pneumatique
WO2020139113A1 (fr) * 2018-12-27 2020-07-02 Public Joint Stock Company "Sibur Holding" (co)polymère contenant des diènes modifiés, son procédé de préparation et son utilisation comme retardateur de flamme
WO2020139114A1 (fr) * 2018-12-27 2020-07-02 Public Joint Stock Company "Sibur Holding" (co)polymère contenant des diènes modifiés, son procédé de préparation et son utilisation comme retardateur de flamme

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103396631B (zh) * 2013-07-16 2015-10-28 安徽济峰节能材料有限公司 阻燃pvc电气胶带基材
JP6623760B2 (ja) * 2014-01-29 2019-12-25 日本ゼオン株式会社 透明粘着シート
CN108884180B (zh) * 2016-03-31 2021-06-29 电化株式会社 组合物
JP6712916B2 (ja) * 2016-07-11 2020-06-24 日東電工株式会社 粘着シート
US12065597B2 (en) * 2019-08-30 2024-08-20 Dic Corporation Adhesive tape

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JPS63152653A (ja) * 1986-12-16 1988-06-25 Sumitomo Chem Co Ltd 難燃性スチレン系樹脂組成物
JPH07268285A (ja) * 1994-04-01 1995-10-17 Toyobo Co Ltd 粘着テープ用ベースフィルム
JPH09143335A (ja) * 1995-11-24 1997-06-03 Asahi Chem Ind Co Ltd 滴下性難燃スチレン系樹脂組成物
JP2006111646A (ja) * 2004-10-12 2006-04-27 Denki Kagaku Kogyo Kk フィルム基材及び粘着テープ
JP2006137883A (ja) * 2004-11-15 2006-06-01 Denki Kagaku Kogyo Kk フィルム基材及び粘着テープ

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JP4937610B2 (ja) * 2005-04-12 2012-05-23 第一工業製薬株式会社 難燃性発泡ポリスチレン系樹脂およびその成形体

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JPS63152653A (ja) * 1986-12-16 1988-06-25 Sumitomo Chem Co Ltd 難燃性スチレン系樹脂組成物
JPH07268285A (ja) * 1994-04-01 1995-10-17 Toyobo Co Ltd 粘着テープ用ベースフィルム
JPH09143335A (ja) * 1995-11-24 1997-06-03 Asahi Chem Ind Co Ltd 滴下性難燃スチレン系樹脂組成物
JP2006111646A (ja) * 2004-10-12 2006-04-27 Denki Kagaku Kogyo Kk フィルム基材及び粘着テープ
JP2006137883A (ja) * 2004-11-15 2006-06-01 Denki Kagaku Kogyo Kk フィルム基材及び粘着テープ

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010001959A1 (fr) * 2008-07-03 2010-01-07 電気化学工業株式会社 Film adhésif sensible à la pression, stratifié utilisant le film adhésif sensible à la pression et procédé de protection d'un article moulé
CN102618182A (zh) * 2011-01-25 2012-08-01 麦克赛尔狮力昂科技股份有限公司 防水用两面粘着带
EP3181630A4 (fr) * 2014-09-08 2018-05-23 Sumitomo Rubber Industries, Ltd. Pneumatique
WO2020139113A1 (fr) * 2018-12-27 2020-07-02 Public Joint Stock Company "Sibur Holding" (co)polymère contenant des diènes modifiés, son procédé de préparation et son utilisation comme retardateur de flamme
WO2020139114A1 (fr) * 2018-12-27 2020-07-02 Public Joint Stock Company "Sibur Holding" (co)polymère contenant des diènes modifiés, son procédé de préparation et son utilisation comme retardateur de flamme

Also Published As

Publication number Publication date
TW200838918A (en) 2008-10-01
CN101528842B (zh) 2011-07-20
CN101528842A (zh) 2009-09-09
JPWO2008047915A1 (ja) 2010-02-25
JP5268647B2 (ja) 2013-08-21
KR20090073145A (ko) 2009-07-02
KR101133001B1 (ko) 2012-04-09
TWI429707B (zh) 2014-03-11

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