Classifications

• • 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
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
  • C09J7/381—Pressure-sensitive adhesives [PSA] 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives
• • 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
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/302—Applications of adhesives in processes or use of adhesives in the form of films or foils for bundling cables
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
• • 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
  • C09J2407/00—Presence of natural rubber
• • 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
  • C09J2433/00—Presence of (meth)acrylic polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
  • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
  • Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof

Definitions

• the present invention relates to a halogen-free pressure-sensitive adhesive tape obtained by applying a pressure-sensitive adhesive to a tape base material having a non-halogen-based resin composition that does not contain a halogen element.
• Patent Document 1 Japanese Patent Application Laid-Open No. 2003-178628
• Patent Document 2 Japanese Patent Laid-Open No. 2003-219533
• the base material is hard salty mulled resin, so a plasticizer is added to give flexibility, and this plasticizer moves to the adhesive side.
• the pressure-sensitive adhesive also has a certain degree of flexibility and has little decrease in adhesive strength. For this reason, the bundling work can be performed even at a low temperature of 0 ° C or less without causing any particular trouble.
• the halogen-free pressure-sensitive adhesive tape is a polyolefin-based resin having a soft base material, so that no plasticizer is added. Therefore, the plasticizer does not migrate from the base material cover to the pressure-sensitive adhesive, particularly at low temperatures. In this bundling operation, the tape is unwound due to insufficient adhesive force, and the sheet is damaged, causing problems that impair the finish and appearance of the wire harness. [0007]
• the present invention has been made in view of such a situation, and an object of the present invention is to increase the adhesive strength of a halogen-free pressure-sensitive adhesive tape at a low temperature and to improve the binding property.
• the present invention provides the following halogen-free pressure-sensitive adhesive tape.
• Natural rubber, acrylic resin, tackifier resin, antioxidant, and molecular weight are present on at least one surface of a tape base material comprising a halogen-containing resin composition containing no halogen element.
• a halogen-free pressure-sensitive adhesive tape characterized by being coated with a pressure-sensitive adhesive containing a plasticizer having a freezing point of 450 to 3000 and a freezing point of -30 ° C to -55 ° C.
• the halogen-free pressure-sensitive adhesive tape of the present invention has excellent bundling performance with less decrease in pressure-sensitive adhesiveness at low temperatures by using a pressure-sensitive adhesive containing a specific plasticizer. for that reason
• the base material of the halogen-free pressure-sensitive adhesive tape of the present invention also has an olefin-based resin composition strength.
• polypropylene, polyethylene, propylene-ethylene copolymer, and other base resins that have strength, metal hydroxides such as magnesium hydroxide and hydroxide, aluminum, flame retardant, phenolic, Suitable examples include non-halogen flame-retardant olefin resins added with amine-based anti-aging agents, triazine-based derivatives and other copper damage inhibitors. Power It is not limited to this.
• the thickness of the base material may be the same as that of a general adhesive tape, and is generally 5-500 ⁇ m.
• An adhesive is applied to the substrate, and the adhesive is composed mainly of natural rubber, acrylic resin, tackifier resin and antioxidant, and has a molecular weight of 450 to 3000.
• a plasticizer with a molecular weight of less than 50 tends to deteriorate the wire coating material as soon as it shifts to the wire coating material.
• a plasticizer with a molecular weight exceeding 3000 reduces the cohesiveness, which is poor in the effect of softening the adhesive at low temperatures.
• the adhesive strength at low temperatures is particularly low.
• plasticizers with a freezing point higher than –30 ° C are too sticky, especially at low temperatures, and can easily cause jibbing when the tape is peeled off and can easily damage the appearance of the wire harness.
• the content of the plasticizer in the pressure-sensitive adhesive is 8 to 12 parts by weight with respect to 100 parts by weight of the total (that is, the main component) of natural rubber, acrylic resin, tackifier resin and antioxidant. It is preferable to do this.
• the plasticizer is contained in the pressure-sensitive adhesive, the plasticizer easily migrates to the coating material of the electric wire, so the upper limit of the plasticizer content is 12 weights. To prevent excessive migration of the wire to the coating.
• the softening effect becomes too high, causing the adhesive to cause cohesive failure when the tape is peeled off, and the adhesive remains on the surface of the wire.
• the content of the plasticizer is less than 8 parts by weight, the softening effect is insufficient, and the binding property at low temperature is inferior.
• the plasticizer is not limited in its composition and type as long as it has the specific molecular weight and freezing point as described above, but polyester, trimellitic acid and phthalic acid plasticizers are particularly preferable.
• polyester plasticizers include adipic acid polyester (molecular weight: 800, freezing point: 45 ° C), polyester 'glutarate (molecular weight: 2500, freezing point: 40 ° C), and trimellitic acid. Triisodecyl 'trimellitate (molecular weight: 630, freezing point: — 40 ° C), triisooctyl' trimellitate (molecular weight: 550, freezing point: — 45 ° C) ) And the like. Such plasticizers can also be obtained from the market. For example, Arakawa Chemical Co., Ltd. plasticizer emulsion “KE-799 (molecular weight: 550, freezing point: ⁇ 50 ° C.)” can be used.
• the main component will be described.
• the acrylic resin a homopolymer mainly composed of acrylic acid or an acrylic acid ester such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.
• the copolymer of the said main monomer and monomers such as vinyl acetate and methyl methacrylate, etc. are mentioned.
• rosin-based rosins such as rosin, gum rosin, tall oil rosin, hydrogenated rosin, maleated rosin, terpene phenol oleagin, —vinene, 13 pinene, limonene, etc.
• Antioxidants include 2,6 di-tert-butyl-p-taresol (BHT), 2,2, -methylenebis (4-methyl-6-tert-butylphenol), triethylene glycol bis [3- (3- t-Butyl-5-methyl-4-hydroxyphenol) propionate] pentaerythrithryl-tetrakis [3— (3,5-di-tert-butyl-4-hydroxyphenol) propionate] and other phenolic (hindered phenol), dilauryl 3, 3 , Sulfuric acid such as dithiodipropionate (DLTDP), distearyl 3, 3, monothiodipropionate (DSTDP), triphenyl phosphite (TPP), triisodecyl phosphite (TDP), tris (2, 4 di — Phosphorus series such as t-butylphenol) phosphite, 2,2-methylenebis (4,6 di-tert-butylphenol) o
• a softening agent can be blended.
• Specific examples include styrene-based oils and petroleum-based softeners, which can be used alone or in appropriate combination.
• a filler can be blended.
• Specific examples include magnesium carbonate, calcium carbonate, aluminum sulfate, calcium sulfate, barium sulfate, calcium sulfite, molybdenum disulfide molybdenum, aluminum silicate, calcium silicate, diatomaceous earth, quartzite powder, talc, silica, and zeolite. These can be used alone or in appropriate combination.
• a pigment can be blended. Specifically, alumina white, graphite, titanium oxide, zinc white, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, resurge, lithobon, barite, cadmium red, cadmium mercury Red, red, red
• Organic pigments such as inorganic pigments such as cerulean blue, manganese violet and cobalt violet, shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, and dyed lakes. Can be used in appropriate combinations.
• an ultraviolet absorber can be blended.
• salicylic acid derivatives such as phenyl salicylate, ⁇ -octylphenyl salicylate, p-t butylphenol salicylate, 2, 4 dihydroxybenzophenone, 2 hydroxy-4-methoxybenzophenone, 2, 2 '-Dihydroxy-4-methoxybenzophenone, 2, 2'-dihydroxy-4,4, -dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2 hydroxy-1-4-methoxy-1- 2'-carboxybenzophenone, 2 hydro 4-hydroxy-1-methoxy-5-sulfobenzophenone 'trihydrate, 2-hydroxy-1-4-oxy-benzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2, 2', 4, 4'- Benzophenone compounds such as tetrahydroxybenzophenone, 4-dode
• various additives for pressure-sensitive adhesives such as antibacterial agents, lubricants, antiblocking agents, and antistatic agents can be blended as necessary. These may be used alone or in appropriate combinations.
• the pressure-sensitive adhesive may be prepared by mixing the above-mentioned main components, plasticizer and additives in the same manner as in the past, for example, using a roll, a Banbury mixer, a brabender, a kneader, or the like. And mix. Further, the above main component, plasticizer and additive may be either emulsion type or solvent type.
• solvents include esters such as methyl formate, ethyl acetate, and butyl acetate, alcohols such as isopropanol, hexane, cyclohexane, and toluene. Examples include hydrocarbons such as rune and xylene, and ketones such as acetone, methyl ethyl ketone, and cyclohexanone.
• the amount used is 5 for the total weight of the adhesive from the viewpoint of coating properties. -900% by weight, preferably 10-400% by weight.
• the viscosity of the coating solution and the viewpoint power in coating are 1000 to 50000 mPa-s (25 ° C.), and 3 ⁇ 4L ⁇ 2000 to 30000 mPa's (25 ° C.).
• the application amount of the pressure-sensitive adhesive may be the same as that of a general pressure-sensitive adhesive tape, and a dry thickness of 10 to 15 O / z m is appropriate.
• adhesiveness with an adhesive can be improved by applying a primer treatment to the substrate.
• Adhesive tapes A to G were prepared using the adhesive prepared with the formulation shown in Table 1.
• Adhesive tapes A to E are obtained by applying an adhesive with the indicated composition to a halogen-free tape base material in which ethylene hydroxide is blended with ethylene hydroxide as a flame retardant. Is a base material for commercially available PVC adhesive tapes coated with the indicated adhesive.Adhesive tape G is the same halogen-free tape base material for commercially available PVC adhesive tapes Street). The following evaluations were made on each adhesive tape. The results are also shown in Table 1.
• the adhesive strength was measured according to JIS C2107 (rear surface adhesive strength test method). Compared to commercially available PVC adhesive tape, “ ⁇ ” indicates that the adhesive strength is high, “ ⁇ ” indicates that it is equivalent, “X” indicates that it is inferior, and “X X” indicates that it is largely inferior without any tackiness.
• the winding work was performed in an atmosphere of 0 ° C. At that time, the case where there was no unraveling was designated as “ ⁇ ”, and the case where there was unraveling was designated as “X”.
• Acrylic resin A “SC-2” manufactured by Musashino Chemical Co., Ltd.
• Acrylic resin B Nippon Carbide Co., Ltd. “TS-805”
• Tackifying resin rough
• E-726 manufactured by 11 Chemical Co., Ltd.
• Antioxidant A “KE-800” manufactured by Arakawa Chemical Co., Ltd.
• Antioxidant B “KM2106” manufactured by API Corporation
• Plasticizer A Octyl adipate plasticizer (freezing point—60 ° C) ”
• Plasticizer B Phthalic acid plasticizer (freezing point 53 ° C, molecular weight 391)
• Plasticizer C Trimellitic acid plasticizer (Freezing point—45 ° C, molecular weight 630)
• Plasticizer D Polyester plasticizer (Freezing point—50 ° C, molecular weight 2000)
• Plasticizer E Polyester plasticizer (Freezing point—40 ° C, molecular weight 2500)
• Plasticizer F Trimellitic acid plasticizer (freezing point 30 ° C, molecular weight 550)
• Plasticizer G Polyester plasticizer (Freezing point—25 ° C, molecular weight 4200)
• Plasticizer H Polyester plasticizer (freezing point 5 ° C, molecular weight 4500)
• Plasticizer I Epoxy plasticizer (freezing point 15 ° C, molecular weight 1000)
• the adhesive tape A coated with an adhesive containing a plasticizer with a freezing point of ⁇ 60 ° C. has a low adhesive strength at low temperatures and is easily unwound and has a poor finish.
• adhesive tape D and adhesive tape E coated with a plasticizer with a freezing point higher than 1-30 ° C cause low-temperature jibing and poor finish.
• Adhesives containing plasticizers having different molecular weights as shown in Table 2 were applied to a halogen-free tape substrate to produce adhesive tapes H to L. Each adhesive tape was evaluated as follows. The results are also shown in Table 2. [0036] (5) Deterioration of wire coating material
• Acrylic resin Musashino Chemical Co., Ltd. “SC-2” Tackifying resin: Ara) 11 Chemical Co., Ltd. “E-726” Antioxidant: Ara) 11 Chemical "KE-800"
• Plasticizer K Octyl adipate plasticizer (freezing point—60 ° C, molecular weight 373)
• Plasticizer L Phthalic acid plasticizer (freezing point 53 (° C, molecular weight 390)
• Plasticizer M Polyester plasticizer (Freezing point—20 ° C, molecular weight 1000)
• Plasticizer N Trimellitic acid plasticizer (freezing point 30 ° C, molecular weight 550)
• Plasticizer O Epoxy plasticizer (freezing point 12 ° C, molecular weight 450)
• Plasticizer P Polyester plasticizer (Freezing point-10 ° C, molecular weight 1100)
• Plasticizer Q Polyester plasticizer (freezing point 20 ° C, molecular weight 4000)
• adhesive tape J and adhesive tape K in which a halogen-free tape base material is coated with an adhesive containing a plasticizer having a molecular weight of 450 to 300 are electric wires.
• the binding property without causing deterioration of the coating material is also good.
• adhesive tape H and adhesive tape I coated with an adhesive containing a plasticizer with a molecular weight of less than 450 the plasticizer migrates to the coating material of the electric wire and immediately causes deterioration of the coating material.
• the adhesive tape L coated with an adhesive containing a plasticizer with a molecular weight exceeding 3000 has poor binding properties.
• the freezing point is 30 ° C to 55 ° C and the molecular weight is 450.
• Adhesive tapes M to S were prepared using the adhesive prepared with the formulation shown in Table 3.
• Adhesive tapes M to Q are a halogen-free tape base material coated with the indicated adhesive.
• Adhesive tape R is applied to a commercially available PVC adhesive tape base material.
• Adhesive tape S is a halogen-free tape base material coated with a commercially available adhesive for PVC adhesive tape (composition is as shown). The following evaluations were made on each adhesive tape V. The results are also shown in Table 3.
• the adhesive strength was measured in accordance with JIS C2107 (back surface adhesive strength test method). Compared to commercially available PVC adhesive tape, “ ⁇ ” indicates that the adhesive strength is high, “ ⁇ ” indicates equivalent, and “ “X”, and “XX” when the tackiness is not so great.
• Bundle 6 wires, wrap the adhesive tape 5 times, leave it in a constant temperature bath at 80 ° C for 24 hours, take out the thermostatic chamber, and if the end of the adhesive tape does not peel off, “X” was used when this occurred.
• Acrylic resin A Musashino Chemical Co., Ltd. “SC-2”
• Acrylic resin B Nippon Carbide Co., Ltd. “TS-805”
• Tackifying resin rough
• E-726 manufactured by 11 Chemical Co., Ltd.
• Antioxidant A “KE-800” manufactured by Arakawa Chemical Co., Ltd.
• Antioxidant B “KM21-6” manufactured by API Corporation
• Plasticizer “KE-799” manufactured by Arakawa Chemical Co., Ltd. (Freezing point—50 ° C, molecular weight 550) [0045] As shown in Table 3, the plasticizer content is 8-12 per 100 parts by weight of the main component. It can be seen that the weight part is preferred. If the content of the plasticizer is less than 8 parts by weight, the zippering is likely to occur and the finish is poor. When the plasticizer content exceeds 12 parts by weight, further dissolution, residual adhesive, and peeling of the end part are added. In addition, even if the plasticizer content is within the scope of the present invention, the adhesive tape R using a PVC adhesive tape substrate, or an adhesive that combines a PVC adhesive tape adhesive and a halogen-free tape substrate. Tape G shows a further decrease in adhesive strength.
• the low-temperature adhesive strength of the halogen-free pressure-sensitive adhesive tape can be increased, and the binding property can be improved.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Adhesive Tapes (AREA)

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Applications Claiming Priority (2)

Publications (1)

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• 2004
  • 2004-12-10 JP JP2004358747A patent/JP4689256B2/ja not_active Expired - Lifetime
• 2005
  • 2005-12-09 TW TW094143552A patent/TW200626698A/zh not_active IP Right Cessation
  • 2005-12-09 CN CN2005800422375A patent/CN101072839B/zh not_active Expired - Lifetime
  • 2005-12-09 WO PCT/JP2005/022680 patent/WO2006062197A1/ja not_active Ceased
  • 2005-12-09 US US11/720,799 patent/US20100129653A1/en not_active Abandoned
  • 2005-12-09 DE DE112005003116.0T patent/DE112005003116B4/de not_active Expired - Lifetime

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