WO2006062196A1 - ハロゲンフリー粘着テープ - Google Patents
ハロゲンフリー粘着テープ Download PDFInfo
- Publication number
- WO2006062196A1 WO2006062196A1 PCT/JP2005/022679 JP2005022679W WO2006062196A1 WO 2006062196 A1 WO2006062196 A1 WO 2006062196A1 JP 2005022679 W JP2005022679 W JP 2005022679W WO 2006062196 A1 WO2006062196 A1 WO 2006062196A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- halogen
- adhesive tape
- adhesive
- resin
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
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
- C09J7/385—Acrylic polymers
-
- 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
-
- 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
-
- 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 adhesive is based on the adhesive of the PVC adhesive tape, and is mainly composed of natural rubber, acrylic resin, and tackifier resin, with antioxidants, plasticizers, and filling. It is formed by adding additives such as materials, anti-aging agents and copper damage inhibitors.
- the adhesive strength of the adhesive to the base material is lower than the adhesive strength of the adhesive to the base material of the PVC tape. As a result, there are problems such as wrinkles and peeling at the end of the tape, which impairs the finish and appearance.
- the adhesive strength has been improved by adjusting the blending ratio of each component, it is still sufficient.
- the present invention has been made in view of such circumstances, and an object of the present invention is to increase the adhesive strength of a halogen-free adhesive tape, particularly the adhesive strength of an adhesive to a base material, and to improve the binding property.
- the present invention provides the following halogen-free pressure-sensitive adhesive tape.
- a copolymer of acrylic acid or an acrylate ester and a monomer that forms a tackifying resin is formed on at least one surface of a tape base material made of a sonohalogen-based resin composition containing no halogen element.
- a halogen-free pressure-sensitive adhesive tape which is coated with a pressure-sensitive adhesive containing the modified acrylic resin.
- the monomer forming the tackified resin is 4 to 8 parts by weight with respect to 100 parts by weight of acrylic acid or acrylic ester. Halogen-free adhesive tape.
- the pressure-sensitive adhesive contains a modified acrylic resin
- the pressure-sensitive adhesive strength of the pressure-sensitive adhesive to the base material is increased. Therefore, for example, when used for bundling wire harnesses, a wire harness excellent in finishing and appearance can be obtained.
- 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.
- a pressure-sensitive adhesive is applied to the base material, and the pressure-sensitive adhesive is a modified acrylic resin obtained by copolymerizing acrylic acid or an acrylate ester and a monomer that forms a tackifying resin.
- Acrylic acid or acrylic acid ester is a monomer that forms acrylic resin.
- Acrylic resin itself is widely used as the main component of adhesives.
- tackifier resin is widely used alone as a main component of the adhesive.
- the adhesive strength can be greatly increased as compared with the case where the acrylic resin and the tackifying resin are compounded as individual resins. .
- Acrylic acid and acrylic acid ester can be used without limitation as long as they are monomers that form acrylic resin used in pressure-sensitive adhesives.
- acrylic acid esters include butyl acrylate and acrylic acid 2- Examples include ethyl hexyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrafurfuryl acrylate, and isanol acrylate. Of these, 2-ethylhexyl acrylate is preferred because of its large effect of improving the adhesive strength of the adhesive to the substrate!
- terpene resin aromatic hydrogenated resin, aliphatic hydrogenated resin, coumarone indene resin, phenolic resin, styrene resin, etc. are generally used as tackifying resin.
- monomers that can be copolymerized with the above-mentioned acrylic acid or acrylate ester are appropriately selected and used among the monomers forming them.
- monomers that form terpene-based resins that give stronger tackifying ability when modified talyl resin specifically (j8-vinene), dipentene, ( ⁇ -vinene), a-vinene Phenol, dipentene phenol, terpene phenol and the like are preferred, and terpene phenol is particularly preferred.
- the amount of the tackifying resin monomer in the modified acrylic resin is preferably 4 to 8 parts by weight with respect to 100 parts by weight of acrylic acid or acrylate ester. If the monomer amount of the tackifying resin is less than 4 parts by weight, sufficient adhesive strength cannot be obtained, and the tape can be unwound or the end of the tape peeled off. This is likely to occur. On the other hand, if the monomer amount of the tackifying resin exceeds 8 parts by weight, the adhesive strength becomes too high and the resistance when peeling the tape becomes excessive, the base material stretches and whitens, and the appearance of the wire harness is impaired. Become.
- Such modified acrylic resin can also be obtained from Sakaiba, for example, using "SC-2 (2-ethylhexyl acrylate Z terpene phenol copolymer)" manufactured by Musashino Chemical Co., Ltd. can do.
- the modified acrylic resin includes butyl acetate, acrylonitrile, acrylamide, styrene, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, methacrylic acid.
- the pressure-sensitive adhesive is generally formed by blending natural rubber, acrylic resin and tackifying resin with various additives such as antioxidants and plasticizers. Can be blended.
- the modified acrylic resin has both an action as an acrylic resin and an action as an adhesive Tomisho resin, and all of the acrylic resin in conventional adhesives is replaced with this modified acrylic resin. Most preferably, a part of the acrylic resin can be replaced with a modified acrylic resin. For the same reason, all or part of the tackifying resin in the conventional pressure-sensitive adhesive can be replaced with modified acrylic resin.
- the pressure-sensitive adhesive includes two types of modified acrylic resin and tackifying resin, which may include all of acrylic resin, modified acrylic resin and tackifying resin as an adhesive component, or acrylic resin and modified resin. Two types of acrylic resin may be used.
- the blending ratio at that time is also appropriately selected within the range of the blending amount of the conventional acrylic resin and the blending amount of the tackifying resin depending on the combination of the acrylic resin, the modified acrylic resin and the tackifying resin.
- the other components of the pressure-sensitive adhesive preferably include natural rubber, a plasticizer and an antioxidant. Any of them may be known ones, but preferred examples are shown below, and the amount of each compound can be appropriately selected.
- a plasticizer is added to give the adhesive layer moderate flexibility, but a plasticizer having a molecular weight of 450 to 3000 is used to maintain the flexibility and suppress the migration to the counterpart material. It is preferable to do. Plasticizers with a molecular weight of less than 450 will migrate, and plasticizers with a molecular weight of more than 3000 will reduce the cohesiveness, which is poor in softening the adhesive at low temperatures.
- the type of plasticizer is not limited as long as it has the specific molecular weight and freezing point as described above, but polyester-based, trimellitic acid-based and phthalic acid-based plasticizers are 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.
- the plasticizer include triisodecyl 'trimellitate (molecular weight: 630, freezing point: —40 ° C), triisooctyl' trimellitate (molecular weight: 550, freezing point: —45 ° C), and the like.
- 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.
- Antioxidants include 2, 6-di-butyl-p-taresol (BHT), 2, 2'-methylene bis (4-methyl-6-t-butylphenol), triethylene glycol bis [3- (3- t Butyl 5-methyl 4-hydroxyphenol) propionate] pentaerythritic rutetrakis [3— (3,5-di-tert-butyl-4-hydroxyphenol) propionate] and other phenols (hindered phenols), dilauryl 3, Sulfur compounds such as 3'-thiodipropionate (D LTDP) and distearyl 3, 3'-thiodipropionate (DSTDP), triphenyl phosphite (TPP), triisodecyl phosphite (TDP), tris (2 , 4 di-tert-butylphenol) phosphite, 2,2-methylenebis (4,6 di-tert-butylphenol) ota Phosphorous compounds such as til
- rosin gum rosin, toll oil rosin, hydrogenated rosin, maleic rosin and other rosin-based rosin, aliphatic, alicyclic, aromatic petroleum rosin, coumarone-indene rosin, styrene
- phenolic resins such as system resin, alkylphenol resin, and rosin-modified phenol resin, and xylene resin, which can be used alone or in appropriate combination.
- terpene rosin can be used.
- various additives conventionally added to pressure-sensitive adhesives can be blended.
- blend a thickener include carboxybule polymer, carboxymethylcellulose, gelatin, dextrin, hydroxypropylmethylcellulose, hydroxypropylcellulose, alginic acid (salt), etc., each of which is used alone or in appropriate combination. it can.
- 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 may 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, Bengala, Molybdenum red, Red lead, Yellow lead, Cadmium yellow, Norium yellow, Strontium yellow, Titanium yellow, Titanium black, Chrome oxide green, Cobalt oxide, Cobalt green, Cobalt 'Chromium
- examples include inorganic pigments such as green, ultramarine blue, bitumen, cobalt blue, cerulean blue, manganese purple, and cobalt purple, and organic pigments such as shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, and dyed lakes. These can be used alone or in appropriate combination.
- a ultraviolet absorber can be mix
- salicylic acid derivatives such as phenyl salicylate, p-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 4-methoxy-1-2'-carboxy Benzophenone, 2-hydroxy-4-methoxy-1-5-sulfobenzophenone 'trihydrate, 2-hydroxy-1-4-oxy-benzophenone, 2-hydroxy-1-octadecyloxybenzophenone, 2, 2' , 4, 4'-Tetrahydroxybenzophenone, 4-dedecyloxy 2-hydroxybenzophenone, 2-hydroxy-1-4- 2-hydroxy-1-
- the pressure-sensitive adhesive can be prepared by mixing the above-mentioned components in a predetermined composition in the same manner as in the prior art.
- a roll, a Banbury mixer, a Brabender, a kneader, etc. may be used.
- the above main component, plasticizer and additive may be any of emulsion type and solvent type.
- Solvents include esters such as methyl formate, ethyl acetate, butyl acetate, alcohols such as isopropanol, hydrocarbons such as hexane, cyclohexane, toluene, xylene, acetone, methyl ethyl ketone, cyclohexanone, etc.
- the amount used is 5 to 900% by weight, preferably 10 to 400% by weight, based on the total weight of the pressure-sensitive adhesive.
- the viscosity of the coating solution is 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 an adhesive prepared with the formulation shown in Table 1.
- Adhesive tapes A to D and F are obtained by applying an adhesive with the indicated composition to a halogen-free tape base material in which ethylene propylene copolymer is blended with magnesium hydroxide as a flame retardant.
- E is a commercially available PVC adhesive tape base material coated with the indicated adhesive
- adhesive tape F is the same halogen-free tape base material commercially available PVC adhesive tape adhesive.
- Modified acrylic resin is a copolymer of 2-ethylhexyl acrylate and terpene phenol at the indicated ratio. What was made to use was used. And the following evaluation was performed about each adhesive tape. The results are also shown in Table 1.
- ⁇ indicates that the adhesive strength is high, ⁇ indicates equivalent, ⁇ indicates slightly inferior, and X indicates inferior. “XX” was assigned when the tackiness was not so great.
- the amount of terylene phenol is the amount of i T in 100SS part of 2-ethylhexyl acrylate (unit: MM)
- Tackifying resin “KE-726” manufactured by Araha 11 Chemical Co., Ltd.
- Antioxidant A “KE-800” manufactured by Arakawa Chemical Co., Ltd.
- Antioxidant B “IB2 Corporation” “KM2106”
- an adhesive containing a modified acrylic resin in which 4 to 8 parts by weight of terpene phenol was copolymerized was applied to a halogen-free tape substrate. All the evaluations of the applied adhesive tape C are good.
- adhesive tapes A and B with a low amount of terpene phenol have low adhesive strength and are easy to unwind, and the finish of the wire harness is also poor.
- Adhesive tapes D and E with an excessive amount of terpene phenol are too strong to cause whitening, resulting in poor wire harness finish.
- the adhesive is specified in the present invention, such as adhesive tape F
- sufficient adhesive strength cannot be obtained when using a PVC adhesive tape base material, it is easy to unravel, and the finish of the wire harness also deteriorates.
- adhesives for PVC adhesive tapes and halogen-free tape base materials are used in combination, such as adhesive tape G, the adhesive strength is particularly low, and the untidy wire harness is poorly finished.
- the adhesive strength of the halogen-free adhesive tape in particular, the adhesive strength of the adhesive to the base material can be increased, and the binding property can be improved.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Insulated Conductors (AREA)
Abstract
Description
Claims
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE112005003023T DE112005003023T5 (de) | 2004-12-10 | 2005-12-09 | Halogenfreies druckempfindliches Klebeband |
| US11/720,947 US7883771B2 (en) | 2004-12-10 | 2005-12-09 | Halogen-free pressure-sensitive adhesive tape |
| CN200580042238XA CN101072840B (zh) | 2004-12-10 | 2005-12-09 | 无卤粘合剂带 |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004358774A JP4624090B2 (ja) | 2004-12-10 | 2004-12-10 | ハロゲンフリー粘着テープ |
| JP2004-358774 | 2004-12-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006062196A1 true WO2006062196A1 (ja) | 2006-06-15 |
Family
ID=36578016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2005/022679 Ceased WO2006062196A1 (ja) | 2004-12-10 | 2005-12-09 | ハロゲンフリー粘着テープ |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7883771B2 (ja) |
| JP (1) | JP4624090B2 (ja) |
| CN (1) | CN101072840B (ja) |
| DE (1) | DE112005003023T5 (ja) |
| TW (1) | TWI326301B (ja) |
| WO (1) | WO2006062196A1 (ja) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS543136A (en) * | 1977-06-08 | 1979-01-11 | Arakawa Chem Ind Co Ltd | Pressure-sensitive adhesives |
| JP2000327708A (ja) * | 1999-03-12 | 2000-11-28 | Arakawa Chem Ind Co Ltd | アクリル系重合体組成物の製造方法および当該製造方法により得られるアクリル系重合体組成物 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5130375A (en) * | 1989-11-01 | 1992-07-14 | Avery Dennison Corporation | Vinyl functional reactive tackifiers for pressure-sensitive adhesives |
| US6274657B1 (en) * | 1992-04-23 | 2001-08-14 | Arizona Chemical Company | Surfactant for forming stable dispersions of rosin esters |
| JP3539765B2 (ja) * | 1994-07-19 | 2004-07-07 | 三井化学株式会社 | 粘着付与樹脂組成物 |
| GB9515827D0 (en) | 1995-08-02 | 1995-10-04 | Scapa Group Plc | Pressure sensitive adhesive tape |
| JP3425524B2 (ja) | 1998-03-12 | 2003-07-14 | 矢崎総業株式会社 | 粘着テープ用粘着組成物及びそれを用いた粘着テープ |
| JP2003128714A (ja) * | 2001-10-26 | 2003-05-08 | Arakawa Chem Ind Co Ltd | アクリル系部分重合体組成物の製造方法、当該製造方法により得られるアクリル系部分重合体組成物および当該組成物を紫外線重合させてなる粘着剤組成物 |
| JP3952446B2 (ja) | 2001-12-12 | 2007-08-01 | 住友電装株式会社 | ワイヤーハーネス保護材及びこれを用いたワイヤーハーネス |
| JP2003219533A (ja) | 2002-01-18 | 2003-07-31 | Sumitomo Wiring Syst Ltd | ワイヤーハーネス保護材及びこれを用いたワイヤーハーネス |
| JP3846471B2 (ja) * | 2003-11-07 | 2006-11-15 | 東洋インキ製造株式会社 | 粘着剤及び該粘着剤を用いてなる粘着加工品 |
-
2004
- 2004-12-10 JP JP2004358774A patent/JP4624090B2/ja not_active Expired - Fee Related
-
2005
- 2005-12-09 TW TW094143551A patent/TWI326301B/zh not_active IP Right Cessation
- 2005-12-09 CN CN200580042238XA patent/CN101072840B/zh not_active Expired - Fee Related
- 2005-12-09 WO PCT/JP2005/022679 patent/WO2006062196A1/ja not_active Ceased
- 2005-12-09 US US11/720,947 patent/US7883771B2/en not_active Expired - Fee Related
- 2005-12-09 DE DE112005003023T patent/DE112005003023T5/de not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS543136A (en) * | 1977-06-08 | 1979-01-11 | Arakawa Chem Ind Co Ltd | Pressure-sensitive adhesives |
| JP2000327708A (ja) * | 1999-03-12 | 2000-11-28 | Arakawa Chem Ind Co Ltd | アクリル系重合体組成物の製造方法および当該製造方法により得られるアクリル系重合体組成物 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI326301B (en) | 2010-06-21 |
| JP4624090B2 (ja) | 2011-02-02 |
| US20100009181A1 (en) | 2010-01-14 |
| DE112005003023T5 (de) | 2007-12-27 |
| CN101072840B (zh) | 2011-01-12 |
| CN101072840A (zh) | 2007-11-14 |
| TW200628582A (en) | 2006-08-16 |
| JP2006161009A (ja) | 2006-06-22 |
| US7883771B2 (en) | 2011-02-08 |
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