WO2011024622A2 - 粘着フィルム - Google Patents

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Publication number
WO2011024622A2
WO2011024622A2 PCT/JP2010/063271 JP2010063271W WO2011024622A2 WO 2011024622 A2 WO2011024622 A2 WO 2011024622A2 JP 2010063271 W JP2010063271 W JP 2010063271W WO 2011024622 A2 WO2011024622 A2 WO 2011024622A2
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WIPO (PCT)
Prior art keywords
film
layer
pressure
adhesive
sensitive adhesive
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PCT/JP2010/063271
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English (en)
French (fr)
Japanese (ja)
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WO2011024622A3 (ja
Inventor
浩明 江崎
大野　真一
孝志 井川
Original Assignee
東洋紡績株式会社
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Application filed by 東洋紡績株式会社 filed Critical 東洋紡績株式会社
Priority to CN201080037736.6A priority Critical patent/CN102597145B/zh
Priority to KR1020127004683A priority patent/KR101781230B1/ko
Publication of WO2011024622A2 publication Critical patent/WO2011024622A2/ja
Publication of WO2011024622A3 publication Critical patent/WO2011024622A3/ja

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    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/403—Adhesives in the form of films or foils characterised by release liners characterised by the structure of the release feature
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • 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
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C09J123/12—Polypropene
    • 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
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene 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
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • 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
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/16—Presence of ethen-propene or ethene-propene-diene copolymers

Definitions

  • the present invention relates to an adhesive film.
  • the pressure-sensitive adhesive film of the present invention protects the surface of an article from undesirable effects such as dust adhesion and scratching by sticking it on the surface of an article such as a synthetic resin plate, a decorative plywood, a metal plate, and a coated steel plate. It can be particularly preferably used as a surface protective film for the purpose and as a surface protective film when the printed circuit board is immersed in solder.
  • the term “adhesive film” in the present invention also means an adhesive sheet or an adhesive tape.
  • adhesive films aimed at protecting the surface of coatings have been used during processing, storage, and transportation of building materials, electrical, electronic products, automobiles, etc. Such adhesive films have good adhesive properties. In addition, after use, each surface must be able to be easily peeled off without being contaminated with an adhesive.
  • adhesive films based on polyolefin resins have been used instead of adhesive films based on plasticized vinyl chloride resins.
  • the pressure-sensitive adhesive film based on these polyolefin resins is mainly composed of a low-crystalline or amorphous pressure-sensitive adhesive layer such as EVA or low-density polyethylene or a pressure-sensitive adhesive layer made of an elastomer such as SIS or SEBS as the base material layer.
  • an amorphous olefin polymer and a specific ethylene-based polymer are used as a pressure-sensitive adhesive that maintains suitable tackiness under extreme low temperature and high temperature conditions regardless of the operating temperature range.
  • a composition made of a polymer is disclosed (for example, see Patent Documents 1, 2, and 3).
  • the above adhesive film also has a problem of blocking due to storage.
  • the film which provided the surface layer which has specific surface roughness on the opposite surface of the adhesion layer, and improved the anti-blocking property is disclosed (for example, refer to references 4, 5, and 6). However, this film was not sufficient in terms of performance.
  • the problem to be solved by the present invention is that there is little blocking between the pressure-sensitive adhesive films, in particular, there is little blocking even after the pressure-sensitive adhesive film is stored in a roll state, it is excellent in processability, and after being bonded to the adherend, it is processed at a high temperature.
  • the present inventors have conducted extensive studies. As a result, when the pressure-sensitive adhesive films are overlapped, the surface of the pressure-sensitive adhesive layer is easily affected by the opposite surface. The present inventors have found that the formation of small bubbles between the body and the film and the bleed from the adhesive layer are related to the adhesive behavior.
  • the present invention is a polypropylene resin film comprising a laminate comprising an adhesive layer on one side of a base material layer comprising a polypropylene resin and a release layer on the opposite side, the average of the surface of the release layer
  • the surface roughness SRa is 0.050 ⁇ m or more and 0.200 ⁇ m or less
  • the average roughness SRa of the surface of the adhesive layer is 0.030 ⁇ m or less
  • the contact area with the adherend as defined in the specification is 90% or more and 100% or less
  • the amount of the antioxidant bleed is b1, the amount of the polymer component bleed on the pressure-sensitive adhesive surface and acrylic plate peeled off after 1 week at 40 ° C. after adhering to the acrylic plate, and the amount of antioxidant b2
  • (a -A1) ⁇ 2- (b2-b1 ) is, -50mg / m 2 or more and 50 mg / m 2 or less, and the film haze of the adhesive film, characterized in that in the range of 1 to 40%.
  • the present invention there is little blocking between pressure-sensitive adhesive films, in particular, there is little blocking even after the pressure-sensitive adhesive film is stored in a roll state, it is excellent in processing suitability, and it is foamed even after being bonded to an adherend and treated at a high temperature. It is difficult to obtain an adhesive film with little change in adhesive strength over time without being affected by the storage state of the adhesive film having excellent transparency and little increase in adhesive strength. Moreover, it has excellent tackiness and excellent processability.
  • the adhesive layer contains a polypropylene-based elastomer.
  • the polypropylene elastomer is amorphous polypropylene or a copolymer of polypropylene and an erene-propylene rubber made of only a polypropylene resin.
  • the average surface roughness SRa of the surface of the release layer is 0.150 ⁇ m or less.
  • the average surface roughness SRa of the surface of the adhesive layer is 0.020 ⁇ m or less.
  • the base material layer, the adhesive layer, and the release layer are melt extruded and laminated from a plurality of extruders by a coextrusion method.
  • a film roll made of the film wherein the film roll has a width of 450 mm or more and a length of 300 m or more is a preferred form.
  • the pressure-sensitive adhesive film according to the present invention has little blocking between the pressure-sensitive adhesive films, in particular, little blocking even after the pressure-sensitive adhesive film is stored in a roll state, excellent processing suitability, and foaming even when treated at a high temperature after being bonded to an adherend. This is advantageous in that it is difficult to be applied, has excellent transparency, and has little change in adhesive force while maintaining the appearance of the adherend.
  • the adhesive film of the present invention requires a base material layer made of polypropylene resin, and examples of the polypropylene resin used here include crystalline polypropylene, random copolymer block copolymer of propylene and a small amount of ⁇ -olefin, and the like.
  • n-heptane-insoluble isotactic propylene homopolymer used in ordinary extrusion molding or the like, or polypropylene containing 60% by weight or more of propylene and other ⁇ -A copolymer with an olefin can be mentioned, and this propylene homopolymer or a copolymer of propylene and another ⁇ -olefin can be used alone or in combination.
  • the insolubility of n-heptane is indicative of the crystallinity of polypropylene and at the same time indicates safety.
  • n-heptane insolubility at 25 ° C., 60 ° C.
  • the ⁇ -olefin copolymerization component of the copolymer of propylene and other ⁇ -olefins includes ⁇ -olefins having 2 to 8 carbon atoms such as ethylene, 1-butene, 1-pentene, 1-hexene, 4 C4 or higher ⁇ -olefins such as -methyl-1-pentene are preferred.
  • the copolymer is preferably a random or block copolymer obtained by polymerizing one or more of the ⁇ -olefins exemplified above with propylene.
  • the melt flow rate (MFR) can be exemplified in the range of 0.1 to 100 g / 10 min, preferably 0.5 to 20 g / 10 min, and more preferably 1.0 to 10 g / 10 min. The range of 2.0 to 7.0 g / 10 min is particularly preferable.
  • Two or more kinds of copolymers of propylene and other ⁇ -olefins can be mixed and used. Use of a 1-butene copolymer polypropylene copolymer makes the film soft and tacky, and is suitable for improving the contact area ratio.
  • the adhesive layer is made of an amorphous polyolefin resin. It is preferable that it contains at least 50% or more and is finely dispersed.
  • a method for containing the polyolefin-based elastomer 1) a method using a block copolymer in which an elastomer component is finely dispersed in islands by multistage polymerization, and 2) diluting the olefin-based elastomer resin with a crystalline olefin resin.
  • a method, and 3) a method of using both in combination examples include “Zeras MC707” and “Zeras MC717” manufactured by Mitsubishi Chemical Corporation.
  • 2) Sumitomo Chemical Co., Ltd. "Tough selenium H3522A" can be mentioned, for example.
  • the amount of the high molecular weight-derived bleed product and the amount of the bleed product of the antioxidant which is one of the requirements of the present invention, are within a specific range, that is, 24 hours at 23 ° C. after adhering to the acrylic plate.
  • A1 is the amount of the bleed material of the polymer component on the adhesive surface and the acrylic plate when peeled after elapse
  • b1 is the amount of the bleed material of the antioxidant
  • the adhesive is peeled off after 1 week at 40 ° C.
  • the amount of the bleed product is a value obtained by extraction with chloroform, and means a very small amount of polymer or additive-derived component on the surface of the adhesive layer, unlike the adhesive residue of the so-called adhesive layer.
  • the measures to bring the amount of the high molecular weight bleed material and the amount of the antioxidant bleed material within a specific range are as follows: 1) Before forming the film, the raw material resin is immersed in water and the high molecular weight low molecular weight material 2) A method in which corona treatment is applied to the surface of the adhesive layer during film formation or after film formation to increase the number of bleeds derived from the initial high molecular weight. 3) Thermal stability in which the amount of bleed out increases after adhesion. The method etc. which add an agent are mentioned. However, since these methods may cause a decrease in the adhesive strength over time depending on the conditions to be carried out, care must be taken.
  • a phenolic antioxidant is preferable.
  • Commercial products can also be used.
  • Irganox 1010 (Ciba Specialty Chemicals Co., Ltd.), Irganox 1076 (Ciba Specialty Chemicals Co., Ltd.), Irganox 1330 (Ciba Specialty Chemicals Co., Ltd.) ), Irganox 3114 (manufactured by Ciba Specialty Chemicals), Irganox 1425WL (manufactured by Ciba Specialty Chemicals), and the like. These have the property that the amount of bleed out increases after sticking.
  • Examples of the adhesive layer include those having a melt flow rate (MFR) in the range of 0.1 to 100 g / 10 min, preferably 0.5 to 20 g / 10 min, and more preferably 1.0 to 10 g / 10 min. it can.
  • MFR melt flow rate
  • the range of 2.0 to 7.0 g / 10 min is particularly preferable.
  • the average surface roughness SRa of the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film of the present invention needs to be 0.030 ⁇ m or less. Preferably, it is 0.025 ⁇ m or less, more preferably 0.020 ⁇ m or less, and particularly preferably 0.015 ⁇ m or less.
  • the contact area is reduced at the time of bonding to the adherend, which causes a decrease in the adhesive strength, which is not preferable.
  • One of the factors that determine the adhesive strength is the force that attracts materials, that is, the van der Waals force, on each surface of the laminated film that is in contact. Yes.
  • the fact that the contact area is small means that the attractive force between the bonded film surface and the adherend surface is reduced, which is not preferable because the adhesive force is lowered. Further, it is necessary to make the surface of the pressure-sensitive adhesive layer as flat as possible, and it is preferable to add as little additive as possible to form surface irregularities. On the other hand, it can be said that it is practically difficult to make the average surface roughness SRa of the surface of the adhesive layer less than 0.010 ⁇ m even in a stretched film without additives.
  • the pressure-sensitive adhesive film of the present invention preferably has a thickness variation rate in the transverse direction, which is a direction orthogonal to the winding direction during film production, in the range of 2.0% or more and 10.0% or less. Is 8.0% or less, more preferably 6.0% or less.
  • a thickness variation rate exceeds 10.0%, when pressure-sensitive adhesive film is pressure-applied to an adherend, pressure unevenness occurs depending on the location, which causes a decrease in adhesive strength, which is not preferable.
  • it can be said that it is practically difficult to suppress the thickness variation rate to less than 2.0%.
  • the film of the present invention preferably has a value of 90% or more when the contact surface property with the adherend is measured by the following method in accordance with the JIS-Z-0237 adhesive tape / adhesive sheet test method. Further, it is preferably 95% or more, particularly preferably 98% or more. Thereby, when it heat-processes on the conditions of 80 degreeC x 24 hr, it is hard to foam and it can suppress the float and peeling from the acrylic board of the stuck film. By increasing the contact area, it is considered that invisible bubbles present at the interface between the adherend and the film were removed.
  • the difference between the initial adhesive strength at 50 ° C. and the initial adhesive strength at 23 ° C. of the film is preferably 10 cN / 25 mm or less, particularly preferably less than 5 cN / 25 mm, and thus at a high temperature.
  • the change in the adhesive strength is small compared to that at room temperature, the change in the adhesive strength over time is small.
  • the pressure-sensitive adhesive strength of the pressure-sensitive adhesive film of the present application is preferably in the range of 3 to 50 cN / 25 cm at 23 ° C. from the viewpoint of protective performance and peelability of the adherend.
  • the adhesive strength can be set by appropriately setting the adhesive strength by controlling the amount and composition of the amorphous component of the resin of the adhesive layer.
  • the adhesive film of this invention can contain a well-known additive as needed in the range which does not impair the effect of this invention.
  • a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, an impact resistance improvement agent and the like may be contained.
  • the low molecular weight substance on the surface of the adhesive layer is preferably less than 1 mg / m2.
  • the pressure-sensitive adhesive film of the present invention forms a release layer on the surface opposite to the pressure-sensitive adhesive layer laminated on one side of the base material layer, so that even if the pressure-sensitive adhesive films are stacked, there is little blocking between the pressure-sensitive adhesive films, In particular, there is little blocking even after the pressure-sensitive adhesive film is stored in a roll state, and the processability is excellent.
  • the average surface roughness SRa of the surface is preferably 0.050 ⁇ m or more.
  • the surface irregularities of the release layer are transferred to the surface of the adhesive layer, and the adhesive force and the above-mentioned adhesion area are reduced, or immediately after being pasted to the adherend and after lapse of time.
  • the average surface roughness SRa is preferably 0.200 ⁇ m or less. By doing so, blocking resistance and the protection performance of a to-be-adhered body can be improved.
  • the surface irregularity of the release layer is preferably a surface having an average surface roughness SRa of 0.150 ⁇ m or less, more preferably 0.060 ⁇ m or more and 0.130 ⁇ m or less, and 0.080 ⁇ m. As mentioned above, 0.130 micrometer or less is the most preferable.
  • the surface was roughened to a layer made of silicone resin or fluororesin or a mat shape obtained by mixing a resin made of propylene ethylene block copolymer and a polyethylene resin. Layers can be stacked. Specific examples of resins suitable for obtaining a mat-like surface include propylene-ethylene block copolymers such as “BC3HF” manufactured by Nippon Polypro Co., Ltd.
  • a 100% propylene-ethylene block copolymer formulation is advantageous, but when used alone, the surface roughness becomes too large. Therefore, it is necessary to dilute with a polypropylene homopolymer or a propylene-ethylene random copolymer so as to be within the range of the above surface roughness.
  • the haze value of the pressure-sensitive adhesive film of the present invention is preferably in the range of 1 to 40, particularly when used for an optical adherend. More preferably, it is 1 to 30%, and particularly preferably 1 to 25%.
  • the thickness of the pressure-sensitive adhesive layer of the present invention is preferably 1 ⁇ m or more and less than 30 ⁇ m.
  • the thickness of the pressure-sensitive adhesive film is less than 1 ⁇ m, there is a problem with adhesion, and when it is 30 ⁇ m or more, there is a problem that the adhesive force on the surface of the pressure-sensitive adhesive layer is too strong.
  • the thickness of the pressure-sensitive adhesive layer is large, the contact area with the adherend tends to be large, which is particularly effective when a hard resin is used for the pressure-sensitive adhesive layer.
  • the thickness of the adhesive layer is preferably 2 ⁇ m or more and 20 ⁇ m or less, more preferably 2 ⁇ m or more and 15 ⁇ m or less, and particularly preferably 2 ⁇ m or more and 5 ⁇ m or less.
  • the thickness of the base material layer of the present invention is preferably 5 ⁇ m or more and less than 100 ⁇ m, and more preferably 15 ⁇ m or more and less than 25 ⁇ m.
  • the tackiness means instantaneous adhesive force and is an index of ease of adhesion at the initial bonding time.
  • the pressure-sensitive adhesive film of the present invention is preferably in the form of a roll in terms of handling.
  • the upper limit of the width and the winding length of the film roll is not particularly limited, but from the viewpoint of ease of handling, the width is generally 1.5 m or less, and the winding length is preferably 6000 m or less when the film thickness is 45 ⁇ m.
  • a winding core a plastic core and metal cores, such as 3 inches, 6 inches, and 8 inches, can usually be used.
  • the adhesive film of the present invention is particularly a synthetic resin plate (for example, for optical members and building materials), a stainless plate (for example, for building materials), an aluminum plate, a decorative plywood, a steel plate, a glass plate, a household appliance, and a precision machine.
  • a synthetic resin plate for example, for optical members and building materials
  • a stainless plate for example, for building materials
  • an aluminum plate for example, a decorative plywood, a steel plate, a glass plate, a household appliance, and a precision machine.
  • secondary processing For example, it can be suitably used in order to prevent damage from bending during bending or pressing.
  • the present invention will be further described with reference to examples.
  • the present invention is not limited to the following examples without departing from the gist thereof.
  • the evaluation method of the physical property in a following example and a comparative example is as follows.
  • a piece was cut out, and using a rubber roll having a mass of 2000 g (with a spring hardness of 80 Hs on the roller surface and a width of 45 mm and a diameter (including the rubber layer) of 95 mm, covered with a rubber layer having a thickness of 6 mm),
  • the test piece was reciprocated once at a speed of 5 mm / sec. After crimping, the initial one is left for 30 minutes in an environment at a temperature of 23 ° C. and a relative humidity of 65%, and the time left for 24 hours is 300 mm using “Tensilon” (UTM-IIIL) manufactured by Toyo Seiki Co., Ltd.
  • the resistance value when peeled 180 degrees at a rate of / min was defined as the adhesive strength [cN / 25 mm].
  • 180 degree peeling means holding the peeling angle between the acrylic plate and the film at the time of measuring the resistance value at the time of peeling at 180 degrees.
  • a polyester sheet having a thickness of 190 ⁇ m and a size of 25 mm ⁇ 170 mm is prepared as a grip margin for the measurement sample, and the width of the paste margin is 15 mm at the end of the measurement sample obtained by pressure-bonding the adhesive film and the acrylic plate. Attached with cellophane tape as a grip for measurement.
  • a schematic diagram of the measurement sample is shown in FIG. The measurement was performed three times for one sample, and the average value was defined as the adhesive strength of the sample.
  • the Kimwipe previously washed with chloroform was dried and then added with n-hexane, the acrylic plate was wiped off, and the Kimwipe was extracted with n-hexane (wiping and extraction were repeated three times). These extracts were collected, dried and the weight of the residue was measured. Further, the residue was dissolved in deuterated chloroform, and an H-NMR spectrum was measured using a 400 MHz-NMR apparatus manufactured by VARIAN. The weight ratio of each component contained in the extract was calculated from the peak area of each component of the H-NMR spectrum. Of these, the total extract weight was multiplied by the weight ratio of the total polymer components and the total weight of the antioxidants to calculate the amount a1 of the bleed product of the polymer components and the amount b1 of the bleed amount of the antioxidant.
  • Example 1 Preparation of base material layer 100 wt% of a homopolypropylene polymer (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, tensile elastic modulus: 1500 MPa) was melt-extruded with a 60 mm ⁇ single screw extruder (L / D: 22.4) to form a base layer.
  • a homopolypropylene polymer manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4, tensile elastic modulus: 1500 MPa
  • the extruded film was sprayed onto a casting roll at a temperature of 20 ° C. with an air knife, taken at a speed of 12 m / min, cooled and solidified, and the substrate layer thickness was 35 ⁇ m, the adhesive layer thickness was 10 ⁇ m, and the release layer thickness was 3 ⁇ m.
  • a seed 3 layer unstretched film was obtained.
  • a smooth adhesive layer is formed, it has adhesiveness at room temperature, there is no contact unevenness between the adherend and the adhesive layer, and the adhesive force increases after sticking to the adherend.
  • the width was small, the appearance was excellent, there was no blocking between the release layer and the adhesive layer, and the handleability was good.
  • the resin of the base material layer is 50 wt% of propylene-1-butene copolymer (manufactured by Sumitomo Chemical: SPX78J1, tensile elastic modulus: 530 MPa) and 50 wt% of homopolypropylene polymer (manufactured by Sumitomo Chemical: FLX80E4, tensile elastic modulus: 1500 MPa).
  • a film was produced in the same manner as in Example 1 except that the content was%. This film also has a smooth adhesive layer, has adhesiveness at room temperature, has no contact unevenness between the adherend and the adhesive layer, has a small increase in adhesive force after sticking to the adherend, and has an appearance. It was excellent in handling property with no blocking between the release layer and the adhesive layer.
  • Example 3 The base layer and the release layer were produced as in Example 1.
  • the adhesive layer and the film were prepared as follows. This film also has a smooth adhesive layer, has adhesiveness at room temperature, has no contact unevenness between the adherend and the adhesive layer, has a small increase in adhesive force after sticking to the adherend, and has an appearance. It was excellent in handling property with no blocking between the release layer and the adhesive layer.
  • Amorphous PP (Sumitomo Chemical: Tough selenium H3522A, crystal melting heat and crystallization heat is 28 J / g) and homopolypropylene resin (Sumitomo Chemical: FLX80E4, tensile elastic modulus: 1500 MPa) at a ratio of 50/50 wt%.
  • the mixture was melt extruded with a 45 mm ⁇ twin screw extruder (L / D: 19) to form an adhesive layer.
  • Example 1 A film was produced in the same manner as in Example 1 except that 100 wt% of an olefin elastomer (Mitsubishi Chemical Co., Ltd .: Zelas MC707) was used. As a result of evaluating the characteristics of this film, a smooth adhesive layer is formed, it has adhesiveness at room temperature, there is no uneven contact between the adherend and the adhesive layer, it has excellent appearance, and blocking between the release layer and the adhesive layer However, the increase in the adhesive strength after sticking to the adherend was large.
  • an olefin elastomer Mitsubishi Chemical Co., Ltd .: Zelas MC707
  • the adhesive layer was formulated with amorphous PP (Sumitomo Chemical: Tough selenium H3522A, crystal melting heat and crystallization heat 28 J / g) and homopolypropylene resin (Sumitomo Chemical: FLX80E4, tensile elastic modulus: 1500 MPa).
  • a film was prepared in the same manner as in Example 3 except that the mixture was mixed at a ratio of 80/20 wt% and the corona treatment was not performed.
  • the adhesive layer is formulated with 95 wt% olefin elastomer (Mitsubishi Chemical: Zelas MC707) and 5 wt% heat stabilizer masterbatch (MB) containing Irganox 1076 50000 ppm, so that the adhesive surface has a surface tension of 45 mN / m.
  • a film was produced in the same manner as in Example 1 except that was subjected to corona treatment. As a result of evaluating the properties of this film, a smooth adhesive layer was formed and had adhesiveness at room temperature. However, the adhesive strength was greatly reduced with time.
  • Example 4 The base material layer and the adhesive layer were the same as in Example 1, except that the release layer and each layer configuration were changed to the following contents, and three types and three layers of unstretched film were obtained by the same production method as Example 1.
  • the adhesiveness at room temperature is slightly lowered, the roughness of the adhesive layer surface is high, contact unevenness between the adherend and the adhesive layer is seen, and the contact area between the adherend and the adhesive surface There were few things. Moreover, it foamed at the time of the high temperature process after sticking, and the deterioration of the external appearance was seen after the heating. There was no blocking between the release layer and the adhesive layer, and the handleability was good.
  • Example 5 The base material layer and the adhesive layer are the same as in Example 1, the release layer is changed to the following contents, a film is prepared by the same production method as in Example 1, the base material layer thickness is 35 ⁇ m, and the adhesive layer thickness is 10 ⁇ m. A three-layer three-layer unstretched film having a release layer thickness of 5 ⁇ m was obtained. (Release layer) 100 wt% of a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4) was melt-extruded with a 65 mm ⁇ single screw extruder (L / D: 25) to form a release layer.
  • a homopolypropylene resin manufactured by Sumitomo Chemical Co., Ltd .: FLX80E4
  • the pressure-sensitive adhesive film of the present invention has little blocking between pressure-sensitive adhesive films, and particularly has little blocking even after the pressure-sensitive adhesive film is stored in a roll state, has excellent processability, and is foamed even when treated at a high temperature after being bonded to an adherend. It can be used in a wide range of application fields such as synthetic resin plates, decorative plywood, metal plates and coated steel plates, as well as in automobile baking coatings and printed circuit boards. It is important to contribute.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2010/063271 2009-08-24 2010-08-05 粘着フィルム WO2011024622A2 (ja)

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CN103889715B (zh) * 2011-10-31 2015-09-02 东洋纺株式会社 聚烯烃系膜
WO2013065578A1 (ja) * 2011-10-31 2013-05-10 東洋紡株式会社 ポリオレフィン系フィルム
KR101355020B1 (ko) * 2012-02-10 2014-01-27 에스케이씨하스디스플레이필름(유) 박막 디스플레이 기판 유리 비산 방지 보호필름
JP5821159B2 (ja) * 2013-03-28 2015-11-24 エルジー・ケム・リミテッド 樹脂組成物及びこれを含む逆波長分散性を有する光学フィルム
WO2015118137A1 (de) * 2014-02-10 2015-08-13 Tesa Se Klebeband
US10556409B2 (en) * 2015-03-26 2020-02-11 Toyobo Co., Ltd. Polyethylene film
KR102494761B1 (ko) * 2017-12-20 2023-02-02 주식회사 케이씨씨글라스 다층 시트 및 이의 제조방법
CN118159421A (zh) * 2021-12-09 2024-06-07 东丽薄膜先端加工股份有限公司 表面保护膜

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JP5600905B2 (ja) 2014-10-08
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