TW201418403A - Self-adhesive surface protection film - Google Patents

Self-adhesive surface protection film Download PDF

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TW201418403A
TW201418403A TW102135943A TW102135943A TW201418403A TW 201418403 A TW201418403 A TW 201418403A TW 102135943 A TW102135943 A TW 102135943A TW 102135943 A TW102135943 A TW 102135943A TW 201418403 A TW201418403 A TW 201418403A
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mass
adhesive
film
resin
layer
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TW102135943A
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TWI600739B (en
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Shigetomo Yamamoto
Hirokazu Ogi
Akira Matsuda
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Toyo Boseki
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions 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
    • C08L53/02Compositions 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
    • C08L53/025Compositions 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives 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
    • C09J123/04Homopolymers or copolymers of ethene
    • C09J123/08Copolymers of ethene
    • C09J123/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00Adhesives 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
    • C09J153/02Vinyl aromatic monomers and conjugated dienes
    • C09J153/025Vinyl aromatic monomers and conjugated dienes modified
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22Plastics; Metallised plastics
    • C09J7/24Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241Polyolefin, e.g.rubber
    • C09J7/243Ethylene or propylene polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00Adhesive articles, e.g. adhesive tapes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312Additional 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/04Presence of homo or copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/10Presence of homo or copolymers of propene
    • C09J2423/106Presence of homo or copolymers of propene in the substrate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00Presence of block copolymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Provided is a self-adhesive surface protection film which exhibits strong adhesion to a body to be covered, with which the adhesive film is stored in a rolled state while being usable with various bodies to be covered, which is not susceptible to problems such as the film partially stretching or deforming when being drawn out from the rolled state, and which has excellent film workability. The self-adhesive surface protection film is characterized by: being formed by using co-extrusion to layer an adhesive layer on one surface of a substrate layer and a release layer on the opposite surface thereof, said substrate layer comprising a polypropylene resin; the maximum adhesion to an acrylic sheet being at least 800cN/25mm; and exhibiting a ratio from 0.003 to 0.18 when the maximum adhesion to the acrylic sheet is taken as the denominator and the peel strength of the release layer and the adhesive layer is taken as the numerator.

Description

自黏性表面保護薄膜 Self-adhesive surface protection film

本發明關於自黏性表面保護薄膜(黏著薄膜)。本發明之黏著薄膜可適用於為了保護光學用途所用之稜鏡片等的構件、合成樹脂板(例如建築材料用)、不銹鋼板(例如建築材料用)、鋁板、裝飾合板、鋼板、玻璃板、家電製品、精密機械及製造時之汽車車身的表面;為了保護物品防止在堆疊、保管、輸送或製程中搬送時受到損傷;以及保護物品防止在二次加工(例如彎曲加工或加壓加工)時受到損傷之情況。 The present invention relates to a self-adhesive surface protective film (adhesive film). The adhesive film of the present invention can be applied to members such as ruthenium sheets used for protecting optical applications, synthetic resin sheets (for example, for building materials), stainless steel sheets (for building materials), aluminum sheets, decorative plywood, steel sheets, glass sheets, and home appliances. Products, precision machinery, and the surface of automobile bodies at the time of manufacture; to protect articles from damage during transport during stacking, storage, transport, or manufacturing; and to protect articles from secondary processing (such as bending or pressurization) The situation of injury.

向來,以被覆體的表面保護作為目的之黏著薄膜,係被使用在建築材料或電氣、電子製品、汽車等之加工、保管、輸送時,如此的黏著薄膜在具有良好的黏著性之同時,必須在使用後各表面不被黏著劑所污染而可容易地撕下。 In the past, the adhesive film for the surface protection of the covering has been used for processing, storage, and transportation of building materials, electrical, electronic products, automobiles, etc., and such an adhesive film has good adhesion and must be After use, the surfaces are not contaminated by the adhesive and can be easily peeled off.

近年來,上述的被覆體係多樣化地進展,不僅是被覆面為平滑者,亦可見到多數具有表面凹凸者。作為具有表面凹凸的被覆體,例如可舉出用於光學構件的稜鏡片之稜鏡型透鏡部等。對於如稜鏡片之具有表面凹凸的被覆體,為了使其展現在使用上為充分的黏著力,係考慮提高黏著層的黏著力,使即便是接觸面積小也可得到黏著力。 In recent years, the above-mentioned coating system has been diversified, and not only the coating surface is smooth, but also many surface irregularities are seen. Examples of the covering having the surface unevenness include a 透镜-type lens portion for a cymbal of an optical member. In the case of a coated body having a surface unevenness such as a ruthenium, in order to exhibit sufficient adhesion in use, it is considered to improve the adhesion of the adhesive layer, so that an adhesive force can be obtained even if the contact area is small.

要提高黏著層的黏著力,作為樹脂,若使用顯示高黏著力的苯乙烯系彈性體等為主成分,則有此可能,但若提高黏著層的黏著力,則在以捲筒狀態保管薄膜,然後捲出薄膜時,會發生黏連,而發生薄膜部分地伸長或變形等問題。 In order to improve the adhesion of the adhesive layer, it is possible to use a styrene-based elastomer exhibiting high adhesion as a main component of the resin. However, if the adhesive force of the adhesive layer is increased, the film is stored in a roll state. When the film is rolled out, adhesion occurs, and problems such as partial elongation or deformation of the film occur.

以往,係藉由在基材薄膜上塗佈黏著層及脫模層,而得到黏著力與從捲筒狀態之薄膜的捲出性優異之黏著薄膜。然而,此等薄膜係承擔著使用有掛慮環境負荷的溶劑或生產步驟繁雜之問題,而近年來積極地開發藉由熔融擠出薄膜全層而製作的黏著薄膜。 Conventionally, by applying an adhesive layer and a release layer to a base film, an adhesive film having excellent adhesion and film-out property from a film in a roll state is obtained. However, these films are responsible for the problem of using a solvent having an environmental load and a complicated production process, and in recent years, an adhesive film produced by melt-extruding a full layer of a film has been actively developed.

藉由熔融擠出薄膜全層來進行黏著薄膜之製作時,作為上述之對策,進行在基材層中添加氟系樹脂、聚矽氧系樹脂(例如參照專利文獻1、2等)或飽和脂肪酸雙醯胺(例如參照專利文獻3等)等之檢討,但皆在以捲筒狀態保管時,此等樹脂有轉移到黏著層之可能性,無法消除使黏著力降低或污染被覆體等之掛慮。 When the adhesive film is produced by melt-extruding the entire film, it is possible to add a fluorine-based resin or a polyfluorene-based resin to the base material layer (see, for example, Patent Documents 1, 2, etc.) or a saturated fatty acid. In the case of reviewing the diterpene amine (for example, refer to Patent Document 3, etc.), when the resin is stored in a roll state, the resin may be transferred to the adhesive layer, and the adhesion may be reduced or the coating may be contaminated. .

又,亦檢討在黏著層中添加聚乙烯系樹脂(例如參照專利文獻4、5等),但皆無法同時滿足對稜鏡的黏著力,與以捲筒狀態保管薄膜,然後捲出薄膜時的上述問題。 In addition, it is also considered to add a polyethylene-based resin to the adhesive layer (for example, refer to Patent Documents 4 and 5), but it is not possible to simultaneously satisfy the adhesion to the crucible, and to store the film in a roll state and then roll out the film. The above question.

先前技術文獻 Prior technical literature 專利文獻 Patent literature

專利文獻1 特開2008-81589號公報 Patent Document 1 JP-A-2008-81589

專利文獻2 特開2008-308559號公報 Patent Document 2, JP-A-2008-308559

專利文獻3 特許第4565058號公報 Patent Document 3, Patent No. 4565058

專利文獻4 特開平08-73822號公報 Patent Document 4 Japanese Patent Publication No. 08-73822

專利文獻5 特開2007-161882號公報 Patent Document 5, JP-A-2007-161882

本發明所欲解決之問題在於提供一種自黏性表面保護薄膜,其一方面顯示對於被覆體之強的黏著力,而可使用於各式各樣的被覆體,又在即使是以捲筒狀態保管黏著薄膜,然後捲出薄膜時,也不易發生薄膜部分地伸長或變形等之問題,且薄膜的加工適合性優異。 The problem to be solved by the present invention is to provide a self-adhesive surface protective film which, on the one hand, exhibits strong adhesion to a covering body, and can be used for a wide variety of coverings, even in a reel state. When the adhesive film is stored and the film is unwound, problems such as partial elongation or deformation of the film are less likely to occur, and the film has excellent processing suitability.

本發明者們專心致力地檢討,結果發現可解決上述問題,而達成本發明。 The present inventors focused on the review and found that the above problems can be solved, and the present invention has been achieved.

即,本發明係關於一種自黏性表面保護薄膜,其特徵為:藉由共擠出而在由聚丙烯系樹脂所構成的基材層之一面上積層黏著層,在相反面上積層脫模層而成,對於壓克力板的最大黏著力為800cN/25mm以上,將對於壓克力板的最大黏著力取作分母,將脫模層與黏著層的剝離力取作分子時之比為0.003至0.18。 That is, the present invention relates to a self-adhesive surface protective film characterized in that an adhesive layer is laminated on one surface of a base material layer composed of a polypropylene-based resin by co-extrusion, and a release layer is laminated on the opposite surface. Layered, the maximum adhesion to the acrylic sheet is 800cN/25mm or more, the maximum adhesion to the acrylic sheet is taken as the denominator, and the ratio of the release force of the release layer to the adhesive layer is taken as the molecular ratio. 0.003 to 0.18.

依照本發明,可得到一種自黏性表面保護薄膜,其一方面對於被覆體顯示強的黏著力,而可使用於各式各樣的被覆體,又在即使是以捲筒狀態保管黏著薄膜,然後捲出薄膜時,也不易發生薄膜部分地伸長或變形等之問題,且薄膜的加工適合性優異。 According to the present invention, it is possible to obtain a self-adhesive surface protective film which, on the one hand, exhibits a strong adhesive force to a covering body, and can be used for a wide variety of covering bodies, and even if the adhesive film is stored in a roll state, When the film is rolled out, problems such as partial elongation or deformation of the film are less likely to occur, and the film has excellent processing suitability.

於此情況下,係以構成黏著層的樹脂係至少含有苯乙烯系彈性體與聚乙烯系樹脂,黏著層中的苯乙烯系彈性體之含量為35質量%以上99質量%以下,聚乙烯系樹脂之含量為1質量%以上65質量%以下,苯乙烯系彈性體中的乙烯成分與聚乙烯系樹脂之和為黏著層成分中35質量%以上且小於70質量%為宜。 In this case, the resin constituting the adhesive layer contains at least a styrene-based elastomer and a polyethylene-based resin, and the content of the styrene-based elastomer in the adhesive layer is 35 mass% or more and 99 mass% or less. The content of the resin is preferably 1% by mass or more and 65% by mass or less, and the sum of the ethylene component and the polyethylene resin in the styrene-based elastomer is preferably 35 mass% or more and less than 70 mass% in the adhesive layer component.

又,於此情況下,前述黏著層中的聚乙烯系樹脂之MFR(melt flow rate;熔體流動速率)(190℃、2.16kgf)宜為0.5~8g/10分鐘。 Moreover, in this case, the MFR (melt flow rate) (190 ° C, 2.16 kgf) of the polyethylene resin in the adhesive layer is preferably 0.5 to 8 g/10 min.

再者,於此情況下,前述黏著層中的苯乙烯系彈性體之MFR(230℃、2.16kgf)宜為0.5~8g/10分鐘。 Further, in this case, the MFR (230 ° C, 2.16 kgf) of the styrene-based elastomer in the adhesive layer is preferably 0.5 to 8 g/10 min.

另外,於此情況下,前述基材層中的聚丙烯系樹脂之MFR(230℃、2.16kgf)宜為1.0~15g/10分鐘。 Further, in this case, the MFR (230 ° C, 2.16 kgf) of the polypropylene resin in the base material layer is preferably 1.0 to 15 g/10 min.

還有,於此情況下,使用於脫模層的樹脂以非聚矽氧系樹脂為宜。 Further, in this case, the resin used for the release layer is preferably a non-polyoxyl resin.

依據本發明之黏著薄膜,係具有以下的優點:一方面對於被覆體顯示強的黏著力,而可使用於各式各樣的被覆體,又在即使是以捲筒狀態保管黏著薄膜,然後捲出薄膜時,也不易發生薄膜部分地伸長或變形等之問題,且薄膜的加工適合性優異。 The adhesive film according to the present invention has the following advantages: on the one hand, it exhibits a strong adhesive force to the covering body, and can be used for a wide variety of covering bodies, and the adhesive film is stored even in a roll state, and then rolled. When the film is formed, problems such as partial elongation or deformation of the film are less likely to occur, and the film has excellent processing suitability.

第1圖係顯黏著力的測定試料之模型圖。 Fig. 1 is a model diagram of a sample for measuring adhesion.

[實施發明的形態] [Formation of the Invention]

本發明係自黏性表面保護薄膜(黏著薄膜),其特徵為:藉由共擠出而在由聚丙烯系樹脂所構成的基材層之一面上積層黏著層,在相反面上積層脫模層而成,對於壓克力板的最大黏著力為800cN/25mm以上,將對於壓克力板的最大黏著力取作分母,將脫模層與黏著層的剝離力取作分子時之比為0.003至0.18。 The present invention is a self-adhesive surface protective film (adhesive film) characterized in that an adhesive layer is laminated on one surface of a substrate layer composed of a polypropylene resin by co-extrusion, and a release layer is laminated on the opposite surface. Layered, the maximum adhesion to the acrylic sheet is 800cN/25mm or more, the maximum adhesion to the acrylic sheet is taken as the denominator, and the ratio of the release force of the release layer to the adhesive layer is taken as the molecular ratio. 0.003 to 0.18.

以下,說明本發明之黏著薄膜的實施形態。 Hereinafter, an embodiment of the adhesive film of the present invention will be described.

若考慮要使用於各式各樣的被覆體,則本發明之黏著薄膜的黏著力係較佳在23℃下,對於壓克力板為800~1200cN/25mm之範圍。用於此評價的壓克力板係使用含有甲基丙烯酸系樹脂88質量%以上者。若黏著力小於800cN/25mm,則依照被覆體而會有在保護時發生捲曲等,無法肩負作為保護薄膜的機能的情形。另一方面,黏著力若超過1200cN/25mm,則在從被覆體剝離薄膜時會有無法順利剝離之虞。 The adhesion of the adhesive film of the present invention is preferably at 23 ° C, and is in the range of 800 to 1200 cN / 25 mm for the acrylic sheet, if it is considered to be used for a wide variety of coatings. The acryl plate used for this evaluation used 88% by mass or more of a methacrylic resin. When the adhesive force is less than 800 cN/25 mm, depending on the covering, curling or the like may occur during protection, and the function as a protective film may not be carried. On the other hand, when the adhesive force exceeds 1200 cN/25 mm, the film may not be smoothly peeled off when the film is peeled off from the covering.

又,若考慮到使用,則於23℃下對於稜鏡片的黏著力較佳為2~20cN/25mm之範圍。若黏著力小於2cN/25mm,則在保護時發生捲曲等,無法肩負作為保護薄膜的機能。另一方面,若黏著力超過20cN/25mm,則在剝離薄膜時有無法順利剝離之虞。黏著力係可藉由變更黏著層的樹脂組成或厚度等而適當地設定黏著力。 Further, in consideration of use, the adhesion to the enamel sheet at 23 ° C is preferably in the range of 2 to 20 cN / 25 mm. If the adhesion is less than 2 cN/25 mm, curling or the like occurs during protection, and the function as a protective film cannot be carried. On the other hand, if the adhesive force exceeds 20 cN/25 mm, there is a possibility that the film cannot be peeled off smoothly when the film is peeled off. The adhesive force can appropriately set the adhesive force by changing the resin composition or thickness of the adhesive layer.

從兼具薄膜之黏著力與成為捲筒形態時之薄膜的捲出性之觀點,將本發明之黏著薄膜對於壓克 力板的最大黏著力取作分母,脫模層與黏著層的剝離力取作分子時之比為0.003至0.18之範圍較佳。若該比大於0.18,則薄膜對於壓克力板的黏著力係與脫模層與黏著層的剝離力成為近似值,會發生由於黏著力不充分,因被覆體而不顯示黏著力,或是剝離力高而在作為捲筒形態時,薄膜的捲出性變差等之問題。該比之下限,以實際之值約為0.003。再者,由於在後述的實施例中,黏著力係以寬度25mm來測定,剝離力係以寬度40mm來測定,故上述之比係取使黏著力為1.6倍(40÷25)之值作為分母而計算之值。 The adhesive film of the present invention is pressed against the viewpoint of the adhesion of the film and the roll-out property of the film when it is in the form of a roll. The maximum adhesion of the force plate is taken as the denominator, and the ratio of the release force of the release layer to the adhesive layer as a molecule is preferably in the range of 0.003 to 0.18. If the ratio is more than 0.18, the adhesion force of the film to the acrylic sheet and the peeling force of the release layer and the adhesive layer become approximate values, and the adhesive force may be insufficient, and the adhesive body may not exhibit adhesive force or peel off. When the force is high, when the film is in the form of a roll, the roll-out property of the film is deteriorated. The lower limit of the ratio is about 0.003 in actual value. Further, in the examples described later, the adhesive force was measured by a width of 25 mm, and the peeling force was measured by a width of 40 mm. Therefore, the above ratio was taken as a denominator with a value of 1.6 times (40 ÷ 25). And calculate the value.

(基材層) (base material layer)

本發明之黏著薄膜需要以聚丙烯系樹脂為主成分之基材層,作為此處所用之聚丙烯系樹脂,可舉出結晶性聚丙烯、丙烯與少量的α-烯烴之無規共聚物或嵌段共聚物等,更詳細地,作為結晶性聚丙烯樹脂,可舉出在通常的擠壓成形等所使用之正庚烷不溶性的同排丙烯均聚物或含有丙烯為60重量%以上之丙烯與其它α-烯烴的共聚物,可單獨或混合而使用此丙烯均聚物或是丙烯與其它α-烯烴的共聚物。 The adhesive film of the present invention requires a base material layer containing a polypropylene resin as a main component, and examples of the polypropylene resin used herein include crystalline polypropylene, a random copolymer of propylene and a small amount of α-olefin, or In particular, as the crystalline polypropylene resin, a n-heptane-insoluble homopolymer propylene homopolymer or propylene containing 60% by weight or more, which is used for ordinary extrusion molding, etc., may be mentioned. The copolymer of propylene and other α-olefins may be used singly or as a mixture of propylene homopolymer or propylene and other α-olefins.

於基材層中較佳含有60質量%以上的丙烯單位,更佳含有70質量%以上的丙烯單位。若丙烯單位小於60質量%,則薄膜變成沒有硬挺感,操作會變得困難。又,若使丙烯單位量小於60質量%而使用聚乙烯系樹脂,則薄膜變柔軟且容易伸展,而在捲出薄膜時,亦容易發生薄膜部分地伸長或變形等之問題。 The base material layer preferably contains 60% by mass or more of propylene units, more preferably 70% by mass or more of propylene units. When the propylene unit is less than 60% by mass, the film does not have a feeling of stiffness, and handling becomes difficult. In addition, when a polyethylene resin is used in a unit amount of propylene of less than 60% by mass, the film becomes soft and easily stretched, and when the film is wound up, problems such as partial elongation or deformation of the film are likely to occur.

於此,所謂的正庚烷不溶性,就是以聚丙烯的結晶性作為指標而同時表示安全性者,於本發明中,係以使用依據日本昭和57年2月厚生省告示第20號,符合正庚烷不溶性(在25℃萃取60分鐘時的溶出分為150ppm以下[使用溫度超過100℃者為30ppm以下])者為較佳的態樣。 In this case, the intrinsic n-heptane insolubleness is a safety in which the crystallinity of the polypropylene is used as an index. In the present invention, it is used in accordance with the No. 20 of the Ministry of Health and Welfare of the Republic of Japan in February, 57, in accordance with the The alkane insoluble property (the elution at 25 ° C for 60 minutes is 150 ppm or less (the use temperature is more than 100 ° C is 30 ppm or less) is preferred.

作為丙烯與其它α-烯烴的共聚物的α-烯烴共聚合成分,可舉出碳數為2~8的α-烯烴,例如乙烯或是1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯等之C4以上的α-烯烴。此處所謂的共聚物,較佳為使丙烯與上述所例示的α-烯烴之1種或2種以上聚合而得之無規或嵌段共聚物。所使用的聚丙烯系樹脂之熔體流動速率(MFR:230℃、2.16kgf)較佳為1.0~15g/10分鐘之範圍,更佳為2.0~10.0g/10分鐘之範圍。又,亦可將丙烯與其它α-烯烴的共聚物混合2種以上來使用。 Examples of the α-olefin copolymerization component of the copolymer of propylene and another α-olefin include an α-olefin having 2 to 8 carbon atoms, such as ethylene or 1-butene, 1-pentene, and 1-hexene. And an α-olefin of C4 or higher such as 4-methyl-1-pentene. The copolymer to be used herein is preferably a random or block copolymer obtained by polymerizing one or two or more kinds of propylene and the above-exemplified α-olefin. The melt flow rate (MFR: 230 ° C, 2.16 kgf) of the polypropylene resin to be used is preferably in the range of 1.0 to 15 g/10 min, more preferably in the range of 2.0 to 10.0 g/10 min. Further, two or more kinds of copolymers of propylene and another α-olefin may be used in combination.

再者,亦可在將本發明中所得之薄膜進行製品加工時,將產生的廢薄膜作為回收原料來再造粒,添加於基材層中。藉由使用回收原料可抑制生產成本。 Further, when the film obtained in the present invention is subjected to product processing, the resulting waste film may be regranulated as a raw material for recovery and added to the substrate layer. Production costs can be suppressed by using recycled raw materials.

(黏著層) (adhesive layer)

作為構成本發明的黏著層之樹脂,為了展現高的黏著力,宜使用苯乙烯系彈性體。又,為了展現黏著力與從捲筒狀態之薄膜的捲出性,宜添加聚乙烯系樹脂。再者,藉由添加聚乙烯系樹脂,可降低從黏著面側對於脫模面之剝離力。又,為了黏著力之控制,亦可視需要混合聚乙烯系樹脂以外之聚烯烴樹脂、增黏樹脂、軟化劑、聚苯乙烯等。 As the resin constituting the adhesive layer of the present invention, in order to exhibit high adhesion, a styrene-based elastomer is preferably used. Moreover, in order to exhibit the adhesive force and the roll-out property of the film from the roll state, it is preferable to add a polyethylene resin. Further, by adding a polyethylene-based resin, the peeling force against the release surface from the adhesive surface side can be reduced. Further, in order to control the adhesion, a polyolefin resin other than a polyethylene resin, a tackifier resin, a softener, polystyrene, or the like may be mixed as needed.

苯乙烯系彈性體係可列舉苯乙烯-丁二烯-苯乙烯等之A-B-A型嵌段聚合物、苯乙烯-丁二烯共聚物等之A-B型嵌段聚合物、苯乙烯系聚合物嵌段與苯乙烯和丁二烯之無規共聚物嵌段的嵌段共聚物等之氫化物、苯乙烯-丁二烯橡膠等的苯乙烯系無規共聚物之氫化物。 Examples of the styrene-based elastomer system include an ABA type block polymer such as styrene-butadiene-styrene, an AB type block polymer such as a styrene-butadiene copolymer, and a styrene polymer block. A hydrogenated product such as a block copolymer of a random copolymer block of styrene and butadiene, or a hydride of a styrene-based random copolymer such as styrene-butadiene rubber.

聚乙烯系樹脂係可列舉低密度聚乙烯、乙烯與α-烯烴的共聚物等。此等之中,在一邊保持黏著力,一邊降低從捲筒狀態的薄膜之剝離力,提高薄膜的捲出性之方面,又以低密度聚乙烯,特別是被稱為LLDPE的直鏈狀低密度聚乙烯或被稱為VLDPE的超低密度聚乙烯更佳。此等係藉由使α-烯烴共聚合而在乙烯鏈中導入短鏈分支者,根據α-烯烴的種類或共聚合量,可對聚乙烯系樹脂賦予柔軟性。作為α-烯烴,並沒有特別的限定,但可舉出1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-辛烯等。 Examples of the polyethylene resin include low density polyethylene, a copolymer of ethylene and an α-olefin, and the like. Among these, while maintaining the adhesive force while reducing the peeling force of the film from the roll state and improving the roll-out property of the film, low-density polyethylene, in particular, a linear low called LLDPE is used. Density polyethylene or ultra low density polyethylene called VLDPE is preferred. These are short-chain branches introduced into the ethylene chain by copolymerization of an α-olefin, and flexibility can be imparted to the polyethylene-based resin depending on the type or copolymerization amount of the α-olefin. The α-olefin is not particularly limited, and examples thereof include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene.

為了展現高的黏著力與展現從捲筒狀態之薄膜的捲出性,黏著層中的苯乙烯系彈性體量宜為35質量%以上99質量%以下。若小於35質量%,則黏著力降低,而難以得到所必要的黏著力。黏著層中的苯乙烯系彈性體量較佳為40質量%以上90質量%以下之範圍。 The amount of the styrene-based elastomer in the adhesive layer is preferably from 35% by mass to 99% by mass in order to exhibit high adhesion and exhibiting the roll-out property of the film from the roll state. If it is less than 35% by mass, the adhesive force is lowered, and it is difficult to obtain the necessary adhesive force. The amount of the styrene-based elastomer in the adhesive layer is preferably in the range of 40% by mass or more and 90% by mass or less.

為了展現高的黏著力與降低從捲筒狀態之薄膜的剝離力,展現捲出性,黏著層中的聚乙烯系樹脂量宜為1質量%以上65質量%以下。若黏著層中的聚乙烯系樹脂量超過65質量%,則黏著力降低,而難以得到所必要的黏著力。黏著層中的聚乙烯系樹脂量較佳為3質量%以上60質量%以下之範圍。 In order to exhibit high adhesion and reduce the peeling force of the film from the roll state, the roll-out property is exhibited, and the amount of the polyethylene-based resin in the adhesive layer is preferably 1% by mass or more and 65% by mass or less. When the amount of the polyethylene-based resin in the adhesive layer exceeds 65% by mass, the adhesive force is lowered, and it is difficult to obtain the necessary adhesive force. The amount of the polyethylene-based resin in the adhesive layer is preferably in the range of 3% by mass to 60% by mass.

苯乙烯系彈性體中的乙烯成分與聚乙烯系樹脂之和為黏著層成分中35質量%以上且小於70質量%之範圍。乙烯成分與聚乙烯系樹脂之和為黏著層成分中70質量%以上時,黏著力降低,得不到充分的黏著力。若乙烯成分與聚乙烯系樹脂之和小於黏著層成分中35質量%,則薄膜黏著層相對於脫模層的剝離力會變高。較佳為乙烯成分與聚乙烯系樹脂之和為黏著層成分中40質量%以上65質量%以下。更佳為乙烯成分與聚乙烯系樹脂之和為黏著層成分中45質量%以上63質量%以下。 The sum of the ethylene component and the polyethylene resin in the styrene elastomer is in the range of 35 mass% or more and less than 70 mass% in the adhesive layer component. When the sum of the ethylene component and the polyethylene resin is 70% by mass or more of the adhesive layer component, the adhesive strength is lowered, and sufficient adhesive force cannot be obtained. When the sum of the ethylene component and the polyethylene resin is less than 35% by mass in the adhesive layer component, the peeling force of the film adhesive layer with respect to the release layer becomes high. The sum of the ethylene component and the polyethylene resin is preferably 40% by mass or more and 65% by mass or less in the adhesive layer component. More preferably, the sum of the ethylene component and the polyethylene resin is 45 mass% or more and 63 mass% or less in the adhesive layer component.

於製膜性方面,所使用的苯乙烯系彈性體之熔體流動速率(MFR:230℃、2.16kgf)較佳為0.5~8g/10分鐘之範圍,更佳為2.0~7.0g/10分鐘之範圍。 In terms of film formability, the melt flow rate (MFR: 230 ° C, 2.16 kgf) of the styrene-based elastomer to be used is preferably in the range of 0.5 to 8 g/10 min, more preferably 2.0 to 7.0 g/10 min. The scope.

所使用的聚乙烯系樹脂之熔體流動速率(MFR:190℃、2.16kgf)較佳為0.5~8g/10分鐘之範圍,更佳為0.8~7.0g/10分鐘之範圍。藉由成為上述範圍,各層厚度均勻之製膜變得容易進行。 The melt flow rate (MFR: 190 ° C, 2.16 kgf) of the polyethylene-based resin to be used is preferably in the range of 0.5 to 8 g/10 min, more preferably in the range of 0.8 to 7.0 g/10 min. By setting it as the above range, film formation in which the thickness of each layer is uniform becomes easy.

苯乙烯系彈性體中的苯乙烯成分,宜為5質量%以上40質量%以下。若小於5質量%,則樹脂(顆粒)製作時之造粒變得困難,若超過40質量%,則黏著力降低,難以得到所必要的黏著力。苯乙烯系彈性體中的苯乙烯成分更佳為10質量%以上30質量%以下之範圍。另一方面,苯乙烯系彈性體中的乙烯成分,係由於在添加聚乙烯系樹脂時容易與聚乙烯系樹脂混合,而被認為若在苯乙烯系彈性體中之含量多,則從捲筒狀態之薄膜 的捲出性改善效果容易變大。因此,苯乙烯系彈性體中的乙烯成分宜為15質量%以上70質量%以下。又,由於認為苯乙烯系彈性體中的乙烯成分係大幅幫助黏著力的展現,而若超過70質量%,則在下述條件下添加聚乙烯系樹脂時,有黏著力變難以降低之傾向。 The styrene component in the styrene-based elastomer is preferably 5% by mass or more and 40% by mass or less. When it is less than 5% by mass, granulation during production of the resin (particles) becomes difficult, and if it exceeds 40% by mass, the adhesive force is lowered, and it is difficult to obtain the necessary adhesive force. The styrene component in the styrene-based elastomer is more preferably in the range of 10% by mass to 30% by mass. On the other hand, the ethylene component in the styrene-based elastomer is easily mixed with the polyethylene-based resin when the polyethylene-based resin is added, and it is considered that if the content in the styrene-based elastomer is large, the reel is obtained from the reel. State film The effect of improving the roll-out property tends to become large. Therefore, the ethylene component in the styrene elastomer is preferably 15% by mass or more and 70% by mass or less. In addition, it is considered that the ethylene component in the styrene-based elastomer greatly contributes to the adhesion. When the amount is more than 70% by mass, when the polyethylene-based resin is added under the following conditions, the adhesive strength tends to be lowered.

又,聚乙烯系樹脂中的乙烯成分較佳為70質量%以上。聚乙烯系樹脂的乙烯成分更佳為75質量%以上,尤佳為80質量%以上。又,聚乙烯系樹脂的乙烯成分較佳為98質量%以下,更佳為96質量%以下,尤佳為95質量%以下。聚乙烯系樹脂中的乙烯成分若小於70質量%,則從捲筒狀態之薄膜的捲出性改善效果有變小之傾向。作為聚乙烯系樹脂中的乙烯成分為70質量%以上之樹脂,可舉出住友化學製的CX3007或VL100等。 Further, the ethylene component in the polyethylene resin is preferably 70% by mass or more. The ethylene component of the polyethylene resin is more preferably 75% by mass or more, and particularly preferably 80% by mass or more. Further, the ethylene component of the polyethylene resin is preferably 98% by mass or less, more preferably 96% by mass or less, and still more preferably 95% by mass or less. When the ethylene component in the polyethylene resin is less than 70% by mass, the effect of improving the roll-out property of the film from the roll state tends to be small. The resin which is 70% by mass or more of the ethylene component in the polyethylene resin is CX3007 or VL100 manufactured by Sumitomo Chemical Co., Ltd., and the like.

附帶一提,聚乙烯系樹脂中的乙烯成分以外之成分較佳為小於30質量%,更佳為25質量%以下。 Incidentally, the component other than the ethylene component in the polyethylene resin is preferably less than 30% by mass, and more preferably 25% by mass or less.

聚乙烯系樹脂之密度較佳為850~920kg/m3,更佳為860~910kg/m3,最佳為880~906kg/m3。藉由成為上述範圍,可變得容易兼具良好的黏著性與捲出性。 The density of the polyethylene resin is preferably 850 to 920 kg/m 3 , more preferably 860 to 910 kg/m 3 , most preferably 880 to 906 kg/m 3 . By being in the above range, it is easy to achieve both good adhesion and roll-out properties.

聚乙烯系樹脂之彎曲彈性模數宜為10MPa以上且小於90MPa。若為10MPa以上,則從捲筒狀態之薄膜的捲出性進一步升高,若小於90MPa,則黏著力進一步升高。聚乙烯系樹脂之彎曲彈性模數更佳為15~80MPa之範圍,尤佳為20~70MPa之範圍。 The flexural modulus of the polyethylene resin is preferably 10 MPa or more and less than 90 MPa. When it is 10 MPa or more, the roll-out property of the film from the roll state is further increased, and if it is less than 90 MPa, the adhesive force is further increased. The flexural modulus of the polyethylene resin is more preferably in the range of 15 to 80 MPa, and particularly preferably in the range of 20 to 70 MPa.

聚乙烯系樹脂以外之聚烯烴系樹脂係沒有特別的限定,可舉出結晶性聚丙烯、丙烯與少量的α-烯烴之共聚物等。此等之樹脂由於一般而言僅少量摻合即有黏著力降低之傾向,較佳為以1質量%以上20質量%以下之比例摻合。 The polyolefin resin other than the polyethylene resin is not particularly limited, and examples thereof include a crystalline polypropylene, a copolymer of propylene and a small amount of an α-olefin, and the like. These resins tend to have a low adhesive strength when they are blended in a small amount, and are preferably blended at a ratio of 1% by mass to 20% by mass.

增黏樹脂例如可列舉石油樹脂、脂肪族烴樹脂、脂環族烴樹脂、芳香族烴樹脂、萜烯樹脂、香豆酮-茚樹脂、苯乙烯系樹脂、松香樹脂等。增黏樹脂之分子量係沒有特別的限制,可適宜地設定,但若分子量若變小,則有成為自黏著層往被覆體之物質轉移或重剝離化等的原因之虞,另一方面,若分子量變大,則有黏著力的提升效果不佳之傾向,故增黏樹脂的數量平均分子量較佳為1000~10萬左右。數量平均分子係可藉由凝膠滲透層析術等來測定。 Examples of the tackifier resin include petroleum resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, terpene resins, coumarone-indene resins, styrene resins, and rosin resins. The molecular weight of the tackifier resin is not particularly limited, and may be appropriately set. However, if the molecular weight is small, there is a possibility that the material from the adhesive layer is transferred to the covering or re-peeled, and the like. When the molecular weight is increased, the adhesion improving effect tends to be poor, so the number average molecular weight of the tackifying resin is preferably about 1,000 to 100,000. The number average molecular system can be determined by gel permeation chromatography or the like.

相對於100質量%的黏著層成分,黏著層中的增黏樹脂之摻合量,較佳為3質量%以上20質量%以下之範圍。若增黏樹脂之摻合量超過20質量%,則由於增黏樹脂為分子量低,而熔融黏度極端地變低,於進行使用T模頭等的共擠出製膜時,不僅與以聚丙烯系樹脂為主成分的基材層之積層變困難,而且黏著層變得發黏,而有難以改善從捲筒狀態之薄膜的捲出性的傾向。又,若黏著層中的增黏樹脂之摻合量小於3質量%,則即使摻合也無助於黏著層的黏著力變化。增黏樹脂之摻合量較佳為5質量%以上15質量%以下。 The blending amount of the tackifier resin in the adhesive layer is preferably in the range of 3% by mass to 20% by mass based on 100% by mass of the adhesive layer component. When the blending amount of the tackifying resin exceeds 20% by mass, since the tackifying resin has a low molecular weight and the melt viscosity is extremely low, when performing co-extrusion film formation using a T die or the like, not only polypropylene is used. It is difficult to laminate the base material layer containing the resin as a main component, and the adhesive layer becomes sticky, and it is difficult to improve the roll-out property of the film from the roll state. Further, if the blending amount of the tackifying resin in the adhesive layer is less than 3% by mass, the adhesion of the adhesive layer does not change even if blended. The blending amount of the tackifier resin is preferably 5% by mass or more and 15% by mass or less.

在由於對黏著層中之增黏樹脂的添加,而熔融黏度有降低之傾向時,可藉由添加1質量%~15質量%左右的聚苯乙烯樹脂,來改善基材層與黏著層之間的熔融黏度差,而使易於積層。聚苯乙烯樹脂摻合量較佳為3質量%以上12質量%以下,更佳為5質量%以上10質量%以下。 When the melt viscosity is lowered due to the addition of the tackifying resin in the adhesive layer, the polystyrene resin of about 1% by mass to 15% by mass may be added to improve the relationship between the substrate layer and the adhesive layer. The melt viscosity is poor, making it easy to laminate. The blending amount of the polystyrene resin is preferably 3% by mass or more and 12% by mass or less, more preferably 5% by mass or more and 10% by mass or less.

軟化劑例如可列舉低分子量之二烯系聚合物、聚異丁烯、氫化聚異戊二烯、氫化聚丁二烯或彼等的衍生物、聚丁烯等。軟化劑之分子量係沒有特別的制限,可適宜地設定,但若分子量變小,則有成為由黏著層往被覆體之物質轉移或重剝離化等的原因之虞,另一方面,若分子量變大,則有黏著力的提升效果不佳之傾向,故軟化劑之數量平均分子量較佳為1000~10萬左右。數量平均分子量係可藉由與增黏樹脂之情況同樣的方法來測定。 Examples of the softening agent include a low molecular weight diene polymer, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene or derivatives thereof, polybutene, and the like. The molecular weight of the softening agent is not particularly limited, and can be appropriately set. However, if the molecular weight is small, there is a cause of transfer or re-peeling of the material from the adhesive layer to the covering, and if the molecular weight is changed, Large, there is a tendency to improve the adhesion effect, so the number average molecular weight of the softener is preferably about 1000 to 100,000. The number average molecular weight can be measured by the same method as in the case of the tackifying resin.

又,使用於黏著層的增黏樹脂或軟化劑係按照種類而為液體或粉體,亦有在擠出時會污染擠壓機之物。由於如此的問題可藉由將增黏樹脂或軟化劑,與聚乙烯系樹脂或聚烯烴系樹脂予以母料化而使用來改善,故較佳將增黏樹脂或軟化劑,與聚乙烯系樹脂或聚烯烴系樹脂予以母料化而使用。 Further, the tackifying resin or softener used in the adhesive layer is a liquid or a powder depending on the type, and may also contaminate the extruder during extrusion. Since such a problem can be improved by using a tackifying resin or a softening agent in combination with a polyethylene resin or a polyolefin resin, it is preferred to use a tackifying resin or a softening agent and a polyethylene resin. Or the polyolefin resin is used as a master batch.

本發明之黏著薄膜係可按照需要含有周知的添加劑。例如,可含有滑劑、防黏連劑、熱安定劑、抗氧化劑、抗靜電劑、耐光劑、耐衝擊改良劑等。惟,此等成分係分子量比較低,會有滲出黏著層表面,降低 黏著層的黏著力之情況。因此,當使用添加劑時,較佳使黏著層表面的低分子量物質小於1mg/m2The adhesive film of the present invention may contain a known additive as needed. For example, it may contain a slip agent, an anti-blocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light stabilizer, an impact modifier, and the like. However, these components have a relatively low molecular weight and may bleed out the surface of the adhesive layer and reduce the adhesion of the adhesive layer. Therefore, when an additive is used, it is preferred that the low molecular weight substance on the surface of the adhesive layer is less than 1 mg/m 2 .

此處,黏著層表面的低分子量物質之測定係用以下的程序來實施。使用乙醇等不侵蝕構成黏著層之樹脂的有機溶劑來洗淨黏著層表面,以蒸發器等自該洗淨液中去除有機溶劑後,將秤量其殘渣所求得之數值除以所洗淨之黏著層表面的表面積來求得。於此,若殘渣存在1mg/m2以上,則黏著層表面與被覆體表面之間有異物存在,而成為接觸面積減少、凡得瓦力降低之原因,因此黏著力降低而不佳。當添加添加劑時,必須要選擇高分子型等的添加劑,或檢討添加量及添加方法等,以使其不對黏著層轉移、轉印。 Here, the measurement of the low molecular weight substance on the surface of the adhesive layer was carried out by the following procedure. The surface of the adhesive layer is washed with an organic solvent such as ethanol which does not attack the resin constituting the adhesive layer, and the organic solvent is removed from the washing liquid by an evaporator or the like, and the value obtained by weighing the residue is divided by the washed amount. The surface area of the surface of the adhesive layer is obtained. When the residue is present at 1 mg/m 2 or more, foreign matter is present between the surface of the adhesive layer and the surface of the coated body, and the contact area is reduced, and the vanaural force is lowered. Therefore, the adhesive strength is not preferable. When adding an additive, it is necessary to select an additive such as a polymer type, or to review the amount of addition, the method of addition, and the like so as not to transfer or transfer the adhesive layer.

(脫模層) (release layer)

本發明之黏著薄膜係在與基材層的一面上所積層之黏著層為相反面上,形成由非聚矽氧系樹脂的聚丙烯系樹脂所構成之脫模層,藉由如此而即使是將黏著薄膜彼此重疊,黏著薄膜彼此的黏連也變少。特別地,即使在捲筒狀態保管黏著薄膜,然後捲出薄膜時,也不易發生薄膜部分地伸長或變形等問題,成為薄膜的加工適合性優異者。再者,要使黏著薄膜彼此即使是重疊也不發生黏著薄膜彼此之黏連,在脫模層上形成表面凹凸而減少與黏著層的接觸面積係為有效。 The adhesive film of the present invention is formed on the opposite side of the adhesive layer laminated on one surface of the base material layer, and forms a release layer composed of a polypropylene resin which is not a polyoxymethylene resin, and thus even The adhesive films are overlapped with each other, and the adhesion of the adhesive films to each other is also reduced. In particular, even when the adhesive film is stored in a roll state and then the film is wound up, problems such as partial elongation or deformation of the film are less likely to occur, and the film has excellent processing suitability. Further, the adhesive films are not adhered to each other even if they are overlapped with each other, and it is effective to form surface irregularities on the release layer and to reduce the contact area with the adhesive layer.

要形成如上述之表面凹凸,在聚丙烯系樹脂中混合非相溶的樹脂係為有效。藉由如此,可形成氈狀的表面為粗糙之層。再者,藉由使用丙烯-乙烯嵌段共 聚物作為聚丙烯系樹脂,可不使用非相溶的樹脂而期待同樣之效果。再者,當然亦可在丙烯-乙烯嵌段共聚物中更添加非相溶的樹脂。 It is effective to form a non-coherent resin in a polypropylene-based resin in order to form the surface unevenness as described above. By doing so, a matte surface can be formed as a rough layer. Furthermore, by using a propylene-ethylene block As a polypropylene resin, the polymer can be expected to have the same effect without using an incompatible resin. Further, it is of course also possible to add an incompatible resin to the propylene-ethylene block copolymer.

作為對聚丙烯系樹脂非相溶的樹脂,宜使用低密度聚乙烯、4-甲基戊烯-1系(共)聚合物等之碳數4以上的α-烯烴(共)聚合物。此外,還可舉出直鏈狀低密度聚乙烯、高密度聚乙烯、乙烯與少量的α-烯烴之共聚物、乙烯與醋酸乙烯酯之共聚物、聚苯乙烯、聚酯系樹脂、聚醯胺系樹脂等。特別是4-甲基戊烯-1系(共)聚合物,不僅使表面粗糙為氈狀,且由於薄膜表面的表面自由能降低,而更可期待剝離性之提升。 As the resin which is incompatible with the polypropylene resin, an α-olefin (co)polymer having a carbon number of 4 or more, such as a low-density polyethylene or a 4-methylpentene-1 (co)polymer, is preferably used. Further, a linear low-density polyethylene, a high-density polyethylene, a copolymer of ethylene and a small amount of an α-olefin, a copolymer of ethylene and vinyl acetate, a polystyrene, a polyester resin, and a polyfluorene may be mentioned. An amine resin or the like. In particular, the 4-methylpentene-1 (co)polymer not only roughens the surface to a felt shape, but also improves the peeling property because the surface free energy of the surface of the film is lowered.

從使黏著薄膜成為捲筒形態時的薄膜之捲出性之點來看,本發明之黏著薄膜的黏著面對於脫模面的剝離力,較佳於23℃下為250cN/40mm以下之範圍。若剝離力超過250cN/40mm,則在使黏著薄膜成為捲筒形態之情形的薄膜之捲出時,會發生薄膜部分地伸長或變形等之問題。再者,作為實際數值,黏著薄膜的黏著面對於脫模面的剝離力的下限為1cN/40mm左右,進一步來說為5cN/40mm左右。 The peeling force of the adhesive surface of the adhesive film of the present invention on the release surface is preferably in the range of 250 cN/40 mm or less at 23 ° C from the viewpoint of the film unwinding property when the adhesive film is in the form of a roll. When the peeling force exceeds 250 cN/40 mm, when the film is wound up in the form of a roll, the film may be partially elongated or deformed. Further, as an actual value, the lower limit of the peeling force of the adhesive surface of the adhesive film to the release surface is about 1 cN/40 mm, and further about 5 cN/40 mm.

從兼具薄膜的黏著力與成為捲筒形態時的薄膜之捲出性之點來看,將本發明之黏著薄膜對於壓克力板的最大黏著力取作分母,脫模層與黏著層的剝離力取作分子之時比,較佳為0.003至0.18之範圍。此比若大於0.18,則薄膜對於壓克力板的黏著力,係與脫模層和黏著層的剝離力成為近似值,會有由於黏著力不充 分,因被覆體而會有不顯示黏著力,或是剝離力高,而在製成捲筒形態時,薄膜的捲出性變差等之問題發生。作為實際數值,該比之下限係0.003左右。再者,如前述,上述比係考慮測定時的試料之寬度來計算,較佳為0.01至0.18之範圍,更佳為0.05至0.15之範圍。 The maximum adhesion of the adhesive film of the present invention to the acrylic sheet is taken as the denominator, the release layer and the adhesive layer, from the point of the adhesion of the film and the roll-out property of the film in the form of a roll. The ratio of the peeling force to the molecule is preferably in the range of 0.003 to 0.18. If the ratio is greater than 0.18, the adhesion of the film to the acrylic sheet is similar to the peeling force of the release layer and the adhesive layer, and the adhesive force may not be charged. In the case of the coating, the adhesion is not exhibited, or the peeling force is high, and when the roll form is formed, the problem that the film is unwound is deteriorated. As the actual value, the lower limit of the ratio is about 0.003. Further, as described above, the above ratio is calculated in consideration of the width of the sample at the time of measurement, and is preferably in the range of 0.01 to 0.18, more preferably in the range of 0.05 to 0.15.

如鑒於本發明的黏著層之樹脂組成,則較佳使脫模層表面的三次元平均表面粗糙度SRa0.10μm以上0.50μm以下。藉由如此,可提升防黏連性與被覆體的保護性能。若脫模層的表面粗糙度低於0.10μm,則在將薄膜製成捲筒形態時之薄膜的捲出性會有變差之情況。若脫模層的表面粗糙度高於0.50μm,則會有脫模層的表面凹凸轉印到黏著層的表面,黏著力顯著降低之情況。此時,更佳為使脫模層的表面凹凸成為如表面的平均表面粗糙度SRa為0.25μm以上0.45μm以下之表面。 In view of the resin composition of the adhesive layer of the present invention, the three-dimensional average surface roughness SRa of the surface of the release layer is preferably 0.10 μm or more and 0.50 μm or less. By doing so, the anti-blocking property and the protective property of the covering body can be improved. When the surface roughness of the release layer is less than 0.10 μm, the film unwinding property may be deteriorated when the film is formed into a roll form. When the surface roughness of the release layer is higher than 0.50 μm, the surface unevenness of the release layer is transferred to the surface of the adhesive layer, and the adhesion is remarkably lowered. In this case, it is more preferable that the surface unevenness of the release layer is such that the average surface roughness SRa of the surface is 0.25 μm or more and 0.45 μm or less.

再者,所謂脫模層表面的三次元平均表面粗糙度SRa,係意味以正弦曲線來近似表面粗糙度曲線時之中心面的平均粗糙度,可藉由表面粗糙度測定裝置等進行測定。 In addition, the ternary mean surface roughness SRa of the surface of the mold release layer means the average roughness of the center surface when the surface roughness curve is approximated by a sinusoid, and can be measured by a surface roughness measuring apparatus or the like.

(黏著薄膜) (adhesive film)

本發明的黏著薄膜之黏著層的厚度較佳為1μm以上且小於30μm。若黏著層的厚度小於1μm,則要藉由共擠出來安定製膜變得困難,若為30μm以上,則成為於成本方面不利之薄膜。 The thickness of the adhesive layer of the adhesive film of the present invention is preferably 1 μm or more and less than 30 μm. When the thickness of the adhesive layer is less than 1 μm, it is difficult to customize the film by co-extrusion, and if it is 30 μm or more, it is a film which is disadvantageous in terms of cost.

此時,當要增大黏著力時,較佳為考慮其黏性而增大厚度。藉由增大黏著層的厚度,與被覆體的接觸面積 容易變大。黏著層之厚度較佳為2μm以上20μm以下,更佳為3μm以上15μm以下,特佳為4μm以上10μm以下。 At this time, when the adhesion is to be increased, it is preferable to increase the thickness in consideration of the viscosity. By increasing the thickness of the adhesive layer, the contact area with the covering It is easy to get bigger. The thickness of the adhesive layer is preferably 2 μm or more and 20 μm or less, more preferably 3 μm or more and 15 μm or less, and particularly preferably 4 μm or more and 10 μm or less.

本發明的黏著薄膜之基材層的厚度較佳為5μm以上且小於100μm,更佳為10μm以上且75μm以下,尤佳為15μm以上且55μm以下。若基材層的厚度小於5μm,則會有硬挺感變弱,在作為保護薄膜貼附於被覆體時容易會有皺折等,所謂無法充分得到黏著力之問題,若為100μm以上,則成為於成本方面不利之薄膜。 The thickness of the base material layer of the adhesive film of the present invention is preferably 5 μm or more and less than 100 μm, more preferably 10 μm or more and 75 μm or less, and still more preferably 15 μm or more and 55 μm or less. When the thickness of the base material layer is less than 5 μm, the feeling of stiffness is weak, and when it is attached to the covering as a protective film, wrinkles are likely to occur, and the problem of insufficient adhesion is not obtained, and if it is 100 μm or more, it becomes a problem. A film that is unfavorable in terms of cost.

本發明的黏著薄膜之脫模層的厚度較佳為1μm以上且小於30μm。若黏著薄膜的厚度小於1μm,則要藉由共擠出來安定製膜變得困難,若為30μm以上,則成為於成本方面不利之薄膜。脫模層的厚度更佳為2μm以上20μm以下,尤佳為3μm以上15μm以下。再者,本發明之自黏性表面保護薄膜的厚度較佳為10μm以上150μm以下,更佳為15μm以上120μm以下,尤佳為20μm以上100μm以下。若薄膜的總厚度過薄,則有不易操作之情況,若過厚則有剛性變高而操作性不佳,同時成為於成本方面不利的薄膜之情況。 The thickness of the release layer of the adhesive film of the present invention is preferably 1 μm or more and less than 30 μm. When the thickness of the adhesive film is less than 1 μm, it is difficult to customize the film by co-extrusion, and if it is 30 μm or more, it is a film which is disadvantageous in terms of cost. The thickness of the release layer is more preferably 2 μm or more and 20 μm or less, and particularly preferably 3 μm or more and 15 μm or less. Further, the thickness of the self-adhesive surface protective film of the present invention is preferably 10 μm or more and 150 μm or less, more preferably 15 μm or more and 120 μm or less, and still more preferably 20 μm or more and 100 μm or less. When the total thickness of the film is too thin, it may be difficult to handle, and if it is too thick, the rigidity becomes high and the workability is poor, and at the same time, it is a case of a film which is disadvantageous in terms of cost.

本發明之自黏性表面保護薄膜係由含有上述樹脂成分的基材層、黏著層、脫模層之各層所構成,構成各層的樹脂係藉由使用例如單軸、雙軸的擠壓機等,直接以熔融狀態對供料頭型或多歧管型的T模頭送出,以被3層以上積層擠壓而得。為了使各層成為熔融 狀態,各層的擠壓機之溫度係可適宜地考慮各層所使用之成分的成形溫度,適宜地調節,例如可在200℃~260℃之範圍調節。T模頭的溫度亦可與上述溫度同樣。 The self-adhesive surface protective film of the present invention is composed of a substrate layer containing the above resin component, an adhesive layer, and a release layer, and the resin constituting each layer is made of, for example, a uniaxial or biaxial extruder. The feed head type or multi-manifold type T die is directly sent out in a molten state, and is obtained by extrusion of three or more layers. In order to make the layers melt In the state, the temperature of the extruder of each layer can be appropriately adjusted in consideration of the forming temperature of the components used in each layer, and can be adjusted, for example, in the range of 200 ° C to 260 ° C. The temperature of the T die can also be the same as the above temperature.

本發明之黏著薄膜在操作上宜製成捲筒之形態。薄膜捲筒的寬度及捲繞長度的上限係沒有特別的限制,但從操作的容易性來看,一般而言較佳為寬度1600mm以下,而在薄膜厚度為40μm時捲繞長度為5000m以下。又,作為捲取芯,通常可使用3吋、6吋、8吋等的塑膠芯或金屬製芯。 The adhesive film of the present invention is preferably handled in the form of a roll. The width of the film roll and the upper limit of the winding length are not particularly limited, but generally, the width is preferably 1600 mm or less from the viewpoint of ease of handling, and the winding length is 5000 m or less when the film thickness is 40 μm. Further, as the winding core, a plastic core or a metal core of 3 吋, 6 吋, or 8 通常 can be usually used.

另外,從加工的適合性來看,較佳為以長度100m以上、寬度450mm以上之尺寸所捲取的薄膜捲筒。 Further, from the viewpoint of processing suitability, a film roll wound up to a size of 100 m or more and a width of 450 mm or more is preferable.

本發明之黏著薄膜可用於為了保護光學用途所用之稜鏡片等的構件、合成樹脂板(例如建築材料用)、不銹鋼板(例如建築材料用)、鋁板、裝飾合板、鋼板、玻璃板、家電製品、精密機械及製造時之汽車車身的表面;為了保護物品防止在堆疊、保管、輸送或製程中搬送時受到損傷;以及保護物品防止在二次加工(例如彎曲加工或加壓加工)時受到損傷之情況。 The adhesive film of the present invention can be used for members such as ruthenium sheets used for protecting optical applications, synthetic resin sheets (for example, for building materials), stainless steel sheets (for building materials), aluminum sheets, decorative plywood, steel sheets, glass sheets, home electric appliances. , precision machinery and the surface of the car body during manufacturing; to protect the article from damage during transport during stacking, storage, transport or process; and to protect the article from damage during secondary processing such as bending or pressurization The situation.

[實施例] [Examples]

接著,舉出實施例來進一步說明本發明。惟本發明只要不脫離其要旨,則不受到下述的實施例所限定。再者,以下的實施例、比較例中的物性之評價方法如下。 Next, the present invention will be further described by way of examples. However, the present invention is not limited by the following examples as long as it does not deviate from the gist of the invention. In addition, the evaluation methods of the physical properties in the following examples and comparative examples are as follows.

(1)黏著性之評價 (1) Evaluation of adhesion

係依據JIS-Z-0237(2000)黏著帶‧黏著片試驗方法,以下述之方法測定。 It was measured in accordance with JIS-Z-0237 (2000) Adhesive tape ‧ Adhesive test method by the following method.

作為被覆體,準備50mm×150mm的壓克力板(三菱縲縈製:Acrylite(註冊商標)3mm厚)、50mm×150mm的稜鏡片(透鏡部由三角柱所構成,三角柱的高度為25μm,三角柱的寬度為50μm),作為試驗片,切出在薄膜製造時之捲取方向為150mm,在與其正交的方向為25mm之試驗片,使用質量2000g的橡膠輥(輥表面的彈簧硬度80Hs,以厚度6mm的橡膠層被覆之寬度45mm、直徑(包含橡膠層)95mm者),使其以5mm/秒之速度來回1次,將試驗片壓黏於被覆體上。壓黏後,使用島津製作所製「Autograph(註冊商標)」(AGS-J),將在溫度23℃、相對濕度65%之環境下放置30分鐘者,以300mm/分鐘之速度進行180度剝離時的阻力最大值當作黏著力[cN/25mm]。所謂180度剝離,係意味在測定剝離時的阻力值之際,保持壓克力板與薄膜的剝離角度為180度。 As a covering, a 50 mm × 150 mm acrylic sheet (made by Mitsubishi Ray: Acrylite (registered trademark) 3 mm thick) and a 50 mm × 150 mm cymbal sheet (the lens portion is composed of a triangular prism, and the height of the triangular prism is 25 μm) Width 50 μm), as a test piece, a test piece having a winding direction of 150 mm at the time of film production and a direction of 25 mm orthogonal thereto was used, and a rubber roller having a mass of 2000 g was used (spring hardness of the roller surface was 80 Hs to thickness) A 6 mm rubber layer was coated with a width of 45 mm and a diameter (including a rubber layer of 95 mm), and the test piece was pressed back to the covering body at a speed of 5 mm/sec. After the pressure-bonding, using Autograph (registered trademark) (AGS-J) manufactured by Shimadzu Corporation, the product was allowed to stand at a temperature of 23 ° C and a relative humidity of 65% for 30 minutes, and was peeled at 180 degrees at a speed of 300 mm/min. The maximum resistance is taken as the adhesion [cN/25mm]. The 180-degree peeling means that the peeling angle of the acrylic sheet and the film is maintained at 180 degrees when the resistance value at the time of peeling is measured.

測定時作為測定試料的夾持部分,準備厚度190μm、尺寸25mm×170mm的聚酯片,於上述壓黏有黏著薄膜與壓克力板的測定試料之黏著薄膜側之邊緣,以黏貼部分15mm之寬度使用賽璐玢膠帶來貼附作為測定時的夾持部分。第1圖中顯示測定試料之模型圖。測定係對一個樣品實施3次,以其平均值作為該樣品的黏著力。 At the time of measurement, a polyester sheet having a thickness of 190 μm and a size of 25 mm×170 mm was prepared as a nip portion for measuring the sample, and the edge of the adhesive film side of the measurement sample to which the adhesive film and the acrylic sheet were pressure-bonded was adhered to a portion of 15 mm. The width is attached using a cellophane tape as a grip portion at the time of measurement. A model diagram of the measurement sample is shown in Fig. 1. The measurement system was performed three times on one sample, and the average value was used as the adhesion of the sample.

(2)樹脂之MFR測定 (2) MFR measurement of resin

係依據JIS-K7210進行測定。 The measurement was carried out in accordance with JIS-K7210.

(3)樹脂之彎曲彈性模數測定 (3) Determination of flexural modulus of resin

係依據ASTM D747-70進行測定。 The measurement was carried out in accordance with ASTM D747-70.

(4)苯乙烯系彈性體中的乙烯成分之測定 (4) Determination of ethylene component in styrene elastomer

將樹脂樣品約330mg溶解於重氯仿中,進行13C-NMR(BRUKER製AVANCE500)測定。根據所得之測定結果,鑑定苯乙烯系彈性體中的乙烯成分量。 About 330 mg of the resin sample was dissolved in heavy chloroform, and 13 C-NMR (AVANCE 500 manufactured by BRUKER) was measured. The amount of the ethylene component in the styrene-based elastomer was identified based on the obtained measurement results.

(5)剝離力之評價 (5) Evaluation of peeling force

於壓克力板(三菱縲縈製:Acrylite(註冊商標)3mm厚)50mm×150mm全面上貼附雙面膠帶(日東電工製),於雙面膠帶之另一面上,以試驗片的黏著面出現之方式,貼附150mm(薄膜製造時的捲取方向)×50mm(與薄膜製造時的捲取方向呈正交的方向)之試驗片。 Double-sided tape (made by Nitto Denko) on the acrylic sheet (Mitsubishi Twist: Acrylite (registered trademark) 3mm thick) 50mm × 150mm, on the other side of the double-sided tape, with the adhesive side of the test piece In the manner in which it was produced, a test piece of 150 mm (winding direction at the time of film production) × 50 mm (direction orthogonal to the winding direction at the time of film production) was attached.

作為新的試驗片,切出於薄膜製造時的捲取方向中為150mm,於與其正交的方向為40mm之試驗片,將其黏著面與隔著雙面膠帶而貼附在壓克力板上的試驗片之脫模面疊合後,使用質量2000g的橡膠輥(捲筒表面的彈簧硬度80Hs,以厚度6mm的橡膠層被覆之寬度45mm、直徑(包含橡膠層)95mm者),使其以5mm/秒之速度來回1次,壓黏脫模面與試驗片。壓黏後,對於捲取方向中100mm及與其正交的方向中40mm之合計面積4000mm2施加60kg的荷重,於溫度40℃、相對濕度65%之環境下放置24小時後,冷卻至23℃者,藉由使用島津製作所製「Autograph(註冊商標)」(AGS-J),以300mm/分鐘之速度180度剝離而評價剝離力。 As a new test piece, it was cut into 150 mm in the winding direction of the film, and a test piece of 40 mm in the direction orthogonal thereto was attached to the acrylic sheet with the adhesive surface and the double-sided tape interposed therebetween. After the release surface of the upper test piece was superposed, a rubber roller having a mass of 2000 g (the spring hardness of the surface of the reel was 80 Hs, the width of the rubber layer covered with a thickness of 6 mm was 45 mm, and the diameter (including the rubber layer) was 95 mm) was used. Back and forth at a speed of 5 mm / sec, pressure-bonded release surface and test piece. After pressure sticky, 2 a load of 60kg for the take-up direction and 100mm in the direction perpendicular thereto in the total area of 40mm 4000mm, at a temperature of 40 ℃, stand for 24 hours at a relative humidity of 65% of the environment by cooling to 23 ℃ The peeling force was evaluated by using "Autograph (registered trademark)" (AGS-J) manufactured by Shimadzu Corporation and peeling at 180 degrees at a speed of 300 mm/min.

測定時,作為測定試料的夾持部分,準備厚度190μm、尺寸40mm×170mm的聚酯片,於150mm×40mm的試驗片之邊緣,以黏貼部分15mm之寬度使用賽璐玢膠帶貼附作為測定時的夾持部分。測定係將試驗片之壓黏部100mm之中,40mm至60mm剝離時的阻力值之平均值當作該試驗片的剝離力[cN/40mm]。測定係實施3次,將其平均值當作最終的剝離力。 At the time of measurement, a polyester sheet having a thickness of 190 μm and a size of 40 mm × 170 mm was prepared as a holding portion of the measurement sample, and was attached to the edge of a test piece of 150 mm × 40 mm by using a cellophane tape at a width of 15 mm of the adhesive portion. The clamping part. In the measurement, the average value of the resistance values at the time of peeling from 40 mm to 60 mm among the pressure-sensitive adhesive portions of the test piece was taken as the peeling force [cN/40 mm] of the test piece. The measurement system was carried out 3 times, and the average value was taken as the final peeling force.

(6)將對於壓克力板的最大黏著力取作分母,脫模層與黏著層的剝離力取作分子時之比 (6) Taking the maximum adhesion force of the acrylic sheet as the denominator, the ratio of the peeling force of the release layer and the adhesive layer to the molecular ratio

考量測定時的試料之寬度來計算。具體而言,係使於上述(5)的剝離力之值為25/40倍之值取作分子而計算。 The width of the sample at the time of measurement is taken into consideration. Specifically, the value of the peeling force of the above (5) is 25/40 times as a value.

(7)從捲筒之捲出性 (7) Rolling out from the reel

經由切割而得到550mm寬度、500m捲繞的薄膜捲繞體後,在溫度23℃、濕度75%之遮光環境下以捲筒狀態保管7日。關於此保管捲筒,在另一塑膠芯(直徑9cm)上重繞300m後立即以手抓住薄膜端部而拉伸,退捲3m。退捲時目視確認在薄膜是否有部分的伸長或變形。將無部分的伸長或變形者當作○(良好),將有部分的伸長或變形者當作×(不良)。 A film wound body having a width of 550 mm and a diameter of 500 m was obtained by cutting, and then stored in a roll state for 7 days in a light-shielding environment having a temperature of 23 ° C and a humidity of 75%. Regarding this storage reel, immediately after rewinding 300 m on another plastic core (diameter 9 cm), the end of the film was grasped by hand and stretched, and unrolled by 3 m. When unwinding, visually confirm whether there is a partial elongation or deformation of the film. A part of the elongation or deformation is regarded as ○ (good), and a part of the elongation or deformation is regarded as × (bad).

[實施例1] [Example 1] (基材層之製作) (Production of substrate layer)

將100質量%的均聚丙烯樹脂(住友化學製:FLX80E4,230℃ MFR:7.5g/10min)用90mmΦ單軸擠壓機,於240℃熔融擠出作為基材層。 100% by mass of a homopolypropylene resin (manufactured by Sumitomo Chemical Co., Ltd.: FLX80E4, 230 ° C MFR: 7.5 g/10 min) was melt-extruded at 240 ° C as a substrate layer using a 90 mm Φ uniaxial extruder.

(黏著層之製作) (production of adhesive layer)

將40質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)、50質量%的乙烯‧α-烯烴共聚物(住友化學製:CX3007,190℃ MFR:3.7g/10min,彎曲彈性模數:26MPa)與10質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)用40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 40% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230 ° C MFR: 4.5 g/10 min), 50% by mass Ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: CX3007, 190 ° C MFR: 3.7 g/10 min, flexural modulus: 26 MPa) and 10% by mass of petroleum resin (Arakawa Chemical Co., Ltd.: Arkon (registered trademark) P125 It was melt extruded at 210 ° C as an adhesive layer using a 40 mm Φ single-axis extruder.

(脫模層之製作) (production of release layer)

將90質量%的丙烯-乙烯嵌段共聚物(日本聚丙烯製:BC3HF)與10質量%的低密度聚乙烯樹脂(宇部興產製:R300)用65mmΦ單軸擠壓機,於230℃熔融擠出作為脫模層。 90% by mass of a propylene-ethylene block copolymer (made of Japanese propylene: BC3HF) and 10% by mass of a low-density polyethylene resin (manufactured by Ube Industries: R300) were melted at 230 ° C using a 65 mm Φ single-axis extruder. Extrusion was carried out as a release layer.

(薄膜之製作) (production of film)

基材層、黏著層、脫模層分別使用各擠壓機以熔融的狀態,在245℃的3層T模頭(供料頭型,唇寬850mm,唇間隙1mm)內進行積層擠壓。將所擠出的薄膜以20m/min速度牽引到溫度30℃的澆鑄輥,冷卻固化而得到基材層厚度為28μm、黏著層厚度為6μm、脫模層厚度為6μm、薄膜寬度為600mm、薄膜長度為1100m的3種3層未延伸薄膜。再者,對此薄膜,以牽引張力40N,以橡膠輥對薄膜寬度施加50N接觸壓力,以50m/min之速度來切割,而得到薄膜寬度為550mm、薄膜長度為500m之未延伸薄膜。 The base material layer, the adhesive layer, and the release layer were each laminated in a molten state at each of 245 ° C using a three-layer T die (feed head type, lip width 850 mm, lip gap 1 mm). The extruded film was drawn at a speed of 20 m/min to a casting roll at a temperature of 30 ° C, and solidified by cooling to obtain a substrate layer thickness of 28 μm, an adhesive layer thickness of 6 μm, a release layer thickness of 6 μm, a film width of 600 mm, and a film. Three 3-layer unstretched films of 1100 m in length. Further, this film was cut at a tensile force of 40 N by a rubber roller to a film width of 50 N at a speed of 50 m/min to obtain an unstretched film having a film width of 550 mm and a film length of 500 m.

[實施例2] [Embodiment 2]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following. Three kinds of three-layer unstretched films were obtained in the same manner as in Example 1.

(黏著層之製作) (production of adhesive layer)

將60質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)與40質量%的乙烯‧α-烯烴共聚物(住友化學製:CX3007,190℃ MFR:3.7g/10min,彎曲彈性模數:26MPa)用40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 60% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230° C. MFR: 4.5 g/10 min) and 40% by mass The ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: CX3007, 190 ° C MFR: 3.7 g/10 min, flexural modulus: 26 MPa) was melt extruded at 210 ° C as an adhesive layer using a 40 mm Φ single-axis extruder.

[實施例3] [Example 3]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following. Three kinds of three-layer unstretched films were obtained in the same manner as in Example 1.

(黏著層之製作) (production of adhesive layer)

將40質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)、50質量%的乙烯‧α-烯烴共聚物(住友化學製:VL100,190℃ MFR:0.8g/10min,彎曲彈性模數:64MPa)與10質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)用40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 40% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230 ° C MFR: 4.5 g/10 min), 50% by mass Ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: VL100, 190 ° C MFR: 0.8 g/10 min, flexural modulus: 64 MPa) and 10% by mass of petroleum resin (Arakawa Chemical Co., Ltd.: Arkon (registered trademark) P125 It was melt extruded at 210 ° C as an adhesive layer using a 40 mm Φ single-axis extruder.

[實施例4] [Example 4]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following. Three kinds of three-layer unstretched films were obtained in the same manner as in Example 1.

(黏著層之製作) (production of adhesive layer)

將85質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1041,苯乙烯成分比30質量%,乙烯成分比49質量%,230℃ MFR:5.0g/10min)、5質量%的乙烯‧α-烯烴共聚物(住友化學製:CX3007,190℃ MFR:0.8g/10min,彎曲彈性模數:26MPa)與10質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)用40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 85% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1041, styrene component ratio: 30% by mass, ethylene component ratio: 49% by mass, 230 ° C MFR: 5.0 g/10 min), 5% by mass Ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: CX3007, 190 ° C MFR: 0.8 g/10 min, flexural modulus: 26 MPa) and 10% by mass of petroleum resin (Arakawa Chemical Co., Ltd.: Arkon (registered trademark) P125 It was melt extruded at 210 ° C as an adhesive layer using a 40 mm Φ single-axis extruder.

[實施例5] [Example 5]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,除了使基材層厚度為24μm,黏著層厚度為10μm,脫模層厚度為6μm以外,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following except that the thickness of the base material layer was 24 μm, the thickness of the adhesive layer was 10 μm, and the thickness of the release layer was 6 μm. In the same manner as in Example 1, three kinds of three-layer unstretched films were obtained.

(黏著層之製作) (production of adhesive layer)

將50質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)、37質量%的乙烯‧α-烯烴共聚物(住友化學製:CX3007,190℃ MFR:3.7g/10min,彎曲彈性模數:26MPa)與13質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)以40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 50% by mass of styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230 ° C MFR: 4.5 g/10 min), 37% by mass Ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: CX3007, 190 ° C MFR: 3.7 g/10 min, flexural modulus: 26 MPa) and 13% by mass of petroleum resin (Arakawa Chemical Co., Ltd.: Arkon (registered trademark) P125 It was melt extruded at 210 ° C as an adhesive layer by a 40 mm Φ single-axis extruder.

[實施例6] [Embodiment 6]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,除了使基材層厚度為30μm,黏著層厚度為4μm,脫模層厚度為6μm以外,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following except that the thickness of the base material layer was 30 μm, the thickness of the adhesive layer was 4 μm, and the thickness of the release layer was 6 μm. In the same manner as in Example 1, three kinds of three-layer unstretched films were obtained.

(黏著層之製作) (production of adhesive layer)

將40質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)、55質量%的乙烯‧α-烯烴共聚物(住友化學製:CX3007,190℃ MFR:3.7g/10min,彎曲彈性模數:26MPa)與5質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)以40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 40% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230 ° C MFR: 4.5 g/10 min), and 55 mass% Ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: CX3007, 190 ° C MFR: 3.7 g/10 min, flexural modulus: 26 MPa) and 5% by mass of petroleum resin (manufactured by Arakawa Chemical Industry Co., Ltd.: Arkon (registered trademark) P125 It was melt extruded at 210 ° C as an adhesive layer by a 40 mm Φ single-axis extruder.

[比較例1] [Comparative Example 1]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following. Three kinds of three-layer unstretched films were obtained in the same manner as in Example 1.

(黏著層之製作) (production of adhesive layer)

將70質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)、20質量%的乙烯‧α-烯烴共聚物(住友化學製:CX3007,190℃ MFR:3.7g/10min,彎曲彈性模數:26MPa)與10質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)以40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 70% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230 ° C MFR: 4.5 g/10 min), 20% by mass Ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: CX3007, 190 ° C MFR: 3.7 g/10 min, flexural modulus: 26 MPa) and 10% by mass of petroleum resin (Arakawa Chemical Co., Ltd.: Arkon (registered trademark) P125 It was melt extruded at 210 ° C as an adhesive layer by a 40 mm Φ single-axis extruder.

[比較例2] [Comparative Example 2]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following. Three kinds of three-layer unstretched films were obtained in the same manner as in Example 1.

(黏著層之製作) (production of adhesive layer)

將70質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)、20質量%的乙烯‧α-烯烴共聚物(住友化學製:VL100,190℃ MFR:0.8g/10min,彎曲彈性模數:64MPa)與10質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)以40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 70% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230 ° C MFR: 4.5 g/10 min), 20% by mass Ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: VL100, 190 ° C MFR: 0.8 g/10 min, flexural modulus: 64 MPa) and 10% by mass of petroleum resin (Arakawa Chemical Co., Ltd.: Arkon (registered trademark) P125 It was melt extruded at 210 ° C as an adhesive layer by a 40 mm Φ single-axis extruder.

[比較例3] [Comparative Example 3]

將20質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)、70質量%的乙烯‧α-烯烴共聚物(住友化學製:CX3007,190℃ MFR:3.7g/10min,彎曲彈性模數:26MPa)與10質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)以40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 20% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230 ° C MFR: 4.5 g/10 min), 70% by mass Ethylene ‧ α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: CX3007, 190 ° C MFR: 3.7 g/10 min, flexural modulus: 26 MPa) and 10% by mass of petroleum resin (Arakawa Chemical Co., Ltd.: Arkon (registered trademark) P125 It was melt extruded at 210 ° C as an adhesive layer by a 40 mm Φ single-axis extruder.

[比較例4] [Comparative Example 4]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following. Three kinds of three-layer unstretched films were obtained in the same manner as in Example 1.

(黏著層之製作) (production of adhesive layer)

將40質量%的苯乙烯系彈性體(旭化成化學製:Tuftec(註冊商標)H1221,苯乙烯成分比12質量%,乙烯成分比18質量%,230℃ MFR:4.5g/10min)、50質量%的均聚丙烯(住友化學製:FLX80E4,190℃ MFR:7.5g/10min)與10質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)以40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 40% by mass of a styrene-based elastomer (manufactured by Asahi Kasei Chemical Co., Ltd.: Tuftec (registered trademark) H1221, styrene component ratio: 12% by mass, ethylene component ratio: 18% by mass, 230 ° C MFR: 4.5 g/10 min), 50% by mass Uniform polypropylene (manufactured by Sumitomo Chemical Co., Ltd.: FLX80E4, 190 ° C MFR: 7.5 g/10 min) and 10% by mass of petroleum resin (manufactured by Arakawa Chemical Industry Co., Ltd.: Arkon (registered trademark) P125) with a 40 mm Φ single-axis extruder at 210 °C melt extrusion as an adhesive layer.

[比較例5] [Comparative Example 5]

基材層、脫模層係維持如實施例1,而將黏著層變更為下述之內容,以與實施例1同樣之製法得到3種3層的未延伸薄膜。 The base material layer and the release layer were maintained as in Example 1, and the adhesive layer was changed to the following. Three kinds of three-layer unstretched films were obtained in the same manner as in Example 1.

(黏著層之製作) (production of adhesive layer)

將80質量%的苯乙烯與丁二烯的無規共聚物之氫化體(JSR製:Dynaron(註冊商標)1320P,苯乙烯成分比10質量%,乙烯成分比22質量%,230℃ MFR:3.5g/10min)、10質量%的石油樹脂(荒川化學工業製:Arkon(註冊商標)P125)與10質量%的乙烯‧α-烯烴共聚物(住友化學製:CX3007,190℃ MFR:3.7g/10min,彎曲彈性模數:26MPa)以40mmΦ單軸擠壓機,於210℃熔融擠出作為黏著層。 a hydrogenated body of a random copolymer of 80% by mass of styrene and butadiene (manufactured by JSR: Dynaron (registered trademark) 1320P, a styrene component ratio of 10% by mass, an ethylene component ratio of 22% by mass, 230 ° C MFR: 3.5 g/10min), 10% by mass of petroleum resin (Arkon (registered trademark) P125 manufactured by Arakawa Chemical Industry Co., Ltd.) and 10% by mass of ethylene ‧α-olefin copolymer (manufactured by Sumitomo Chemical Co., Ltd.: CX3007, 190°C MFR: 3.7g/ 10 min, bending elastic modulus: 26 MPa) was melt extruded at 210 ° C as an adhesive layer in a 40 mm Φ single-axis extruder.

將上述結果顯示於表1、2。 The above results are shown in Tables 1 and 2.

如由表1可明知,實施例1~6所得之薄膜在作為保護薄膜而使用時,係具有實用上充分的黏著力,將薄膜作為捲筒而捲出時之捲出性亦良好。 As is clear from Table 1, the films obtained in Examples 1 to 6 have a practically sufficient adhesive force when used as a protective film, and the roll-out property when the film is wound up as a roll is also good.

另一方面,比較例1、2及5所得之薄膜,將薄膜作為捲筒捲出時之捲出性不能說是良好。比較例3及4所得之薄膜,對於被覆體的黏著力不能說是充分。如此地,比較例所得之薄膜係皆為品質差、實用性低之物。 On the other hand, in the films obtained in Comparative Examples 1, 2, and 5, the unwinding property when the film was taken up as a roll could not be said to be good. The films obtained in Comparative Examples 3 and 4 were not sufficient for the adhesion of the covering. As described above, the film systems obtained in the comparative examples were all of poor quality and low practicality.

Claims (6)

一種自黏性表面保護薄膜,其特徵為:藉由共擠出而在由聚丙烯系樹脂所構成的基材層之一面上積層黏著層,在相反面上積層脫模層而成,對於壓克力板的最大黏著力為800cN/25mm以上,將對於壓克力板的最大黏著力取作分母,將脫模層與黏著層的剝離力取作分子時之比為0.003至0.18。 A self-adhesive surface protective film characterized in that an adhesive layer is laminated on one surface of a base material layer made of a polypropylene resin by co-extrusion, and a release layer is laminated on the opposite surface. The maximum adhesion of the gram board is 800 cN/25 mm or more. The maximum adhesion to the acrylic sheet is taken as the denominator, and the ratio of the peeling force of the release layer to the adhesive layer is taken as the ratio of 0.003 to 0.18. 如請求項1之自黏性表面保護薄膜,其中構成黏著層的樹脂至少含有苯乙烯系彈性體與聚乙烯系樹脂,黏著層中的苯乙烯系彈性體之含量為35質量%以上99質量%以下,聚乙烯系樹脂之含量為1質量%以上65質量%以下,苯乙烯系彈性體中的乙烯成分與聚乙烯系樹脂之和為黏著層成分中35質量%以上且小於70質量%。 The self-adhesive surface protection film according to claim 1, wherein the resin constituting the adhesive layer contains at least a styrene-based elastomer and a polyethylene-based resin, and the content of the styrene-based elastomer in the adhesive layer is 35 mass% or more and 99 mass%. In the following, the content of the polyethylene resin is 1% by mass or more and 65% by mass or less, and the sum of the ethylene component and the polyethylene resin in the styrene elastomer is 35 mass% or more and less than 70 mass% in the adhesive layer component. 如請求項2之自黏性表面保護薄膜,其中黏著層中的聚乙烯系樹脂之MFR(melt flow rate;熔體流動速率)(190℃、2.16kgf)為0.5~8g/10分鐘。 The self-adhesive surface protective film of claim 2, wherein the polyethylene resin in the adhesive layer has a MFR (melt flow rate) (190 ° C, 2.16 kgf) of 0.5 to 8 g/10 min. 如請求項2或3之自黏性表面保護薄膜,其中黏著層中的苯乙烯系彈性體之MFR(230℃、2.16kgf)為0.5~8g/10分鐘。 The self-adhesive surface protective film according to claim 2 or 3, wherein the styrene-based elastomer in the adhesive layer has an MFR (230 ° C, 2.16 kgf) of 0.5 to 8 g/10 min. 如請求項1至4中任一項之自黏性表面保護薄膜,其中基材層中的聚丙烯系樹脂之MFR(230℃、2.16kgf)為1.0~15g/10分鐘。 The self-adhesive surface protective film according to any one of claims 1 to 4, wherein the polypropylene resin in the base material layer has an MFR (230 ° C, 2.16 kgf) of 1.0 to 15 g/10 min. 如請求項1至5中任一項之自黏性表面保護薄膜,其中使用於脫模層的樹脂係非聚矽氧系樹脂。 The self-adhesive surface protective film according to any one of claims 1 to 5, wherein the resin-based non-polyoxynenoid resin used for the release layer is used.
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WO2014054700A1 (en) 2014-04-10

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