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TWI891633B - Surface-protective film - Google Patents

Surface-protective film

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Publication number
TWI891633B
TWI891633B TW109113289A TW109113289A TWI891633B TW I891633 B TWI891633 B TW I891633B TW 109113289 A TW109113289 A TW 109113289A TW 109113289 A TW109113289 A TW 109113289A TW I891633 B TWI891633 B TW I891633B
Authority
TW
Taiwan
Prior art keywords
acrylate
layer
substrate
meth
adhesive layer
Prior art date
Application number
TW109113289A
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Chinese (zh)
Other versions
TW202104489A (en
Inventor
長倉毅
春日充
Original Assignee
日商藤森工業股份有限公司
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Publication of TW202104489A publication Critical patent/TW202104489A/en
Application granted granted Critical
Publication of TWI891633B publication Critical patent/TWI891633B/en

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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
    • C09J7/30—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
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    • 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
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/405—Adhesives in the form of films or foils characterised by release liners characterised by the substrate of the release liner
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2451/00—Presence of graft polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Polarising Elements (AREA)

Abstract

A separator-less type surface-protective film is provided. The surface-protective film is a roll body wound in a roll shape, wherein a back surface layer of a substrate is excellent in printing property. Even if the surface-protective film does not have a release layer containing silicone, the peeling force between the back surface layer of the substrate and the adhesive layer is reduced, and has reduced contamination to the adherend. Wherein the acrylic polymer is copolymerized by (A) an alkyl (meth)acrylate monomer having an C5-C14alkyl group, (B) a polyalkylene glycol chain-containing mono(meth)acrylate monomer, and (C) a copolymerizable vinyl monomer, the copolymerizable vinyl monomer does not have a carboxyl group, but has hydroxyl group as a functional group. The back surface layer of the substrate is a release layer laminated without a silicone compound, and has a contact angle with water of 110° or less.

Description

表面保護膜surface protective film

本發明涉及一種不使用隔片(脫模膜)的無隔片型的表面保護膜。更詳細而言，涉及一種無隔片型的、被卷成輥狀的輥體的表面保護膜，其中，所述基材的背面層的印字性優異，即使不具備含有矽酮的剝離層，也能夠降低所述基材的背面層與所述黏著劑層的剝離力，且能夠降低對被黏物污染性。 進一步，本發明涉及一種能夠取得低速度剝離區域與高速度剝離區域中的黏著力平衡，即使從被黏物上高速剝離時，也能夠以較小的力進行再剝離的無隔片型的表面保護膜。The present invention relates to a spacerless surface protection film that does not utilize a spacer (release film). More specifically, the film is rolled into a roll and has excellent printability on the backside layer of the substrate. Even without a silicone release layer, the film is capable of reducing the peeling force between the backside layer of the substrate and the adhesive layer, and also reduces adherend contamination. Furthermore, the present invention relates to a spacerless surface protection film that achieves a balance of adhesive force between low- and high-speed peeling zones, allowing it to be re-peeled from an adherend with minimal force even when peeled at high speed.

在製造被用作液晶顯示面板的構成構件的偏振片或相位差板等光學膜的步驟中，會在該光學膜的表面黏貼表面保護膜，從而防止對光學膜的表面造成污染或損傷。此外，有時會不剝離所黏貼的表面保護膜而對偏振片或相位差板等光學膜進行外觀檢查。因此，在製造表面保護膜的步驟中，要求以確保高度清潔度的方式進行管理，防止污染物的混入及附著。During the manufacturing process of optical films such as polarizers and retardation plates, components of liquid crystal display panels, a surface protective film is applied to the film to prevent contamination or damage. Furthermore, the film is sometimes inspected without removing the applied surface protective film. Therefore, the surface protective film manufacturing process requires high cleanliness management to prevent contaminants from entering or adhering to the film.

有時，表面保護膜具有典型的在基材膜的單面上設有微黏著性的黏著劑層的構成。黏著劑層為用於將表面保護膜黏貼在偏振片或相位差板等光學膜上的層。將黏著劑層設為微黏著性是為了在從偏振片或相位差板等光學膜上剝離去除使用後的表面保護膜時，能夠順利地剝離，且不會產生殘膠。 此外，用於保護偏振片或相位差板等光學膜的表面的表面保護膜具有「基材膜層/黏著劑層/經剝離處理的脫模膜層」的基本的層構成，並以該狀態捲繞並作為輥體，提供給偏振片或相位差板等光學膜的製造者。 此外，作為表面保護膜利用者的偏振片或相位差板等光學膜的製造者在將所述輥體的表面保護膜重卷後，剝離經剝離處理的脫模膜層，並經由黏著劑層，將成為「基材膜層/黏著劑層」的構成的表面保護膜貼附在偏振片或相位差板等光學膜上。 因此，經剝離處理的脫模膜僅起到用於保護表面保護膜的黏著劑層的作用，其在從表面保護膜的黏著劑層上剝離後被廢棄。Surface protection films typically have a slightly sticky adhesive layer applied to one side of a base film. The adhesive layer is used to adhere the surface protection film to an optical film such as a polarizer or retardation plate. The slightly sticky adhesive layer ensures smooth removal of the used surface protection film from the optical film, such as a polarizer or retardation plate, without leaving adhesive residue. Surface protection films used to protect the surfaces of optical films such as polarizing plates and retardation plates have a basic layer structure of "base film layer/adhesive layer/release film layer treated with a releasable coating." These films are wound in this state and provided to manufacturers of optical films such as polarizing plates and retardation plates in a roll. Furthermore, the manufacturers of optical films such as polarizing plates and retardation plates, who use the surface protection films, rewind the roll of surface protection film, peel off the release film layer treated with a releasable coating, and then adhere the surface protection film, which has the "base film layer/adhesive layer" structure, to the optical film such as polarizing plates and retardation plates via the adhesive layer. Therefore, the release film that has been subjected to the peeling treatment only serves as an adhesive layer for protecting the surface protection film and is discarded after being peeled off from the adhesive layer of the surface protection film.

因此，經剝離處理的脫模膜並不直接有助於對偏振片或相位差板等光學膜的表面的保護。 此外，經剝離處理的脫模膜由於在從表面保護膜的黏著劑層上剝離後，難以在以確保高度清潔度的方式進行管理的同時對脫模膜進行再利用，因此不能重複捲繞進行再利用。 上述不能重複再利用的經剝離處理的脫模膜在資源的有效利用的角度上存在改善的餘地。Therefore, release films treated with a release treatment do not directly contribute to the protection of the surface of optical films such as polarizers and retardation plates. Furthermore, after being peeled from the adhesive layer of the surface protective film, it is difficult to manage the release film in a manner that ensures high cleanliness while reusing it, and therefore it cannot be rewound for reuse. These non-reusable release films have room for improvement in terms of efficient resource utilization.

此外，通常，以往的表面保護膜中，為了使用於保護表面保護膜的黏著劑層而貼合的脫模膜易於從該黏著劑層上剝離，使用剝離性優異的矽酮類剝離劑形成剝離層。其結果，當經由表面保護膜的該黏著劑層，將剝離了脫模膜後的表面保護膜貼合在作為被黏物的光學膜的表面上時，從脫模膜的剝離層移動至該黏著劑層的表面的矽酮會附著在被黏物的表面上，存在引起因矽酮造成污染的擔憂。因此，為了防止矽酮對被黏物造成的污染，作為表面保護膜構成構件的脫模膜的剝離層需要以不使用矽酮類剝離劑的方式而形成。Furthermore, conventional surface protection films typically use a release film attached to the adhesive layer of the surface protection film to facilitate peeling from the adhesive layer. This release film is formed using a silicone-based release agent with excellent releasability. Consequently, when the surface protection film, after peeling the release film, is attached to the surface of an adherend (optical film) through the adhesive layer of the surface protection film, silicone migrates from the release film to the surface of the adhesive layer and adheres to the adherend, causing concern about silicone contamination. Therefore, in order to prevent silicone from contaminating the adherend, the release layer of the release film, which is a component of the surface protection film, needs to be formed without using a silicone-based release agent.

另一方面，在通常的黏著膠帶等技術領域中，廣泛使用有黏著膠帶的輥體，其具有「剝離層/基材膜層/黏著劑層」的層構成，並由將無隔片型的黏著膠帶捲繞成輥狀而製造。 例如，專利文獻1中公開了一種不使用隔片的表面保護膜，其具備黏著劑層，並將聚對苯二甲酸乙二醇酯(以下，稱為PET)作為基材。 此外，專利文獻2中公開了一種將表面保護膜捲繞為輥狀的表面保護膜輥，其不具備用於防止在堆疊樹脂製膜(片)或塗佈加工產品時或捲繞成輥狀時的黏連(blocking)、或用於保護產品表面的隔片。 ［現有技術文獻］ ［專利文獻］On the other hand, in the conventional adhesive tape technology, adhesive tape rolls are widely used. These rolls are manufactured by winding a separatorless adhesive tape into a roll, comprising a layered structure consisting of a release layer, a base film layer, and an adhesive layer. For example, Patent Document 1 discloses a separatorless surface protective film having an adhesive layer and a polyethylene terephthalate (PET) base material. Furthermore, Patent Document 2 discloses a surface protection film roll formed by winding a surface protection film into a roll. This roll does not include a spacer for preventing blocking when stacking resin films (sheets) or coating processed products, or when rolled into a roll, or for protecting the product surface. [Prior Art Document] [Patent Document]

［專利文獻1］：日本特開第2008-266554號公報 ［專利文獻2］：日本特開第2008-266591號公報[Patent Document 1]: Japanese Patent Application Publication No. 2008-266554 [Patent Document 2]: Japanese Patent Application Publication No. 2008-266591

［本發明要解決的技術問題］[Technical Problems to be Solved by the Present Invention]

專利文獻1中記載的發明藉由在構成黏著劑層的黏著劑中添加作為交聯劑的金屬螯合劑，能夠將放卷強度維持在所需的強度，並且能夠抑制放卷時黏著劑層發生內聚破壞。 然而，在專利文獻1的發明的表面保護膜中，由於實施例1~14的剝離速度為300mm/分鐘時的放卷強度全部超過了0.17N/25mm，因此存在需要進一步降低放卷強度，從而提高放卷時的操作性的問題。The invention described in Patent Document 1 maintains the desired unwinding strength and suppresses cohesive failure of the adhesive layer during unwinding by adding a metal chelate as a crosslinking agent to the adhesive constituting the adhesive layer. However, in the surface protection film of the invention of Patent Document 1, the unwinding strength of Examples 1 to 14 all exceeded 0.17 N/25 mm at a peeling speed of 300 mm/min. Therefore, the unwinding strength needed to be further reduced to improve unwinding workability.

專利文獻2中記載的發明藉由添加反應性稀釋劑，並藉由照射電子束而使黏著劑層交聯，從而不需要表面保護膜的熟化，能夠形成不經由隔片而可直接捲繞成輥狀的硬度的黏著劑層。 然而，在專利文獻2的發明的表面保護膜輥中，在基材的與積層有黏著劑層的面為相反側的面上，積層有熱固化型的矽酮類脫模劑層，因此存在有可能引起矽酮對被黏物造成污染的問題。The invention described in Patent Document 2 crosslinks the adhesive layer by adding a reactive diluent and irradiating it with an electron beam. This eliminates the need for curing the surface protective film and enables the formation of a hard adhesive layer that can be directly rolled into a roll without a separator. However, the surface protective film roll of the invention in Patent Document 2 has a thermosetting silicone release agent layer deposited on the surface of the substrate opposite to the surface on which the adhesive layer is deposited. This poses the problem of silicone contamination of the adherend.

如上所述，在以往技術中，對於無隔片型的表面保護膜，難以同時謀求放卷強度的降低及對被黏物的污染性的降低。As described above, in the conventional technology, it is difficult to simultaneously achieve a reduction in unwinding strength and a reduction in contamination to the adherend for a spacer-less surface protection film.

此外，在偏振片或相位差板等光學膜的製造步驟中，為了防止其表面的污垢或損傷，在經由表面保護膜的黏著劑層黏貼表面保護膜後，在光學膜的相反面上積層第二黏著劑層(第二黏著劑層的表面為被剝離膜覆蓋的狀態)，從而形成積層體，並將其裁切為目標大小。 此外，積層體的層構成為「表面保護膜/光學膜/第二黏著劑層/剝離膜」。在直至供於之後的步驟之前，以堆疊的狀態處理積層體的裁切品。 然而，在上述積層體中，當使用油性油墨在裁切品的表面保護膜上標記偏振角度或相位角度或蓋檢測印時，需要能夠不產生收縮(cissing)而清晰地進行印字。 然而，在無隔片型的表面保護膜中，難以同時謀求放卷強度的降低及優異的印字性。Furthermore, during the manufacturing process of optical films such as polarizers and retardation plates, to prevent surface contamination and damage, a surface protective film is applied via an adhesive layer. A second adhesive layer is then deposited on the opposite side of the optical film (with the second adhesive layer's surface covered by a release film). This creates a laminate, which is then cut to the desired size. The laminate's layer structure is "surface protective film/optical film/second adhesive layer/release film." The cut laminate is handled in a stacked state until it is supplied to the next step. However, when using oil-based ink to mark polarization angles, phase angles, or detect patterns on the surface protection film of cut products in these laminates, it is necessary to ensure clear printing without cissing. However, with spacer-less surface protection films, it is difficult to simultaneously achieve low unwinding strength and excellent printability.

鑒於上述狀況，本發明的技術問題在於提供一種無隔片型的、被卷成輥狀的輥體的表面保護膜，其中，所述基材的背面層的印字性優異，即使不具備含有矽酮的剝離層，也能夠降低所述基材的背面層與所述黏著劑層的剝離力，且能夠降低對被黏物的污染性。 進一步，本發明的技術問題在於提供一種無隔片型的表面保護膜，其能夠取得低速度剝離區域與高速度剝離區域中的黏著力的平衡，即使從被黏物上高速剝離時，也能夠以較小的力進行再剝離。 ［解決技術問題的技術手段］In view of the above-mentioned situation, the technical problem of the present invention is to provide a spacerless surface protection film in a roll-shaped form, wherein the back layer of the substrate has excellent printability, and even without a silicone-containing release layer, the peeling force between the back layer of the substrate and the adhesive layer is reduced, thereby reducing the risk of adherend contamination. Furthermore, the technical problem of the present invention is to provide a spacerless surface protection film that achieves a balance of adhesive forces between low- and high-speed peeling zones, allowing for re-peeling with minimal force even when peeling from an adherend at high speed. [Technical Means for Solving the Technical Problem]

本發明的技術構思在於，藉由在依次積層黏著劑層、基材、及基材的背面層而成的無隔片型的表面保護膜中，使所述黏著劑層由使含有丙烯酸類聚合物與交聯劑的黏著劑組合物交聯而形成，並將所述基材的背面層製成不含矽酮化合物而積層的、對水的接觸角為110°以下的剝離層，從而具備優異的印字性與剝離力，其中，所述丙烯酸類聚合物為使(甲基)丙烯酸烷基酯單體、含聚伸烷基二醇鏈(polyalkylene glycol chain)的單(甲基)丙烯酸酯單體、及不含有羧基而含有羥基作為官能團的共聚性乙烯基單體共聚而成的丙烯酸類聚合物。The technical concept of the present invention is to provide a spacerless surface protective film comprising an adhesive layer, a substrate, and a backing layer stacked in sequence. The adhesive layer is formed by crosslinking an adhesive composition comprising an acrylic polymer and a crosslinking agent. Furthermore, the backing layer of the substrate is formed as a release layer having a contact angle with water of 110° or less, which is formed without a silicone compound. This provides excellent printability and release strength. The acrylic polymer is a copolymer of an alkyl (meth)acrylate monomer, a mono(meth)acrylate monomer containing a polyalkylene glycol chain, and a copolymerizable vinyl monomer containing hydroxyl groups instead of carboxyl groups.

為了解決所述技術問題，本發明提供一種表面保護膜，其為由將由含有丙烯酸類聚合物與(D)交聯劑的黏著劑組合物交聯而成的黏著劑層積層在聚酯膜的基材的單面上而形成的表面保護膜，其特徵在於，所述丙烯酸類聚合物為由(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體、(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體、及(C)不含有羧基而含有羥基作為官能團的共聚性乙烯基單體共聚而成的丙烯酸類聚合物，在所述基材的與積層有所述黏著劑層的面為相反側的面上，積層基材的背面層，所述基材的背面層為不含矽酮化合物而積層的剝離層，其對水的接觸角為110°以下，所述表面保護膜為不使用脫模膜而進行捲繞，且所述基材的背面層與所述黏著劑層相接而成的輥體，對所述輥體進行重卷，以0.3m/min的剝離速度從所述黏著劑層上剝離所述基材的背面層時的剝離力為0.1N/25mm以下。To solve the above technical problems, the present invention provides a surface protective film formed by laminating an adhesive layer formed by crosslinking an adhesive composition containing an acrylic polymer and (D) a crosslinking agent on one side of a polyester film substrate. The surface protective film is characterized in that the acrylic polymer is a copolymer of (A) an alkyl (meth)acrylate monomer having an alkyl group with carbon atoms of C5 to C14, (B) a mono(meth)acrylate monomer containing a polyalkylene glycol chain, and (C) a copolymerizable vinyl monomer containing no carboxyl group but a hydroxyl group as a functional group. An acrylic polymer is formed on the surface of the substrate opposite to the surface on which the adhesive layer is layered, and a back layer of the substrate is layered. The back layer of the substrate is a peeling layer that does not contain a silicone compound and has a contact angle with water of 110° or less. The surface protective film is wound without a release film, and the back layer of the substrate and the adhesive layer are in contact with each other on a roll. The roll is rewound, and a peeling force of 0.1 N/25 mm or less is achieved when the back layer of the substrate is peeled off from the adhesive layer at a peeling speed of 0.3 m/min.

此外，較佳所述基材的背面層是將不含矽酮化合物，而含有長鏈烷基懸垂(pendant)化合物的樹脂組合物製成剝離層而進行積層。Furthermore, the back surface of the substrate is preferably formed by laminating a release layer made of a resin composition containing no silicone compound but a long-chain alkyl pendant compound.

此外，較佳：所述丙烯酸類聚合物為：相對於合計100重量份的作為所述(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體的、選自由丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸正壬酯、丙烯酸異壬酯、丙烯酸正辛酯、丙烯酸異辛酯組成的化合物組中的至少一種以上，共聚合計1.0~20重量份的作為所述(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體的、構成聚環氧烷(polyalkylene oxide)的環氧烷的平均重複數為4~14的化合物中的至少一種以上，及合計1.0~10重量份的作為所述(C)不含有羧基而含有羥基作為官能團的共聚性乙烯基單體的、選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯組成的化合物組中的至少一種以上而成的丙烯酸類聚合物，所述黏著劑組合物相對於100重量份的所述丙烯酸類聚合物，以合計0.5~5重量份的比例含有作為所述(D)交聯劑的、選自由六亞甲基二異氰酸酯的縮二脲改性體、異氰脲酸酯改性體、加合物改性體組成的組中的至少一種以上化合物的三官能度以上的異氰酸酯化合物，並且以合計0.001~0.5重量份的比例含有作為(E)交聯促進劑的、選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的組中的至少一種以上，以及以0.1~300重量份的比例含有(F)酮-烯醇互變異構體化合物，所述(F)/所述(E)的重量份比率為70~1000。In addition, it is preferred that the acrylic polymer is copolymerized with 1.0 to 20 parts by weight of the (B) mono(meth)acrylate monomer containing a polyalkylene glycol chain, which constitutes a polyalkylene oxide, relative to 100 parts by weight of at least one compound selected from the group consisting of n-hexyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-octyl acrylate, and isooctyl acrylate as the (A) alkyl (meth)acrylate monomer having an alkyl group with a carbon number of C5 to C14. The adhesive composition comprises at least one of compounds having an average repeating number of 4 to 14 alkylene oxides and 1.0 to 10 parts by weight of an acrylic polymer as the copolymerizable vinyl monomer (C) containing no carboxyl group but containing a hydroxyl group as a functional group, selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl acrylate, and 2-hydroxyethyl (meth)acrylate, wherein the adhesive composition contains 0.5 to 5 parts by weight of the acrylic polymer relative to 100 parts by weight of the acrylic polymer. The crosslinking agent (D) comprises a trifunctional or higher-functional isocyanate compound of at least one compound selected from the group consisting of biuret-modified, isocyanurate-modified, and adduct-modified forms of hexamethylene diisocyanate, and the crosslinking accelerator (E) comprises at least one compound selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds in a total amount of 0.001 to 0.5 parts by weight, and the keto-enol tautomer compound (F) is comprised in a total amount of 0.1 to 300 parts by weight. The weight ratio of (F) to (E) is 70 to 1000.

此外，較佳：作為所述基材的背面層的所述剝離層的附著量為0.005g/m2 以上且0.1g/m2 以下，所述黏著劑層的厚度為1~20μm，以30m/min的剝離速度從所述黏著劑層上剝離所述基材的背面層時的剝離力為0.3N/25mm以下。Furthermore, it is preferred that: the adhesion amount of the peeling layer serving as the back layer of the substrate is greater than or equal to 0.005 g/m 2 and less than or equal to 0.1 g/m 2 , the thickness of the adhesive layer is 1 to 20 μm, and the peeling force when peeling the back layer of the substrate from the adhesive layer at a peeling speed of 30 m/min is less than or equal to 0.3 N/25 mm.

此外，較佳：所述聚酯膜的基材的厚度為38μm，以0.3m/min的剝離速度進行剝離時，所述黏著劑層對鈉鈣玻璃(非錫面)的黏著力為0.01N/25mm以上且0.1N/25mm以下，且以30m/min的剝離速度進行剝離時，所述黏著劑層對鈉鈣玻璃(非錫面)的黏著力為1.0N/25mm以下。Furthermore, it is preferred that the polyester film substrate has a thickness of 38 μm, and when peeled at a peeling speed of 0.3 m/min, the adhesive layer has an adhesion force to the sodium calcium glass (non-tin surface) of 0.01 N/25 mm to 0.1 N/25 mm, and when peeled at a peeling speed of 30 m/min, the adhesive layer has an adhesion force to the sodium calcium glass (non-tin surface) of 1.0 N/25 mm or less.

此外，本發明提供一種光學膜，其特徵在於，其由貼合上述表面保護膜而成。 ［發明效果］Furthermore, the present invention provides an optical film characterized by being formed by laminating the above-mentioned surface protection film. [Effects of the Invention]

根據本發明，能夠提供一種無隔片型的、被卷成輥狀的表面保護膜，其中，所述基材的背面層的印字性優異，即使不具備含有矽酮的剝離層也能夠降低所述基材的背面層與所述黏著劑層的剝離力，且能夠降低對被黏物的污染性。 此外，根據本發明，能夠提供一種無隔片型的表面保護膜，其能夠取得低速度剝離區域與高速度剝離區域中的黏著力的平衡，且即使從被黏物上高速剝離時，也能夠以較小的力進行再剝離。The present invention provides a spacerless, roll-shaped surface protection film, wherein the backside layer of the substrate has excellent printability, the peeling force between the backside layer of the substrate and the adhesive layer is reduced even without a silicone-containing release layer, and the adherend contamination is reduced. Furthermore, the present invention provides a spacerless surface protection film that achieves a balance of adhesive forces between low- and high-speed peeling zones, and can be re-peeled from an adherend with minimal force even when peeled at high speed.

以下，根據較佳的實施方式對本發明進行說明。The present invention is described below based on preferred embodiments.

本實施方式的表面保護膜，其為由將由含有丙烯酸類聚合物與(D)交聯劑的黏著劑組合物交聯而成的黏著劑層積層在聚酯膜的基材的單面上而形成的表面保護膜，其特徵在於，所述丙烯酸類聚合物為由(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體、(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體、及(C)不含有羧基而含有羥基作為官能團的共聚性乙烯基單體共聚而成的丙烯酸類聚合物，在所述基材的與積層有所述黏著劑層的面為相反側的面上積層基材的背面層，所述基材的背面層為不含矽酮化合物而積層的剝離層，其對水的接觸角為110°以下，所述表面保護膜為不使用脫模膜而進行捲繞，且所述基材的背面層與所述黏著劑層相接而成的輥體，對所述輥體進行重卷，以0.3m/min的剝離速度從所述黏著劑層上剝離所述基材的背面層時的剝離力為0.1N/25mm以下。The surface protection film of the present embodiment is formed by laminating an adhesive layer formed by crosslinking an adhesive composition containing an acrylic polymer and (D) a crosslinking agent on one side of a polyester film substrate. The surface protection film is characterized in that the acrylic polymer is an acrylic polymer copolymerized with (A) an alkyl (meth)acrylate monomer having an alkyl group with carbon atoms of C5 to C14, (B) a mono(meth)acrylate monomer containing a polyalkylene glycol chain, and (C) a copolymerizable vinyl monomer containing no carboxyl group but a hydroxyl group as a functional group. A polymer is formed on the surface of the substrate opposite to the surface on which the adhesive layer is formed, and a back layer of the substrate is formed. The back layer of the substrate is a peeling layer that does not contain a silicone compound and has a contact angle with water of 110 degrees or less. The surface protective film is wound without using a release film, and the back layer of the substrate and the adhesive layer are in contact with each other to form a roll. The roll is rewound, and the peeling force when the back layer of the substrate is peeled off from the adhesive layer at a peeling speed of 0.3 m/min is 0.1 N/25 mm or less.

本實施方式的表面保護膜的黏著劑層的丙烯酸類聚合物為由(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體、(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體、及(C)不含有羧基而含有羥基作為官能團的共聚性乙烯基單體共聚而成的丙烯酸類聚合物。在本說明書中，(甲基)丙烯酸酯為丙烯酸酯及甲基丙烯酸酯的總稱。The acrylic polymer in the adhesive layer of the surface protection film of this embodiment is a copolymerized acrylic polymer comprising (A) an alkyl (meth)acrylate monomer having an alkyl group with carbon atoms ranging from C5 to C14, (B) a mono(meth)acrylate monomer containing a polyalkylene glycol chain, and (C) a copolymerizable vinyl monomer containing a hydroxyl group as a functional group instead of a carboxyl group. In this specification, "(meth)acrylate" is a general term for both acrylic acid esters and methacrylic acid esters.

作為所述(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體，可列舉出(甲基)丙烯酸正戊酯、(甲基)丙烯酸異戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸異己酯、(甲基)丙烯酸正庚酯、(甲基)丙烯酸異庚酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十一烷基酯、(甲基)丙烯酸異十一烷基酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸異十二烷基酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸異十三烷基酯、(甲基)丙烯酸正十四烷基酯、(甲基)丙烯酸異十四烷基酯等中的至少一種以上。(甲基)丙烯酸烷基酯單體的烷基可以為直鏈狀、支鏈狀、環狀中的任一種。 較佳所述(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體的至少一部分或全部為選自由丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸正壬酯、丙烯酸異壬酯、丙烯酸正辛酯、丙烯酸異辛酯組成化合物組中的至少一種以上。Examples of the (meth)acrylic acid alkyl ester monomer in which the alkyl group (A) has a carbon number of C5 to C14 include at least one of n-pentyl (meth)acrylate, iso-pentyl (meth)acrylate, n-hexyl (meth)acrylate, iso-hexyl (meth)acrylate, n-heptyl (meth)acrylate, iso-heptyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, iso-nonyl (meth)acrylate, n-decyl (meth)acrylate, iso-decyl (meth)acrylate, n-undecyl (meth)acrylate, iso-undecyl (meth)acrylate, n-dodecyl (meth)acrylate, iso-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, iso-tridecyl (meth)acrylate, n-tetradecyl (meth)acrylate, and iso-tetradecyl (meth)acrylate. The alkyl group of the alkyl (meth)acrylate monomer can be linear, branched, or cyclic. Preferably, at least some or all of the alkyl (meth)acrylate monomers (A) having an alkyl group with carbon atoms of C5 to C14 are at least one selected from the group consisting of n-hexyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-octyl acrylate, and isooctyl acrylate.

所述(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體只要為聚伸烷基二醇所具有的多個羥基中的1個羥基被酯化為(甲基)丙烯酸酯的化合物即可。由於(甲基)丙烯酸酯基為聚合性基團，因此能夠與所述丙烯酸類聚合物進行共聚。其他羥基可以保持為OH，也可成為甲醚或乙醚等烷基醚或者乙酸酯等飽和羧酸酯等。The (B) polyalkylene glycol chain-containing mono(meth)acrylate monomer may be a compound in which one of the multiple hydroxyl groups present in the polyalkylene glycol is esterified to a (meth)acrylate ester. Since the (meth)acrylate group is a polymerizable group, it can copolymerize with the acrylic polymer. The remaining hydroxyl groups may remain OH groups, or may be alkyl ethers such as methyl ether or ethyl ether, or saturated carboxylic acid esters such as acetate.

在所述(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體中，作為聚伸烷基二醇所具有的伸烷基，可列舉出乙烯基、丙烯基、丁烯基等，但不限於此。聚伸烷基二醇可以為聚乙二醇-聚丙二醇、聚乙二醇-聚丁二醇、聚丙二醇-聚丁二醇等、在1分子中具有兩種以上的伸烷基的聚伸烷基二醇。所述(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體較佳為構成聚環氧烷的環氧烷的平均重複數為4~14的化合物中的至少一種以上。In the mono(meth)acrylate monomer (B) containing a polyalkylene glycol chain, examples of the alkylene group of the polyalkylene glycol include, but are not limited to, vinyl, propylene, and butylene. The polyalkylene glycol may be a polyalkylene glycol having two or more alkylene groups per molecule, such as polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, or polypropylene glycol-polybutylene glycol. The mono(meth)acrylate monomer (B) containing a polyalkylene glycol chain is preferably at least one compound having an average repeating number of 4 to 14 alkylene oxides constituting polyalkylene oxide.

作為所述(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體，較佳為選自由聚伸烷基二醇單(甲基)丙烯酸酯、甲氧基聚伸烷基二醇(甲基)丙烯酸酯、乙氧基聚伸烷基二醇(甲基)丙烯酸酯中的至少一種以上。更具體而言，可列舉出聚乙二醇單(甲基)丙烯酸酯、聚丙二醇單(甲基)丙烯酸酯、聚丁二醇單(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯、甲氧基聚丁二醇(甲基)丙烯酸酯、乙氧基聚乙二醇(甲基)丙烯酸酯、乙氧基聚丙二醇(甲基)丙烯酸酯、乙氧基聚丁二醇(甲基)丙烯酸酯等。 相對於合計100重量份的作為所述(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體的、選自由丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸正壬酯、丙烯酸異壬酯、丙烯酸正辛酯、丙烯酸異辛酯組成的化合物組中的至少一種以上，較佳以合計1.0~20重量份的比例、更佳以1.0~16重量份的比例、特佳以2.0~14重量份的比例含有作為所述(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體的、構成聚環氧烷的環氧烷的平均重複數為4~14的化合物中的至少一種以上。The (B) polyalkylene glycol chain-containing mono(meth)acrylate monomer is preferably at least one selected from polyalkylene glycol mono(meth)acrylate, methoxypolyalkylene glycol (meth)acrylate, and ethoxypolyalkylene glycol (meth)acrylate. More specifically, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, and ethoxypolybutylene glycol (meth)acrylate can be cited. The at least one compound selected from the group consisting of n-hexyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-octyl acrylate, and isooctyl acrylate as the (B) polyalkylene glycol chain-containing mono(meth)acrylate monomers, wherein the average number of repeats of the alkylene oxide in the polyalkylene oxide is 4 to 14, is preferably present in a total ratio of 1.0 to 20 parts by weight, more preferably 1.0 to 16 parts by weight, and particularly preferably 2.0 to 14 parts by weight, relative to a total of 100 parts by weight of the at least one compound selected from the group consisting of n-hexyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-octyl acrylate, and isooctyl acrylate as the (A) alkyl (meth)acrylate monomers having an alkyl group with a carbon number of C5 to C14.

作為所述(C)不含有羧基而含有羥基作為官能團的共聚性乙烯基單體，可列舉出(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、 (甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯等含羥基的(甲基)丙烯酸烷基酯類或N-羥基(甲基)丙烯醯胺、N-羥基甲基(甲基)丙烯醯胺、N-羥基乙基(甲基)丙烯醯胺等含羥基的(甲基)丙烯醯胺類等中的至少一種以上。當所述(B)可具有羥基時，較佳所述(C)不具有聚伸烷基二醇鏈。 作為所述(C)不含有羧基而含有羥基作為官能團的共聚性乙烯基單體，較佳為選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基乙酯組成的化合物組中的至少一種以上，較佳含有選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、丙烯酸4-羥基丁酯組成的化合物組中的至少一種以上。 相對於合計100重量份的作為所述(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體的、選自由丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸正壬酯、丙烯酸異壬酯、丙烯酸正辛酯、丙烯酸異辛酯組成的化合物組中的至少一種以上，較佳以合計1.0~10重量份的比例、更佳以1.0~8重量份的比例、特佳以1.0~6重量份的比例含有所述(C)不含有羧基而含有羥基作為官能團的共聚性乙烯基單體中的至少一種以上。Examples of the copolymerizable vinyl monomer (C) containing a hydroxyl group as a functional group instead of a carboxyl group include at least one of hydroxyl-containing alkyl (meth)acrylates such as 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate, and hydroxyl-containing (meth)acrylamides such as N-hydroxy (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, and N-hydroxyethyl (meth)acrylamide. When (B) may contain a hydroxyl group, (C) preferably does not contain a polyalkylene glycol chain. The copolymerizable vinyl monomer (C) containing no carboxyl group but a hydroxyl group as a functional group is preferably at least one selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl acrylate, and 2-hydroxyethyl (meth)acrylate, and more preferably contains at least one selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 4-hydroxybutyl acrylate. The at least one copolymerizable vinyl monomer (C) having a hydroxyl group as a functional group and not a carboxyl group is preferably contained in an amount of 1.0 to 10 parts by weight, more preferably 1.0 to 8 parts by weight, and particularly preferably 1.0 to 6 parts by weight, per 100 parts by weight of the at least one selected from the group consisting of n-hexyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, n-octyl acrylate, and isooctyl acrylate, which are the (A) alkyl (meth)acrylate monomers having an alkyl group with a carbon number of C5 to C14.

丙烯酸類聚合物的聚合方法沒有特別限定，可適當使用溶液聚合法、乳液聚合法等公知的聚合方法。丙烯酸類聚合物較佳由使(甲基)丙烯酸酯單體等丙烯酸類單體以50~100重量%的比例進行共聚而成。 構成丙烯酸類聚合物的單體不限於所述(A)~(C)，也可僅為所述(A)~(C)。丙烯酸類聚合物較佳不使(甲基)丙烯酸等含羧基單體進行共聚。例如，從避免對透明導電膜ITO表面等易發生腐蝕的被黏物的腐蝕性的影響的角度出發，較佳丙烯酸類聚合物的酸值為1以下。The polymerization method for the acrylic polymer is not particularly limited; known polymerization methods such as solution polymerization and emulsion polymerization can be appropriately used. The acrylic polymer is preferably formed by copolymerizing an acrylic monomer such as a (meth)acrylate monomer at a ratio of 50 to 100% by weight. The monomers constituting the acrylic polymer are not limited to (A) to (C) described above, and may be solely (A) to (C). The acrylic polymer preferably does not copolymerize with a carboxyl group-containing monomer such as (meth)acrylic acid. For example, to avoid affecting the corrosion resistance of adherends susceptible to corrosion, such as the surface of a transparent conductive film (ITO), the acrylic polymer preferably has an acid value of 1 or less.

丙烯酸類聚合物較佳被由異氰酸酯類交聯劑、環氧類交聯劑、鋁螯合物類交聯劑等中的至少一種以上組成的(D)交聯劑交聯。作為異氰酸酯類交聯劑，可列舉出六亞甲基二異氰酸酯(HDI)、異佛爾酮二異氰酸酯(IPDI)、二苯基甲烷二異氰酸酯(MDI)、甲苯二異氰酸酯(TDI)、伸茬基二異氰酸酯(XDI)等雙官能度異氰酸酯(二異氰酸酯化合物)或這些成分的縮二脲改性體、異氰脲酸酯改性體、與三羥甲基丙烷、丙三醇等多元醇的加合物等。The acrylic polymer is preferably crosslinked with a crosslinking agent (D) consisting of at least one of an isocyanate crosslinking agent, an epoxy crosslinking agent, and an aluminum chelate crosslinking agent. Examples of the isocyanate crosslinking agent include difunctional isocyanates (diisocyanate compounds) such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), and stilbene diisocyanate (XDI), or their biuret-modified and isocyanurate-modified forms, or adducts thereof with polyols such as trihydroxymethylpropane and glycerol.

(D)交聯劑中，較佳為三官能度以上的異氰酸酯化合物，其中，較佳為選自由六亞甲基二異氰酸酯的縮二脲改性體、異氰脲酸酯改性體、加合物改性體組成的組中的至少一種以上的三官能度以上的異氰酸酯化合物。相對於100重量份丙烯酸類聚合物，所述黏著劑組合物較佳以合計0.5~5重量份的比例含有所述(D)交聯劑中的至少一種以上。The crosslinking agent (D) is preferably a trifunctional or higher isocyanate compound, particularly preferably at least one trifunctional or higher isocyanate compound selected from the group consisting of biuret-modified, isocyanurate-modified, and adduct-modified forms of hexamethylene diisocyanate. The adhesive composition preferably contains at least one of the crosslinking agents (D) in a total amount of 0.5 to 5 parts by weight per 100 parts by weight of the acrylic polymer.

所述黏著劑組合物較佳進一步含有(E)交聯促進劑。在將三官能度以上的異氰酸酯化合物等多異氰酸酯化合物作為(D)交聯劑時，所述(E)交聯促進劑只要為對丙烯酸類聚合物與(D)交聯劑的反應(交聯反應)作為催化劑發揮功能的物質即可，可列舉出三級胺等胺類化合物、金屬螯合化合物、有機錫化合物、有機鉛化合物、有機鋅化合物等有機金屬化合物等。The adhesive composition preferably further contains a (E) crosslinking accelerator. When a polyisocyanate compound such as a trifunctional or higher-functional isocyanate compound is used as the crosslinking agent (D), the crosslinking accelerator (E) can be any substance that functions as a catalyst for the reaction (crosslinking reaction) between the acrylic polymer and the crosslinking agent (D). Examples of the crosslinking accelerator include amine compounds such as tertiary amines, metal chelate compounds, organotin compounds, organolead compounds, and organozinc compounds, and organometallic compounds.

作為所述(E)交聯促進劑，較佳金屬螯合化合物，其中較佳為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的組中的至少一種以上。藉由不使用有機錫化合物，容易應對要求使用安全性更高的物質的規定等。 作為用作所述(E)交聯促進劑的金屬螯合化合物，較佳具有選自乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油醇酯(acetoacetate oleyl)、乙醯乙酸月桂酯、乙醯乙酸硬脂醇酯(acetoacetate stearyl)等β-酮酯或乙醯丙酮(別名為2,4-戊二酮)、2,4-己二酮、苯甲醯丙酮等β-二酮等中的至少一種以上的酮-烯醇互變異構體化合物、或該烯醇經脫質子後的烯醇化物(例如乙醯丙酮化物)作為多齒配位體(multidentate ligand)。 相對於100重量份的丙烯酸類聚合物，所述黏著劑組合物較佳以合計0.001~0.5重量份的比例含有所述(E)交聯促進劑中的至少一種以上。The crosslinking accelerator (E) is preferably a metal chelate compound, preferably at least one selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds. By omitting the use of organotin compounds, it is easier to comply with regulations requiring the use of safer substances. The metal chelate compound used as the crosslinking promoter (E) preferably has as a multidentate ligand at least one keto-enol tautomer compound selected from β-ketoesters such as methyl acetylacetate, ethyl acetylacetate, octyl acetylacetate, oleyl acetylacetate, lauryl acetylacetate, and stearyl acetylacetate, or β-diketones such as acetylacetone (also known as 2,4-pentanedione), 2,4-hexanedione, and benzoyl acetone, or a deprotonated enolate of the enol (e.g., acetylacetonate). The adhesive composition preferably contains at least one of the crosslinking promoters (E) in an amount of 0.001 to 0.5 parts by weight relative to 100 parts by weight of the acrylic polymer.

所述黏著劑組合物較佳進一步含有(F)酮-烯醇互變異構體化合物。所述(F)酮-烯醇互變異構體化合物在將三官能度以上的異氰酸酯化合物等聚異氰酸酯化合物作為(D)交聯劑時，藉由對(D)交聯劑所具有的異氰酸酯基進行封端，能夠抑制在摻合(D)交聯劑後黏著劑組合物的黏度過度上升或凝膠化，延長黏著劑組合物的適用期。 作為所述(F)酮-烯醇互變異構體化合物，可列舉出乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸辛酯、乙醯乙酸油醇酯、乙醯乙酸月桂酯、乙醯乙酸硬脂醇酯等β-酮酯、或乙醯丙酮、2,4-己二酮、苯甲醯丙酮等β-二酮等。相對於100重量份的丙烯酸類聚合物，所述黏著劑組合物較佳以合計0.1~300重量份的比例含有所述(F)酮-烯醇互變異構體化合物中的至少一種以上。The adhesive composition preferably further contains (F) a keto-enol tautomer compound. When a polyisocyanate compound such as a trifunctional or higher-functional isocyanate compound is used as the crosslinking agent (D), the (F) keto-enol tautomer compound can block the isocyanate groups of the crosslinking agent (D). This can inhibit excessive viscosity increases or gelation of the adhesive composition after the crosslinking agent (D) is incorporated, thereby extending the shelf life of the adhesive composition. Examples of the keto-enol tautomer compound (F) include β-ketoesters such as methyl acetylacetate, ethyl acetylacetate, octyl acetylacetate, oleyl acetylacetate, lauryl acetylacetate, and stearyl acetylacetate, or β-diketones such as acetylacetone, 2,4-hexanedione, and benzoyl acetone. The adhesive composition preferably contains at least one of the keto-enol tautomer compounds (F) in a total amount of 0.1 to 300 parts by weight per 100 parts by weight of the acrylic polymer.

此外，(F)酮-烯醇互變異構體化合物與(E)交聯促進劑相反，具有抑制交聯的效果，因此較佳適當地設定(F)酮-烯醇互變異構體化合物相對於(E)交聯促進劑的比例。為了延長黏著劑組合物的適用期，提高貯藏穩定性，(F)/(E)的重量份比率較佳為70~1000，更佳為70~700，特佳為80~600。其中，(F)/(E)的重量份比率是指(F)酮-烯醇互變異構體化合物的重量份除以(E)交聯促進劑的重量份而得到的商的值。Furthermore, the (F) keto-enol tautomer compound has the opposite effect of inhibiting crosslinking as the (E) crosslinking accelerator. Therefore, the ratio of the (F) keto-enol tautomer compound to the (E) crosslinking accelerator is preferably appropriately determined. To extend the shelf life of the adhesive composition and improve storage stability, the (F)/(E) weight ratio is preferably 70-1000, more preferably 70-700, and particularly preferably 80-600. The (F)/(E) weight ratio refers to the quotient obtained by dividing the weight of the (F) keto-enol tautomer compound by the weight of the (E) crosslinking accelerator.

所述黏著劑組合物可適當摻合作為任意成分的抗氧化劑、表面活性劑、抗靜電劑、固化促進劑、增塑劑、填充劑、交聯催化劑、交聯延遲劑、固化延遲劑、加工助劑、抗老化劑等公知添加劑。這些添加劑可單獨使用，也可同時使用兩種以上。所述黏著劑組合物較佳不含有聚矽氧烷等矽酮化合物。The adhesive composition may be appropriately blended with any of the following known additives: antioxidants, surfactants, antistatic agents, curing accelerators, plasticizers, fillers, crosslinking catalysts, crosslinking retarders, curing retarders, processing aids, anti-aging agents, and the like. These additives may be used singly or in combination. The adhesive composition preferably does not contain silicone compounds such as polysiloxane.

本實施方式的黏著劑層可藉由在基材或脫模膜上塗佈所述黏著劑組合物後，對所述黏著劑組合物進行交聯而製成。在脫模膜上製成黏著劑層時，可使黏著劑層從脫模膜轉印至基材上。用於轉印該黏著劑層的脫模膜較佳為不具有剝離層的膜或具有不含矽酮化合物的剝離層的膜。 在基材的單面上積層有黏著劑層的黏著膜可用作表面保護膜。表面保護膜中的黏著劑層的厚度較佳為1~20μm，更佳為1~18μm，特佳為3~18μm。The adhesive layer of this embodiment can be formed by coating the adhesive composition onto a substrate or a release film and then crosslinking the adhesive composition. When the adhesive layer is formed on a release film, the adhesive layer can be transferred from the release film to the substrate. The release film used to transfer the adhesive layer is preferably a film without a release layer or a film with a release layer that does not contain a silicone compound. The adhesive film with the adhesive layer laminated on one side of the substrate can be used as a surface protective film. The thickness of the adhesive layer in the surface protective film is preferably 1-20 μm, more preferably 1-18 μm, and particularly preferably 3-18 μm.

作為所述基材，較佳具有透明性及可撓性的樹脂膜。由此，能夠易於將表面保護膜製成輥體，且能夠以將由輥體重卷的表面保護膜貼合在作為被黏物的光學膜上的狀態進行光學膜的外觀檢查。用作所述基材的具有透明性的樹脂膜可較佳列舉出聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚間苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯等聚酯膜。除了聚酯膜以外，只要具有所需的強度且具有光學適性，則也可使用其他樹脂膜。所述基材可以為不拉伸膜，也可以為以經單軸或雙軸拉伸的膜。此外，所述基材可將拉伸膜的拉伸倍率或伴隨拉伸膜的結晶化而形成的軸方向的取向角度控制在特定的值。The substrate is preferably a transparent and flexible resin film. This allows the surface protection film to be easily rolled, and the optical film can be inspected while the rolled surface protection film is attached to the adherend. Preferred examples of transparent resin films for use as the substrate include polyester films such as polyethylene terephthalate, polyethylene naphthalate, polyethylene isophthalate, and polybutylene terephthalate. In addition to polyester films, other resin films may be used as long as they have the required strength and optical suitability. The substrate may be an unstretched film or a uniaxially or biaxially stretched film. In addition, the substrate can control the stretching ratio of the stretched film or the orientation angle in the axial direction formed by crystallization of the stretched film to a specific value.

所述基材的厚度沒有特別限定，例如較佳為12~100μm左右的厚度，由於當為20~50μm左右的厚度時易於操作，因而更佳。更具體而言，所述聚酯膜的基材的厚度可為38μm。 此外，可對所述基材的積層有所述黏著劑層的一側的表面、或後文所述的積層有剝離層的一側的背面，實施基於電暈放電的表面改性、塗佈錨固劑(anchor coat agent)等易黏合處理。The thickness of the substrate is not particularly limited; for example, a thickness of approximately 12 to 100 μm is preferred, with a thickness of approximately 20 to 50 μm being particularly preferred due to ease of handling. More specifically, the polyester film substrate may have a thickness of 38 μm. Also, the surface of the substrate on which the adhesive layer is laminated, or the back surface on which the release layer (described later) is laminated, may be subjected to an adhesion-enhancing treatment such as surface modification based on coma discharge or application of an anchor coating agent.

此外，以0.3m/min的低剝離速度進行剝離時的、所述黏著劑層對鈉鈣玻璃(非錫面)的黏著力較佳為0.01N/25mm以上且0.1N/25mm以下，更佳為0.01N/25mm以上且0.08N/25mm以下，特佳為0.01N/25mm以上且0.06N/25mm以下。此外，以30m/min的高剝離速度進行剝離時的、所述黏著劑層對鈉鈣玻璃(非錫面)的黏著力較佳為1.0N/25mm以下，更佳為0.8N/25mm以下，特佳為0.6N/25mm以下。由此，可得到黏著力相對於剝離速度的變化少的性能。此外，為了重新貼合而暫時剝離所述表面保護膜時，能夠藉由更低剝離速度、以更小的力進行剝離。Furthermore, when peeling at a low peeling speed of 0.3 m/min, the adhesive layer has an adhesion strength to the sodium calcium glass (non-tin surface) of preferably 0.01 N/25 mm or more and 0.1 N/25 mm or less, more preferably 0.01 N/25 mm or more and 0.08 N/25 mm or less, and particularly preferably 0.01 N/25 mm or more and 0.06 N/25 mm or less. Furthermore, when peeling at a high peeling speed of 30 m/min, the adhesive layer has an adhesion strength to the sodium calcium glass (non-tin surface) of preferably 1.0 N/25 mm or less, more preferably 0.8 N/25 mm or less, and particularly preferably 0.6 N/25 mm or less. This allows for minimal variation in adhesive force with respect to peeling speed. Furthermore, when the surface protection film is temporarily peeled off for re-lamination, it can be peeled off at a lower peeling speed and with less force.

在本實施方式的表面保護膜中，在所述基材的、與積層有所述黏著劑層的面(表面)為相反側的面(背面)上積層基材的背面層。由此，所述表面保護膜能夠構成不使用脫模膜而進行捲繞，且由所述基材的背面層與所述黏著劑層相接而成的輥體。In the surface protection film of this embodiment, the backside layer of the substrate is deposited on the surface (backside) of the substrate opposite to the surface (front side) on which the adhesive layer is deposited. This allows the surface protection film to be wound without a release film, with the backside layer of the substrate and the adhesive layer in contact with each other in a roll.

所述基材的背面層為不含矽酮化合物而積層的剝離層。作為除矽酮類剝離劑以外的非矽酮類剝離劑，可列舉出氟類剝離劑、石蠟化合物等蠟類剝離劑、烷基懸垂類剝離劑等。烷基懸垂類剝離劑為使用了長鏈烷基懸垂化合物的剝離劑，作為其具體例，例如可列舉出中京油脂(CHUKYO YUSHI)股份有限公司的Resem(產品名稱)、Lion Specialty Chemicals股份有限公司的Peeloil (註冊商標)、日本觸媒(Nippon Shokubai)股份有限公司的十八烷基異氰酸酯改性聚乙烯亞胺(產品名稱：RP-20)、或未特別舉出產品名稱但具有作為側鏈的多個長鏈烷基的丙烯酸類的高分子化合物等。認為在側鏈上具有長鏈烷基的高分子化合物的組藉由其長鏈烷基起到了剝離效果。因此，長鏈烷基的碳原子數為5以上，較佳為12以上，上限沒有特別限制，但由於存在若碳原子數變大則融點變高、且對溶劑的溶解性變差的傾向，因此通常較佳為24以下。The back surface of the substrate is a release layer formed without containing a silicone compound. Examples of non-silicone release agents other than silicone release agents include fluorine-based release agents, wax-based release agents such as wax compounds, and alkyl pendant-based release agents. Alkyl pendant strippers are strippers that utilize compounds with long-chain alkyl pendants. Specific examples include Resem (product name) from Chukyo Yushi Co., Ltd., Peeloil (registered trademark) from Lion Specialty Chemicals Co., Ltd., octadecyl isocyanate-modified polyethyleneimine (product name: RP-20) from Nippon Shokubai Co., Ltd., and other unspecified acrylic polymers with multiple long-chain alkyl groups as pendant chains. It is believed that polymers with long-chain alkyl groups on their pendant chains exert a stripping effect through the long-chain alkyl groups. Therefore, the number of carbon atoms in the long-chain alkyl group is 5 or more, preferably 12 or more. There is no particular upper limit, but a larger number of carbon atoms tends to increase the melting point and deteriorate the solubility in solvents. Therefore, it is usually preferably 24 or less.

所述剝離層可在所述基材的背面，以在面內的任意方向為連續的平坦狀積層在整個面上，也可以圓點狀(點狀)、線條狀(條紋狀)等圖案狀積層在所述基材的背面。所述剝離層的附著量較佳為0.005g/m2 以上且0.1g/m2 以下。在對剝離劑進行塗佈與乾燥而形成剝離層時的附著量為去除揮發成分後的乾燥後的附著量。藉由將所述基材的背面層設為不含有矽酮化合物而積層的、對水的接觸角為110°以下的剝離層，能夠具備優異的印字性與剝離力。所述剝離層較佳對水的接觸角為110°以下，更佳為108°以下，特佳為106°以下。The release layer can be applied to the back of the substrate in a continuous, flat, and uniform manner across the entire surface, or in a patterned pattern such as dots or lines. The release layer preferably has a weight of 0.005 g/ m² to 0.1 g/ m² . The release layer is formed by applying and drying the release agent, and the weight after volatile components have been removed and the film is dried. By using a release layer on the back side of the substrate that does not contain a silicone compound and has a water contact angle of 110° or less, excellent printability and release force can be achieved. The release layer preferably has a water contact angle of 110° or less, more preferably 108° or less, and particularly preferably 106° or less.

將所述輥體重卷，以0.3m/min的剝離速度從所述黏著劑層上剝離所述基材的背面層時的剝離力較佳為0.1N/25mm以下。此外，以30m/min的剝離速度從所述黏著劑層上剝離所述基材的背面層時的剝離力較佳為0.3N/25mm以下。由此，能夠得到剝離力相對於剝離速度的變化少的性能。此外，在由輥體重卷表面保護膜時等，即使以高剝離速度也能夠容易地順利剝離。When the roll is rewound, the peeling force when peeling the back layer of the substrate from the adhesive layer at a peeling speed of 0.3 m/min is preferably 0.1 N/25 mm or less. Furthermore, when peeling the back layer of the substrate from the adhesive layer at a peeling speed of 30 m/min, the peeling force is preferably 0.3 N/25 mm or less. This achieves performance with minimal variation in peeling force with respect to peeling speed. Furthermore, even at high peeling speeds, such as when rewinding a surface protective film from a roll, it can be easily and smoothly peeled.

所述剝離層中可含有抗靜電劑而對其賦予抗靜電性能。由此，可將所述表面保護膜適用作抗靜電表面保護膜。所述剝離層的表面電阻值較佳為1.0×10＋ 11 Ω/□以下。藉由充分減小所述剝離層的表面電阻率，能夠降低伴隨著當從所述剝離層上剝離所述黏著劑層時所產生的靜電而生成的剝離帶電壓，因此在將所述表面保護膜貼合在被黏物上後，也能夠抑制對被黏物的電氣控制電路等造成影響。 作為抗靜電劑，可列舉出具有吡啶鎓陽離子、咪唑鎓陽離子、銨陽離子、鹼金屬陽離子等陽離子、以及六氟磷酸鹽(PF6 - )、硫化氰酸鹽(SCN- )、烷基苯磺酸鹽(RC6 H4 SO3 - )、過氯酸鹽(ClO4 - )、四氟硼酸鹽(BF4 - )、雙(氟磺醯基)醯亞胺鹽(FSI)、雙(三氟甲烷磺醯基)醯亞胺鹽(TFSI)、三氟甲烷磺酸鹽(TF)等陰離子的離子化合物。 此外，所述黏著劑層中可含有抗靜電劑。此外，在對不含有抗靜電劑的所述黏著劑層積層含有抗靜電劑的所述剝離層後，藉由隨著時間的推移而使抗靜電劑的一部分從所述剝離層移動至所述黏著劑層上，即使在從所述黏著劑層上剝離所述剝離層後，也可使抗靜電劑轉印至所述黏著劑層的表面。當所述黏著劑層或其表面具有抗靜電劑時，所述黏著劑層的表面電阻值較佳為1.0×10＋ 11 Ω/□以下。另外，所述剝離層或所述黏著劑層的抗靜電性能並非為必須的構成，可適當省略。The release layer may contain an antistatic agent to impart antistatic properties. This allows the surface protective film to be used as an antistatic surface protective film. The surface resistance of the release layer is preferably 1.0×10 + 11 Ω/□ or less. By sufficiently reducing the surface resistivity of the release layer, the peeling charge voltage generated by static electricity when the adhesive layer is peeled off from the release layer can be reduced. This reduces the impact on the adherend's electrical control circuits, etc., after the surface protective film is attached to the adherend. Examples of antistatic agents include ionic compounds having cations such as pyridinium cations, imidazolium cations, ammonium cations, and alkali metal cations, and anions such as hexafluorophosphate ( PF6- ) , thiocyanate ( SCN- ), alkylbenzenesulfonate ( RC6H4SO3- ), perchlorate ( ClO4- ) , tetrafluoroborate ( BF4- ), bis(fluorosulfonyl ) imide ( FSI ), bis(trifluoromethanesulfonyl)imide (TFSI), and trifluoromethanesulfonate (TF). The adhesive layer may contain an antistatic agent. Furthermore, after laminating the release layer containing the antistatic agent onto the adhesive layer that does not contain the antistatic agent, a portion of the antistatic agent migrates from the release layer onto the adhesive layer over time. This allows the antistatic agent to be transferred to the surface of the adhesive layer even after the release layer is peeled off from the adhesive layer. When the adhesive layer or its surface contains the antistatic agent, the surface resistance of the adhesive layer is preferably 1.0×10 + 11 Ω/□ or less. In addition, the anti-static properties of the peeling layer or the adhesive layer are not essential components and can be omitted as appropriate.

作為所述表面保護膜的黏著劑層所貼合的被黏物，可列舉出光學玻璃、光學膜或含有其的積層體、面板等。作為光學膜，可列舉出偏振膜、相位差膜、抗反射膜、防眩(防眩光)膜、紫外線吸收膜、紅外線吸收膜、光學補償膜、亮度提高膜、硬塗膜、透明導電膜等。作為可在製造步驟或產品中使用所述表面保護膜的電子裝置，可列舉出液晶面板、有機EL面板、觸控面版、電子紙等、或這些裝置的零件等。 為了將貼合有所述表面保護膜的光學膜安裝在電子裝置等產品中，可在光學膜的、與所述表面保護膜為相反側的面上積層第二黏著劑層。在該第二黏著劑層上可貼合其他光學構件，或者也可在貼合其他光學構件前覆蓋剝離膜。即，可構成「表面保護膜/光學膜/第二黏著劑層/剝離膜」、「表面保護膜/光學膜/第二黏著劑層/其他光學構件」等積層體。在這些積層體的表面露出表面保護膜的、所述基材的背面層。由於所述基材的背面層的印字性優異，因此能夠在所述基材的背面層上印字出管理積層體時所需的資訊等。由於油性油墨的印字性優異，因此印字的固著性優異。另外，印字的手段沒有特別限定，可使用利用了版的印刷、未利用版的噴墨等印刷、印或戳印(stamp)等。印字資訊不限於文字、數位，也可使用花樣、記號等。Examples of adherends to which the adhesive layer of the surface protection film is bonded include optical glass, optical films, laminates containing the same, and panels. Examples of optical films include polarizing films, retardation films, antireflection films, antiglare films, UV-absorbing films, infrared-absorbing films, optical compensation films, brightness-enhancing films, hard-coated films, and transparent conductive films. Examples of electronic devices that can utilize the surface protection film in manufacturing processes or products include liquid crystal panels, organic EL panels, touch panels, electronic paper, and components for these devices. To install the optical film, with the surface protection film attached, in products such as electronic devices, a second adhesive layer can be applied to the surface of the optical film opposite the surface protection film. Other optical components can be attached to this second adhesive layer, or a release film can be applied before attaching other optical components. In other words, a laminated structure such as "surface protection film/optical film/second adhesive layer/release film" or "surface protection film/optical film/second adhesive layer/other optical component" can be formed. On the surface of these laminated structures, the back surface of the substrate, the surface protection film, is exposed. The excellent printability of the backside layer of the substrate allows for printing information required for laminate management, etc. The excellent printability of the oil-based ink ensures excellent adherence of the printed information. Furthermore, the printing method is not particularly limited and can include printing using a plate, inkjet printing without a plate, stamping, or other methods. Printed information is not limited to text or numbers; patterns and symbols can also be used.

當所述表面保護膜的用途將偏振片(偏振膜)作為被黏物時，所述黏著劑層可貼合在偏振片的偏振鏡的保護層上。其中，作為偏振片的偏振鏡的保護層，可列舉出選自由三乙醯纖維素(TAC)類膜、聚甲基丙烯酸甲酯(PMMA)類膜、聚對苯二甲酸乙二醇酯(PET)類膜組成的組中的至少一種以上。此外，對偏振片的偏振鏡的保護層的表面實施的表面處理可以為選自由未處理的未修飾層(Plain)、防眩光(AG)處理、低反射(LR)處理、抗反射(AR)處理、防眩光-低反射(AG- LR)處理、防眩光-抗反射(AG-AR)處理組成的組中的至少一種以上。When the surface protection film is used with a polarizing plate (polarizing film) as an adherend, the adhesive layer can be bonded to the protective layer of the polarizer of the polarizing plate. Examples of the protective layer of the polarizer of the polarizing plate include at least one selected from the group consisting of triacetyl cellulose (TAC) films, polymethyl methacrylate (PMMA) films, and polyethylene terephthalate (PET) films. Furthermore, the surface treatment applied to the surface of the polarizer of the polarizing plate protective layer can be at least one selected from the group consisting of an untreated, unmodified layer (plain), an anti-glare (AG) treatment, a low-reflection (LR) treatment, an anti-reflection (AR) treatment, an anti-glare-low-reflection (AG-LR) treatment, and an anti-glare-anti-reflection (AG-AR) treatment.

在偏振片(偏振膜)等被黏物的表面上，可具有使用含有氟化合物的低折射率層形成用組合物而形成的低折射率層。作為用於低折射率層形成用組合物的氟化合物，可列舉出為氟化烯烴類、氟化乙烯醚類、氟化(甲基)丙烯酸烷基酯等中的一種或兩種以上的聚合物的含氟共聚物、含氟化烷基的矽烷化合物等的縮合物。除了被氟化的單體，含氟共聚物也可共聚有烯烴類、乙烯醚類、(甲基)丙烯酸酯等未被氟化的單體。低折射率層可與高折射率層等進行組合而構成抗反射層。Adherends such as polarizing films can have a low-refractive-index layer formed on their surfaces using a low-refractive-index layer-forming composition containing a fluorine compound. Examples of fluorine compounds used in the low-refractive-index layer-forming composition include fluorinated copolymers of one or more polymers of fluorinated olefins, fluorinated vinyl ethers, and fluorinated alkyl (meth)acrylates, and condensates of fluorinated alkyl-containing silane compounds. In addition to fluorinated monomers, fluorinated copolymers can also be copolymerized with non-fluorinated monomers such as olefins, vinyl ethers, and (meth)acrylates. The low-refractive-index layer can be combined with a high-refractive-index layer to form an antireflection layer.

所述表面保護膜的製造方法具有在所述基材的表面積層黏著劑層的步驟、以及在所述基材的背面積層剝離層的步驟。積層所述黏著劑層的步驟與積層所述剝離層的步驟的順序沒有特別限定，可先實施任一個步驟，也可同時實施兩個步驟。當在積層所述剝離層的步驟前實施積層所述黏著劑層的步驟時，為了保護所述黏著劑層，可貼合其他脫模膜。用於保護該黏著劑層的脫模膜較佳為不具有剝離層的膜或具有不含矽酮化合物的剝離層的膜。 ［實施例］The method for producing the surface protection film comprises the steps of depositing an adhesive layer on the surface of the substrate and depositing a release layer on the backside of the substrate. The order of depositing the adhesive layer and the release layer is not particularly limited; either step may be performed first, or both steps may be performed simultaneously. When depositing the adhesive layer before depositing the release layer, a separate release film may be applied to protect the adhesive layer. The release film used to protect the adhesive layer is preferably a film without a release layer or a film with a release layer that does not contain a silicone compound. [Example]

以下，藉由實施例對本發明進行具體說明。Hereinafter, the present invention will be described in detail through examples.

＜丙烯酸類聚合物的製備＞ [實施例1] 向具備攪拌機、溫度計、回流冷凝器及氮氣導入管的反應裝置中導入氮氣，用氮氣置換反應裝置內的空氣。然後，向反應裝置中加入90重量份的丙烯酸2-乙基己酯、10重量份的丙烯酸異壬酯、5重量份的聚丙二醇單丙烯酸酯(環氧烷的平均重複數n=12)、4.0重量份的丙烯酸8-羥基辛酯及60重量份的溶劑(乙酸乙酯)。然後，以2小時滴加0.1重量份的作為聚合引發劑的偶氮雙異丁腈，以65℃反應6小時，得到用於實施例1的丙烯酸類聚合物溶液。 [實施例2~4及比較例1~4] 除了以表1的(A)組~(C)組的記載設定各單體的組成以外，以與上述用於實施例1的丙烯酸類聚合物溶液相同的方式得到用於實施例2~4及比較例1~4的丙烯酸類聚合物溶液。<Preparation of Acrylic Polymer> [Example 1] Nitrogen was introduced into a reaction apparatus equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube to replace the atmosphere within the reaction apparatus with nitrogen. Then, 90 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of isononyl acrylate, 5 parts by weight of polypropylene glycol monoacrylate (average number of repeats of alkylene oxide n = 12), 4.0 parts by weight of 8-hydroxyoctyl acrylate, and 60 parts by weight of solvent (ethyl acetate) were added to the reaction apparatus. Subsequently, 0.1 parts by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and the reaction was carried out at 65°C for 6 hours to obtain the acrylic polymer solution used in Example 1. [Examples 2-4 and Comparative Examples 1-4] Except that the monomer compositions were set as described in Groups (A) to (C) in Table 1, acrylic polymer solutions for Examples 2-4 and Comparative Examples 1-4 were prepared in the same manner as the acrylic polymer solution for Example 1.

＜表面保護膜的製造＞ [實施例1] 對藉由上述方式製備的實施例1的丙烯酸類聚合物溶液，添加2.0重量份的CORONATE HX、0.1重量份的參乙醯丙酮鈦、9重量份的乙醯丙酮，並進行攪拌混合，從而得到黏著劑組合物。在將該黏著劑組合物塗佈在聚酯膜的表面上後，以90℃進行乾燥，由此去除溶劑，其中，所述聚酯膜預先在背面以0.03g/m2 的附著量塗佈長鏈烷基懸垂化合物(中京油脂股份有限公司製造，產品名稱：Resem P-677)而積層剝離層。然後，在23℃、50%RH的氣氛下進行7天熟化，由此交聯黏著劑組合物，得到實施例1的表面保護膜。黏著劑層的厚度示於表4。 [實施例2~4及比較例1~4] 除了以表1的(D)組~(F)組的記載分別設定針對黏著劑組合物的添加劑的組成、以表1的(G)組的記載設定用於剝離層的剝離劑及附著量以外，以與上述的實施例1的表面保護膜相同的方式得到實施例2~4及比較例1~4的表面保護膜。<Production of Surface Protective Film> [Example 1] To the acrylic polymer solution of Example 1 prepared as described above, 2.0 parts by weight of CORONATE HX, 0.1 parts by weight of titanium trisacetylacetonate, and 9 parts by weight of acetylacetone were added and stirred to obtain an adhesive composition. This adhesive composition was applied to the surface of a polyester film, which had previously been coated with a long-chain alkyl pendant compound (manufactured by Chungyo Oil & Fats Co., Ltd., product name: Resem P-677) at a coverage of 0.03 g/ m² on the back surface, and then dried at 90°C to remove the solvent. The adhesive composition was then aged for 7 days at 23°C and 50% RH to crosslink the adhesive composition, thereby obtaining the surface protection film of Example 1. The thickness of the adhesive layer is shown in Table 4. [Examples 2-4 and Comparative Examples 1-4] Surface protection films of Examples 2-4 and Comparative Examples 1-4 were obtained in the same manner as the surface protection film of Example 1, except that the composition of the additives for the adhesive composition was set according to Groups (D) to (F) in Table 1, and the release agent and the amount of adhesion for the release layer were set according to Group (G) in Table 1.

[表1]   (A) (B) (C) (D) (E) (F) (G) 實施例1 2EHA 90 INA 10 B-1 5 8HOA 4.0 HX 2.0 (1.83) TI 0.1 (0.09) AA 9 (8.26) G-1 0.03 實施例2 NA 20 IOA 20 2EHA 60 B-2 8 6HHA 4.5 HL 2.0 (1.78) FE 0.05 (0.04) AA 8 (7.11) G-2 0.02 實施例3 HA 55 2EHA 45 B-3 4 4HBA 1.0 HEA 3.0 D-165N 1.5 (1.39) FE 0.04 (0.04) AA 6.0 (5.56) G-3 0.008 實施例4 2EHA 90 OA 10 B-2 10 4HBA 0.5 HEA 4.0 HX 2.0 (1.75) TI 0.04 (0.03) AA 5.0 (4.37) G-1 0.04 比較例1 2EHA 80 MA 20 B-1 5 8HOA 5.5 HX 2.0 (1.81) TI 0.1 (0.09) AA 9 (8.14) G-1 0.03 比較例2 2EHA 90 OA 10 B-4 5 4HBA 0.5 HEA 4.0 D-110N 1.5 (1.37) FE 0.02 (0.02) AA 15.0 (13.7) G-3 0.01 比較例3 2EHA 90 OA 10 B-2 10 4HBA 0.5 HEA 4.0 HX 2.0 (1.75) TI 0.04 (0.03) AA 5.0 (4.37) G-4 0.02 比較例4 2EHA 90 OA 10 B-2 10 4HBA 0.5 HEA 4.0 HX 2.0 (1.75) FE 0.04 (0.03) AA 6.0 (5.24) G-1 0.04 [Table 1] (A) (B) (C) (D) (E) (F) (G) Example 1 2EHA 90 INA 10 B-1 5 8HOA 4.0 HX 2.0 (1.83) TI 0.1 (0.09) AA 9 (8.26) G-1 0.03 Example 2 NA 20 IOA 20 2EHA 60 B-2 8 6HHA 4.5 HL 2.0 (1.78) FE 0.05 (0.04) AA 8 (7.11) G-2 0.02 Example 3 HA 55 2EHA 45 B-3 4 4HBA 1.0 HEA 3.0 D-165N 1.5 (1.39) FE 0.04 (0.04) AA 6.0 (5.56) G-3 0.008 Example 4 2EHA 90 OA 10 B-2 10 4HBA 0.5 HEA 4.0 HX 2.0 (1.75) TI 0.04 (0.03) AA 5.0 (4.37) G-1 0.04 Comparative example 1 2EHA 80 MA 20 B-1 5 8HOA 5.5 HX 2.0 (1.81) TI 0.1 (0.09) AA 9 (8.14) G-1 0.03 Comparative example 2 2EHA 90 OA 10 B-4 5 4HBA 0.5 HEA 4.0 D-110N 1.5 (1.37) FE 0.02 (0.02) AA 15.0 (13.7) G-3 0.01 Comparative example 3 2EHA 90 OA 10 B-2 10 4HBA 0.5 HEA 4.0 HX 2.0 (1.75) TI 0.04 (0.03) AA 5.0 (4.37) G-4 0.02 Comparative example 4 2EHA 90 OA 10 B-2 10 4HBA 0.5 HEA 4.0 HX 2.0 (1.75) FE 0.04 (0.03) AA 6.0 (5.24) G-1 0.04

在表1中，示出將(A)組的合計設為100重量份而求出的重量份的數值。在(D)組~(F)組中，在括弧( )內示出將丙烯酸類聚合物設為100重量份而求出的重量份的數值。此外，在(G)組中示出附著量(g/m2 )的數值。Table 1 shows the values in parts by weight based on 100 parts by weight for Group (A). In Groups (D) to (F), the values in parentheses ( ) show the values in parts by weight based on 100 parts by weight of the acrylic polymer. Furthermore, the values for the adhesion amount (g/m 2 ) are shown for Group (G).

此外，將表1中使用的各成分的縮寫符號的化合物名稱示於表2。另外，CORONATE(註冊商標)HX及HL為TOSOH股份有限公司的產品名稱，TAKENATE(註冊商標)D-165N及D-110N為三井化學(Mitsui Chemicals)股份有限公司的產品名稱。Resem P-677為中京油脂股份有限公司的產品名稱，RP-20為日本觸媒股份有限公司的產品名稱，Peeloil (註冊商標)1010為Lion Specialty Chemicals股份有限公司的產品名稱。Table 2 shows the compound names of the abbreviations of the components used in Table 1. CORONATE (registered trademark) HX and HL are product names of TOSOH Co., Ltd., TAKENATE (registered trademark) D-165N and D-110N are product names of Mitsui Chemicals Co., Ltd., Resem P-677 is a product name of Chukyo Oil & Fats Co., Ltd., RP-20 is a product name of Nippon Catalyst Co., Ltd., and Peeloil (registered trademark) 1010 is a product name of Lion Specialty Chemicals Co., Ltd.

[表2] 組 縮寫符號 化合物名 (A) NA 丙烯酸正壬酯 HA 丙烯酸正己酯 2EHA 丙烯酸2-乙基己酯 INA 丙烯酸異壬酯 IOA 丙烯酸異辛酯 OA 丙烯酸辛酯 MA 丙烯酸甲酯 (B) B-1 聚丙二醇單丙烯酸酯(n=12) B-2 甲氧基聚乙二醇丙烯酸酯(n=8) B-3 甲氧基聚乙二醇甲基丙烯酸酯(n=9) B-4 甲氧基聚乙二醇甲基丙烯酸酯(n=23) (C) 8HOA 丙烯酸8-羥基辛酯 6HHA 丙烯酸6-羥基己酯 4HBA 丙烯酸4-羥基丁酯 HEA 丙烯酸2-羥基乙酯 (D) HX CORONATE HX(HDI異氰脲酸酯體) HL CORONATE HL(HDI加合物) D-165N TAKENATE D-165N(HDI縮二脲體) D-110N D-110N(XDI加合物) (E) TI 三乙醯丙酮鈦 FE 參(2,4-戊二酮)鐵(III) (F) AA 乙醯丙酮 (G) G-1 Resem P-677(長鏈烷基懸垂化合物) G-2 ＲP-20(長鏈烷基懸垂化合物) G-3 Peeloil 1010(長鏈烷基懸垂化合物) G-4 矽酮剝離劑 [Table 2] Group abbreviations Compound name (A) NA n-nonyl acrylate HA n-Hexyl acrylate 2EHA 2-Ethylhexyl acrylate INA Isononyl acrylate IOA Isooctyl acrylate OA Octyl acrylate MA Methyl acrylate (B) B-1 Polypropylene glycol monoacrylate (n=12) B-2 Methoxy polyethylene glycol acrylate (n=8) B-3 Methoxy polyethylene glycol methacrylate (n=9) B-4 Methoxy polyethylene glycol methacrylate (n=23) (C) 8HOA 8-Hydroxyoctyl acrylate 6HHA 6-Hydroxyhexyl acrylate 4HBA 4-Hydroxybutyl acrylate HEA 2-Hydroxyethyl acrylate (D) HX CORONATE HX (HDI isocyanurate) HL CORONATE HL(HDI adduct) D-165N TAKENATE D-165N (HDI biuret) D-110N D-110N (XDI adduct) (E) TI Titanium triacetone FE Tris(2,4-pentanedione)iron(III) (F) AA acetylacetone (G) G-1 Resem P-677 (Long-chain alkyl pendant compound) G-2 RP-20 (Long-chain alkyl pendant compound) G-3 Peeloil 1010 (Long-chain alkyl pendant compound) G-4 Silicone strippers

＜測定方法及評價＞ 藉由下述方法評價實施例1~4及比較例1~4中的表面保護膜。<Measurement Methods and Evaluation> The surface protection films of Examples 1-4 and Comparative Examples 1-4 were evaluated using the following methods.

＜接觸角的測定方法＞ 滴加1滴純水使其與表面保護膜的剝離層的表面接觸，在經過10秒後使用接觸角計(協和界面科學(Kyowa Interface Science)股份有限公司製造，型號：DMo-701)，測定接觸角(°)。Contact Angle Measurement Method: Add one drop of pure water to the surface of the release layer of the surface protective film. After 10 seconds, measure the contact angle (°) using a contact angle meter (Kyowa Interface Science Co., Ltd., Model: DMo-701).

＜剝離力的測定方法＞ 測定作為以180°方向、0.3m/min或30m/min的速度從黏著劑層上剝離表面保護膜的基材的背面層時的剝離強度的、剝離力(N/25mm)。<Peel Force Measurement Method> The peel force (N/25mm) was measured when the back layer of a surface protective film was peeled from the adhesive layer at a 180° angle at a speed of 0.3 m/min or 30 m/min.

＜印字性的評價方法＞ 使用戳印用的油性油墨(製造者：Shachihata 股份有限公司，產品名稱：XQTR-20-SG-R)，在表面保護膜的剝離層的表面上印字，在使油性油墨自然乾燥後，以肉眼觀察印字的清晰性、有無滲色。 關於印字性的評價基準，將印字清晰且無滲色的情況評價為「○」，將印字不清晰、存在滲色的情況評價為「×」。<Printability Evaluation Method> Using stamp-printing oil-based ink (manufacturer: Shachihata Co., Ltd., product name: XQTR-20-SG-R), we printed on the release layer of the surface protective film. After the oil-based ink dried naturally, the print was visually inspected for clarity and the presence of bleeding. The printability evaluation criteria were: "O" for clear printing with no bleeding, and "X" for unclear printing with bleeding.

＜黏著力的測定方法＞ 隔著表面保護膜的黏著劑層，用壓輥將表面保護膜貼合在用丙酮清洗過的鈉鈣玻璃的非錫面上，以50℃、0.5MPa×20分鐘的條件進行壓熱處理(autoclave treatment)後，恢復至23℃×50%RH的空氣氣氛下，經過1小時。然後，使用拉伸試驗機，以JIS Z0237「黏著膠帶-黏著片試驗方法」為基準測定表面保護膜的剝離強度，將沿180°方向以0.3m/min或30m/min的速度進行剝離時的剝離強度設為黏著劑層的黏著力(N/25mm)。Adhesion Measurement Method: The surface protective film was applied to the non-tin surface of a sodium calcium glass sheet cleaned with acetone using a roller, with the adhesive layer interposed between them. The sheet was then autoclaved at 50°C and 0.5 MPa for 20 minutes. The sheet was then returned to an air atmosphere of 23°C and 50% RH for one hour. The peel strength of the surface protective film was then measured using a tensile tester in accordance with JIS Z0237, "Adhesive Tapes - Adhesive Sheets - Test Methods." The peel strength measured when peeled at a 180° angle at a speed of 0.3 m/min or 30 m/min was defined as the adhesive layer's adhesion (N/25 mm).

＜低污染性的評價方法＞ 使用貼合機，經由雙面黏著膠帶等黏著劑層，在玻璃板的單面上貼合被黏物的偏振片。然後，使用貼合機在所述偏振片的表面上貼合表面保護膜的黏著劑層。在23℃×50%RH的空氣氣氛下經過3天及30天期間的保管後，剝離表面保護膜，以肉眼觀察所述偏振片的表面的污染狀態。其中，被黏物的偏振片的偏振鏡的保護層由三乙醯纖維素(TAC)類膜構成，所述保護層的表面上所實施的表面處理為未處理(Plain)。 關於低污染性的評價基準，對於所述偏振片的表面，將在3天及30天保管時均無污染的情況評價為「○」，將在3天或30天保管中的任一情況下有少許污染的情況評價為「△」，將在3天或30天保管時均有污染的情況評價為「×」。<Evaluation Method for Low Contamination> A polarizing plate (adherent) was bonded to one side of a glass plate using a laminating machine via an adhesive layer such as double-sided adhesive tape. A surface protective film (adherent adhesive layer) was then bonded to the surface of the polarizing plate using the laminating machine. After storage in an atmosphere of 23°C and 50% RH for 3 and 30 days, the surface protective film was removed and the surface contamination of the polarizing plate was visually inspected. The protective layer of the polarizing filter of the adherend was composed of a triacetyl cellulose (TAC) film, and the surface treatment applied to the protective layer was untreated (plain). Regarding the evaluation criteria for low contamination, the surface of the polarizer was evaluated as "○" if there was no contamination after both 3 days and 30 days of storage, "△" if there was slight contamination after either 3 days or 30 days of storage, and "×" if there was contamination after both 3 days and 30 days of storage.

表3中，對於為表面保護膜的基材的背面層的剝離層，示出了藉由上述方法測定的接觸角、剝離力及印字性的試驗結果。Table 3 shows the test results of the contact angle, peeling force, and printability measured by the above-mentioned method for the peeling layer of the back surface layer of the substrate, which is a surface protective film.

[表3] 表面保護膜的基材的背面層(剝離層)的試驗結果   接觸角 剝離力 [N/25mm] 印字性   ［°］ 0.3m/min 30m/min   實施例1 105 0.03 0.25 ○ 實施例2 103 0.02 0.20 ○ 實施例3 102 0.02 0.15 ○ 實施例4 105 0.02 0.21 ○ 比較例1 105 0.04 0.60 ○ 比較例2 102 0.03 0.25 ○ 比較例3 112 0.01 0.10 × 比較例4 105 0.03 0.40 ○ [Table 3] Test results of the back layer (peel-off layer) of the surface protection film substrate Contact angle peeling force [N/25mm] Printing [°] 0.3m/min 30m/min Example 1 105 0.03 0.25 ○ Example 2 103 0.02 0.20 ○ Example 3 102 0.02 0.15 ○ Example 4 105 0.02 0.21 ○ Comparative example 1 105 0.04 0.60 ○ Comparative example 2 102 0.03 0.25 ○ Comparative example 3 112 0.01 0.10 × Comparative example 4 105 0.03 0.40 ○

此外，表4中，對於表面保護膜的黏著劑層，示出了黏著劑層的厚度、及藉由上述方法測定的黏著力及低污染性的試驗結果。Table 4 shows the thickness of the adhesive layer of the surface protection film, and the test results of the adhesive strength and low-staining properties measured by the above-mentioned method.

[表4] 表面保護膜的黏著劑層的試驗結果   厚度 黏著力 [N/25mm] 低污染性   [μm] 0.3m/min 30m/min TAC-Plain 實施例1 15 0.04 0.5 ○ 實施例2 10 0.03 0.3 ○ 實施例3 5 0.02 0.2 ○ 實施例4 15 0.03 0.4 ○ 比較例1 15 0.04 2.8 ○ 比較例2 15 0.12 1.5 △ 比較例3 15 0.03 0.4 ○ 比較例4 25 0.06 0.8 ○ [Table 4] Test results of the adhesive layer of the surface protection film thickness Adhesion [N/25mm] Low pollution [μm] 0.3m/min 30m/min TAC-Plain Example 1 15 0.04 0.5 ○ Example 2 10 0.03 0.3 ○ Example 3 5 0.02 0.2 ○ Example 4 15 0.03 0.4 ○ Comparative example 1 15 0.04 2.8 ○ Comparative example 2 15 0.12 1.5 △ Comparative example 3 15 0.03 0.4 ○ Comparative example 4 25 0.06 0.8 ○

本發明的實施例1~4的表面保護膜由於以0.3m/min的剝離速度從黏著劑層上剝離基材的背面層時的剝離力為0.1N/25mm以下，以30m/min的剝離速度從黏著劑層上剝離基材的背面層時的剝離力為0.3N/25mm以下，因此能夠提高由輥體放卷時的操作性。 此外，本發明的實施例1~4的表面保護膜由於以0.3m/min的低剝離速度進行剝離時的黏著劑層對鈉鈣玻璃(非錫面)的黏著力為0.01N/25mm以上且0.1N/25mm以下，且以30m/min的高剝離速度進行剝離時的黏著劑層對鈉鈣玻璃(非錫面)的黏著力為1.0N/25mm以下，因此在低剝離速度與高剝離速度下的黏著力的平衡優異，能夠提高在將表面保護膜貼合在被黏物前的再操作(重新貼合)時或在將使用後的表面保護膜從被黏物上剝離去除時的操作性(handling ability)。 此外，本發明的實施例1~4的表面保護膜的基材的背面層為不含矽酮化合物而積層的剝離層，不存在引起因矽酮對被黏物造成污染擔憂，印字性也優異。The surface protection films of Examples 1 to 4 of the present invention exhibit a peeling force of 0.1 N/25 mm or less when peeling the back layer of the substrate from the adhesive layer at a peeling speed of 0.3 m/min, and a peeling force of 0.3 N/25 mm or less when peeling the back layer of the substrate from the adhesive layer at a peeling speed of 30 m/min. This improves operability when unwinding the film from a roll. Furthermore, the surface protection films of Examples 1 to 4 of the present invention exhibit adhesion strength of the adhesive layer to sodium calcium glass (non-tin surface) of 0.01 N/25 mm or more and 0.1 N/25 mm or less when peeled at a low peeling speed of 0.3 m/min, and adhesion strength of the adhesive layer to sodium calcium glass (non-tin surface) of 1.0 N/25 mm or less when peeled at a high peeling speed of 30 m/min. Consequently, the surface protection films exhibit an excellent balance of adhesion strength at both low and high peeling speeds, improving handling during re-lamination before attaching the surface protection film to an adherend or when peeling the surface protection film from an adherend after use. Furthermore, the backside layer of the substrate of the surface protection films of Examples 1 to 4 of the present invention is a release layer that is laminated without containing a silicone compound, thereby eliminating concerns about silicone contamination of the adherend and providing excellent printability.

即，根據本發明的實施例1~4的表面保護膜，能夠達成本發明的技術問題，即提供一種無隔片型的、被卷成輥狀的輥體的表面保護膜，其中，所述基材的背面層的印字性優異，即使不具備含有矽酮的剝離層，也能夠降低所述基材的背面層與所述黏著劑層的剝離力，且降低對被黏物的污染性。 此外，根據本發明的實施例1~4的表面保護膜，能夠達成本發明的另一個技術問題，即提供一種無隔片型的表面保護膜，其能夠取得低速度剝離區域與高速度剝離區域中的黏著力的平衡，即使從被黏物上高速剝離時，也能夠以較小的力進行再剝離。Specifically, the surface protection films of Examples 1 to 4 of the present invention achieve the technical problem of the present invention, namely, providing a spacer-less, roll-shaped surface protection film, wherein the back layer of the substrate exhibits excellent printability, and even without a silicone-containing release layer, the release force between the back layer of the substrate and the adhesive layer is reduced, thereby reducing contamination to adherends. Furthermore, the surface protection films of Examples 1 to 4 of the present invention can achieve another technical problem of the present invention, namely, providing a spacer-less surface protection film that can achieve a balance of adhesive forces between the low-speed peeling area and the high-speed peeling area. Even when peeling from the adherend at high speed, it can be peeled off again with less force.

比較例1的表面保護膜在以30m/min的剝離速度從黏著劑層上剝離基材的背面層時的剝離力較高，為0.60N/25mm，在以30m/min的高剝離速度進行剝離時的黏著劑層對鈉鈣玻璃(非錫面)的黏著力較高，為2.8N/25mm。因此，比較例1的表面保護膜未能降低基材的背面層與黏著劑層的剝離力，且從被黏物上高速剝離時難以再剝離。 比較例2的表面保護膜以0.3m/min的低剝離速度進行剝離時的黏著劑層對鈉鈣玻璃(非錫面)的黏著力為0.12N/25mm，以30m/min的高剝離速度進行剝離時的黏著劑層對鈉鈣玻璃(非錫面)的黏著力為1.5N/25mm。因此，比較例2的表面保護膜在從被黏物上高速剝離時難以再剝離。此外，降低對被黏物的污染性的效果稍差。 比較例3的表面保護膜由於基材的背面層為含有矽酮類剝離劑的剝離層，因此對水的接觸角較大，為112°，此外，印字性差。 比較例4的表面保護膜以30m/min的剝離速度從黏著劑層上剝離基材的背面層時的剝離力為0.40N/25mm。因此，比較例4的表面保護未能降低基材的背面層與黏著劑層的剝離力。The surface protection film of Comparative Example 1 exhibited a relatively high peeling force of 0.60 N/25 mm when peeling the back layer of the substrate from the adhesive layer at a peeling speed of 30 m/min. Furthermore, the adhesive layer exhibited a relatively high adhesion force of 2.8 N/25 mm to sodium calcium glass (non-tin surface) when peeled at a high peeling speed of 30 m/min. Therefore, the surface protection film of Comparative Example 1 failed to reduce the peeling force between the back layer of the substrate and the adhesive layer, and was difficult to remove from the adherend at high speed. The surface protection film of Comparative Example 2 exhibited adhesion of 0.12 N/25 mm to sodium calcium glass (non-tin surface) when peeled at a low peeling speed of 0.3 m/min, and 1.5 N/25 mm when peeled at a high peeling speed of 30 m/min. Therefore, the surface protection film of Comparative Example 2 was difficult to remove from the adherend at high speed. Furthermore, its effectiveness in reducing adherend contamination was somewhat limited. Because the surface protection film in Comparative Example 3 contains a silicone-based release agent on the backside of the substrate, its contact angle with water is relatively large, at 112°, and its printing properties are poor. The surface protection film in Comparative Example 4 exhibited a peeling force of 0.40 N/25 mm when peeling the backside layer from the adhesive layer at a peeling speed of 30 m/min. Therefore, the surface protection film in Comparative Example 4 failed to reduce the peeling force between the backside layer of the substrate and the adhesive layer.

因此，比較例1~4的表面保護膜未能達成本發明的技術問題，即提供一種無隔片型的、被卷成輥狀的輥體的表面保護膜，其中，所述基材的背面層的印字性優異，即使不具備含有矽酮的剝離層，也能夠降低所述基材的背面層與所述黏著劑層的剝離力，且降低對被黏物的污染性。 此外，在比較例1、2的表面保護膜未能達成本發明的另一個技術問題，即提供一種無隔片型的表面保護膜，其能夠取得低速度剝離區域與高速度剝離區域中的黏著力的平衡，即使從被黏物上高速剝離時，能夠以較小的力進行再剝離。Therefore, the surface protection films of Comparative Examples 1-4 fail to achieve the technical problem of the present invention, namely, to provide a spacerless, roll-shaped surface protection film, wherein the backside layer of the substrate has excellent printability, and even without a silicone-containing release layer, the peeling force between the backside layer of the substrate and the adhesive layer is reduced, thereby reducing adherend contamination. Furthermore, the surface protection films of Comparative Examples 1 and 2 fail to achieve another technical problem of the present invention, namely, to provide a spacerless surface protection film that achieves a balance of adhesive forces between low- and high-speed peeling zones, allowing for re-peeling with minimal force even when peeled from an adherend at high speed.

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無。without.

Claims (3)

一種表面保護膜，其為將由黏著劑組合物交聯而成的黏著劑層積層在聚酯膜的基材的單面上而形成的表面保護膜，所述黏著劑組合物含有丙烯酸類聚合物、(D)交聯劑、(E)交聯促進劑及(F)酮-烯醇互變異構體化合物，所述表面保護膜的特徵在於，所述丙烯酸類聚合物為：相對於合計100重量份的作為(A)烷基的碳原子數為C5~C14的(甲基)丙烯酸烷基酯單體的、選自由丙烯酸正己酯、丙烯酸2-乙基己酯、丙烯酸正壬酯、丙烯酸異壬酯、丙烯酸正辛酯、及丙烯酸異辛酯組成的化合物組中的至少二種以上，共聚合計1.0~20重量份的作為(B)含聚伸烷基二醇鏈的單(甲基)丙烯酸酯單體的、構成聚環氧烷的環氧烷的平均重複數為4~14的化合物中的至少一種以上，及合計1.0~10重量份的作為(C)不含有羧基而含有羥基作為官能團的共聚性乙烯基單體的、選自由(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸6-羥基己酯、丙烯酸4-羥基丁酯、及(甲基)丙烯酸2-羥基乙酯組成的化合物組中的至少一種以上共聚而成的丙烯酸類聚合物，所述(D)交聯劑為選自由六亞甲基二異氰酸酯的縮二脲改性體、異氰脲酸酯改性體、加合物改性體組成的組中的至少一種以上化合物的三官能度以上的異氰酸酯化合物，所述(E)交聯促進劑為選自由鋁螯合化合物、鈦螯合化合物、鐵螯合化合物組成的組中的至少一種以上，所述黏著劑組合物相對於100重量份的所述丙烯酸類聚合物，以0.5~5重量份的比例含有所述(D)交聯劑，以0.001~0.5重量份的比例含有所述(E)交聯促進劑，並且以0.1~300重量份的比例含有所述(F)酮-烯醇互變異構體化合物，所述(F)酮-烯醇互變異構體化合物/所述(E)交聯促進劑的重量份比率為70~1000，在所述基材的與積層有所述黏著劑層的面為相反側的面上，積層有基材的背面層，所述基材的背面層為不含矽酮化合物，含有長鏈烷基懸垂化合物的樹脂組合物製成剝離層而進行積層，且對水的接觸角為110°以下，作為所述基材的背面層的所述剝離層的附著量為0.005g/m2以上且0.1g/m2以下，所述黏著劑層的厚度為3~18μm，所述表面保護膜為不使用脫模膜而進行捲繞，且所述基材的背面層與所述黏著劑層相接而成的輥體，對所述輥體進行重卷，以0.3m/min的剝離速度從所述黏著劑層上剝離所述基材的背面層時的剝離力為0.1N/25mm以下，且以30m/min的剝離速度從所述黏著劑層上剝離所述基材的背面層時的剝離力為0.3N/25mm以下。A surface protective film is formed by laminating an adhesive layer formed by crosslinking an adhesive composition on one side of a polyester film substrate. The adhesive composition contains an acrylic polymer, (D) a crosslinking agent, (E) a crosslinking promoter, and (F) a keto-enol tautomer compound. The surface protective film is characterized in that the acrylic polymer is: (A) an alkyl (meth)acrylate monomer having a carbon number of C5 to C14 selected from the group consisting of n-hexyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, isononyl acrylate, and n-octyl acrylate, relative to a total of 100 parts by weight of the alkyl (meth)acrylate monomer having an alkyl group with a carbon number of C5 to C14. , and isooctyl acrylate, copolymerized with 1.0 to 20 parts by weight of at least one compound selected from the group consisting of (B) a mono(meth)acrylate monomer containing a polyalkylene glycol chain, wherein the average number of repetitions of the alkylene oxide constituting the polyalkylene oxide is 4 to 14, and 1.0 to 10 parts by weight of at least one compound selected from the group consisting of 8-hydroxyoctyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 4-hydroxybutyl acrylate, and 2-hydroxyethyl (meth)acrylate as a copolymerizable vinyl monomer containing a hydroxyl group as a functional group instead of a carboxyl group. The acrylic polymer obtained by copolymerization of the above, the crosslinking agent (D) is a trifunctional or higher isocyanate compound selected from the group consisting of biuret-modified, isocyanurate-modified, and adduct-modified hexamethylene diisocyanate, the crosslinking accelerator (E) is at least one selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds, and the adhesive composition contains the crosslinking agent (D) in a ratio of 0.5 to 5 parts by weight and the crosslinking accelerator (E) in a ratio of 0.001 to 0.5 parts by weight based on 100 parts by weight of the acrylic polymer. ) crosslinking accelerator, and containing the (F) keto-enol tautomer compound in a ratio of 0.1 to 300 parts by weight, the (F) keto-enol tautomer compound/the (E) crosslinking accelerator being 70 to 1000 parts by weight, a back layer of the substrate being layered on the surface of the substrate opposite to the surface on which the adhesive layer is layered, the back layer of the substrate being a release layer made of a resin composition containing no silicone compound and a long-chain alkyl pendant compound, and having a contact angle with water of 110° or less, and an adhesion amount of the release layer as the back layer of the substrate being 0.005 g/m 2 and less than 0.1 g/m 2 , the thickness of the adhesive layer is 3 to 18 μm, the surface protective film is wound without using a release film, and the back layer of the substrate and the adhesive layer are in contact with each other to form a roll, the roll is rewound, and the peeling force when the back layer of the substrate is peeled off from the adhesive layer at a peeling speed of 0.3 m/min is less than 0.1 N/25 mm, and the peeling force when the back layer of the substrate is peeled off from the adhesive layer at a peeling speed of 30 m/min is less than 0.3 N/25 mm. 如請求項1所述的表面保護膜，其中，所述聚酯膜的基材的厚度為38μm，以0.3m/min的剝離速度進行剝離時，所述黏著劑層對鈉鈣玻璃(非錫面)黏著力為0.01N/25mm以上且0.1N/25mm以下，且以30m/min的剝離速度進行剝離時，所述黏著劑層對鈉鈣玻璃(非錫面)黏著力為1.0N/25mm以下。The surface protection film according to claim 1, wherein the thickness of the polyester film substrate is 38 μm, and when peeling at a peeling speed of 0.3 m/min, the adhesion of the adhesive layer to sodium calcium glass (non-tin surface) is greater than 0.01 N/25 mm and less than 0.1 N/25 mm, and when peeling at a peeling speed of 30 m/min, the adhesion of the adhesive layer to sodium calcium glass (non-tin surface) is less than 1.0 N/25 mm. 一種光學膜，其特徵在於，其由貼合如請求項1或2所述的表面保護膜而成。An optical film is characterized in that it is formed by laminating the surface protection film as described in claim 1 or 2.
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