TW201033322A - Surface protective film - Google Patents

Abstract

The present invention relates a surface protective film which is useful for protecting the surface of various resin plate, glass plate, metal plate and the like used in the fields of building materials, electrical appliances and electronic components when adhered onto their surface to prevent the adherend from scratches, contamination and the like during storage, transportation and post-processing. In particular, the present invention provides a surface-protective film as a resin of an adhesive layer used to surface protective film, wherein the resins obtain by using a specific mixing ratio to mix a styrene base elastomer or the resin of tree components having a block copolymer with specific crystallinity olefin block, an amorphous α -olefinic polymer and a crystallinity olefinic polymer. The surface protective film has extreme adhesiveness to the surface of concave-convex adherend and also exhibiting excellent automatic performance.

Description

201033322 VI. Description of the Invention: [Technical Field] The present invention relates to a surface protective film based on various optical films, various resin plates, glass plates, and metal plates used for protection in electrical/electronic fields, construction materials, and the like. The surface is adhered to the surface for the purpose of surface cleaning, and the protective adhesive is scratched and contaminated during storage, handling, and post-processing. In particular, a surface protective film exhibits good adhesion to an object having irregularities on the surface of the adherend, and has good handleability. ® [Prior Art] For the basic performance requirements of the surface protective film, for the above-mentioned various adherends, it is not involved in wrinkles or air, and it also has superior adhesion workability; During storage, transportation, etc., there is an appropriate adhesive force that does not float or peel off; the environmental change during storage of the adherend or the change in adhesion due to the subsequent processing is small, and it is easy to peel off. Moreover, it does not contaminate the surface of the adherend after peeling. G A conventional surface protective film is a film made of a polyvinyl chloride resin, a polyethylene resin, a polypropylene resin or the like as a substrate, and is adhered to an urethane-based, an acrylic-based or a rubber-based adhesive. The agent is applied to one side of the article. However, such a surface protective film has a problem in that the adhesion between the film and the adhesive of the substrate is deteriorated, or the cohesive force of the adhesive itself is lowered, and the adhesive is peeled off from the adherend. One part of the adhesive remains on the surface of the adherend. Further, the surface protective film produced by applying the adhesive to the film has the following problems and the like: since the minimum of 2 steps of the step of manufacturing the film for the substrate and the step of applying the adhesive is -4-201033322 The manufacturing cost becomes high; in the coating step of the adhesive, the environmental load is increased as necessary to remove a large amount of solvent. In order to improve the above problems, a self-adhesive surface protective film which simultaneously extrudes a film layer and an adhesive layer of a substrate by a co-extrusion lamination method has been proposed. Such a surface protective film, for example, has proposed an adhesive film which is characterized by having 10 to 50 parts by mass of a polyethylene resin based on 100 parts by mass of the hydrogenated product of the styrene-conjugated diene polymer. Adhesive composition of the adhesive layer (for example, refer to the patent document Qin 1 0) °

However, in the case of the surface protective film provided in Patent Document 1, there is a problem that the adhesion to the object having irregularities on the surface of the adherend becomes insufficient. [Problem to be Solved by the Invention] The problem to be solved by the present invention is to provide a surface protective film which is an adherend having a concave-convex shape on a surface. It has a practical adhesive force, and after being taken up in a roll shape, it is slowly taken out and used, so that the so-called agglomeration which causes the base layer and the adhesive layer to adhere to each other does not cause condensation, and is peeled off after being peeled off. On the surface of the adhesive, the solidification of the paste is small and the workability is good. Means for Solving the Problems The present inventors have found the following facts in order to solve the above problems, and have found the following facts: a surface protective film can be obtained, and styrene-based elasticity is mixed at a specific blending ratio. When a block or a block copolymer having a specific crystalline olefin block, a non-crystalline ex-olefin polymer, and a resin of three components of a crystalline olefin polymer are used, the adhesive layer used for the surface protection 201033322 film Even when the surface of the adherend has an uneven shape, it has a practical adhesive force. The paste on the surface of the adherend after agglomeration or peeling has little residue and good workability, that is, the present invention is a surface protection. a film characterized by having a surface protective film of a substrate layer (A) and an adhesive layer (B), and the adhesive layer (b) is obtained by mixing the following composition as a main component: 50 to 85% by mass of hydrogenated benzene a copolymer (B1-1) of a styrene-based random copolymer block having a double bond portion of a vinyl polymer block and a random copolymer of styrene and a conjugated diene compound, or a hydrogenated formula aba or ab Styrene intercalation as shown in (a olefin polymer block, b-based conjugated diene polymer block or double bond portion of a conjugated diene polymer) a segment copolymer (B1-2), or a block copolymer obtained by blocking a crystalline olefin polymer block of a hydrogenated conjugated diene polymer block and a conjugated diene polymer (Β1·3); 5 to 45% by mass of the amorphous α-dilute hydrocarbon polymer (Β2); and 5 to 45% by mass of the crystalline olefin polymer (Β3). Advantageous Effects of Invention The surface protective film of the present invention is attached to an optical film having various irregularities on the surface, various resin plates, glass plates, gold enamel plates, etc., and the adhesive force changes little with time even when exposed to a high temperature environment. And there is no floating or peeling from the adherend, and the bending does not occur in the heat resistance of the adherend or the like, and the non-stick residue on the surface of the adherent after peeling can be visually confirmed, and further, After being taken up in a roll shape, the agglomerates which are used without being extracted again have excellent anti-caking properties. [Embodiment] Hereinafter, the present invention will be described in detail. The surface protective film of the present invention is a multilayer film having at least a substrate layer and an adhesive layer. 201033322 The resin used for the base material layer (A) of the surface protective film in the present invention is not particularly limited, and it is preferred to use an olefin polymer as a main component, for example, a propylene homopolymer, A propylene-based copolymer such as a propylene-gasethylene copolymer or a propylene-ethylene-1-butene copolymer; a vinyl-based polymer such as a low-density polyethylene, a medium-density polyethylene or a high-density polyethylene. These olefin-based polymers may be used singly or in combination of two or more. Among these olefin-based polymers, the surface protective film of the present invention is adhered to various optical films, resin sheets, glass plates, metal sheets, etc., and then subjected to drying, heat forming, etc., and exposed to a high temperature environment. In the case of use, it is preferable to use a crystalline propylene-based polymer in the case of being wound into a roll for long-term storage, and it is more preferable to use a propylene homopolymer from the viewpoint of improving the heat resistance of the surface protective film. Further, in the application of the present invention, the term "crystallinity" means a peak of 0.5 J/g or more in the range of 95 to 25 °C in D S C (measured by differential scanning calorimetry). Further, the above-mentioned propylene-based polymer means a melt flow rate (hereinafter referred to as "MFR of 230 ° C." According to JIS K7210: 199 99, preferably measured at 230 ° C, 21.18 N) is 0.5~ 30.0 g/10 min, the melting point is 120 to 165 ° C, more preferably 230 ° C, the MFR is 2.0 to 15.0 g/10 min, and the melting point is 125 to 162 ° C. If the MFR and the melting point are in this range, even if it is exposed to a high temperature environment by drying, heating, or the like after being adhered to the adherend, the film shrinks due to the shrinkage of the film, and there is no floating or peeling, and the bending does not occur in the film. In the adhesive, the film forming property of the laminated film is also improved. On the other hand, in the case where the surface protective film is adhered to the adherend in the state of the adherend, the surface of the adhesive film is cut and processed, and the surface protective film is placed on the surface to be cut off, and no threading occurs. From the viewpoint of the heat-resistant property of 201033322, it is more preferable to use low-density polyethylene and high-density grease from the viewpoint of the cuttability of poor appearance such as fluffing. Further, the above ethylene-based polymer means that the melt flow is referred to as "MFR at 190 °C". It is easy and preferable to form 〇·5 to 30.0 g/10 according to jIS K7210: °C, 21.18N); more preferably MFRi minutes at 190 °C. Further, the melting point of these ethylene-based polymers is preferably from 105 to 130 °C. When the melting point is in this range, it is dried by drying, heating, or the like after being adhered. Since the shrinkage of the film is small, it is possible to suppress the bending of the adherend or the adherend. Further, in the application of the present invention, "the mass ratio of the specific resin or the mixed fat or the mixture thereof in each layer is 65% by mass or more as the main component body mass. In order to take the surface of the adherend The surface of the present invention (B) must be mixed with the following copolymer as a main component of the reduction of the follow-up residue of the unevenness/the anti-caking property: the hydrogenated styrene-based polymer block and the benzene-ethylate a styrene-based copolymer (B1-1) having a double bond portion of a copolymer, a hydrogenated formula aba or ab (a block, a b-based conjugated diene polymer block or a conjugated double bond) a polymer (B1-2) represented by an olefin polymer block), or a block of a hydrogenated conjugated diene polymer hydrocarbon polymer block and a conjugated diene polymer, and j (Bl-3); 5~ 45% by mass of amorphous alpha-olefin polyethylene mixed tree rate (below '1 999, due to 1 90 minutes, so that the extrusion is poisonous 2.0~1 5.0g/10 blue is 90~135 °C, even if By sticking to a high temperature environment, the floating or peeling of the object means the specific tree relative to the whole thing: preferably Adhesive layer of 80-mass and paste-protected film after peeling: 50 to 85% by mass of styrene-based block co-embedded in a-type styrene-polymerized diene polymer of olefin and conjugated diene-regulated copolymer block a segmental crystalline olefin copolymer copolymer (B2); 201033322 and 5 to 45 mass% of a crystalline olefin polymer (B3). The copolymer (B1-1) or the styrene The conjugated diene compound used for the raw material of the block copolymer (Bi 2 ) may, for example, be hydrazine, 3-butadiene, isoprene or 2,3-dimethyl-1,3-pentane. Alkene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3_xin And chloroprene, etc., 1,3-butadiene and isoprene are preferably used from the viewpoint of ease of industrial availability. Further, a styrene-based compound which forms a styrene block is exemplified, for example. : styrene, α-methylstyrene, p-methylstyrene, tert-butylstyrene, divinylstyrene, 1,1-diphenylstyrene, N,N-dimethyl-amino-amine Styrene, N,N-diethyl-p-amine Styrene, etc., preferably styrene. In the case of using the copolymer (B1-1) or the styrenic block copolymer (Bl_2), the viewpoint based on the superiority of the follow-up property to the finer surface irregularities The mass ratio of the structure derived from the styrene-based compound/structure derived from the conjugated diene in the copolymer is preferably in the range of from 5/95 to 60/40. Further, the block copolymer (B1- 3) The crystalline olefin block (I) which is a hydrogenated conjugated diene polymer block and the conjugated diene polymer block (II) are (Ι-Π) ni or (Ι-Π) n2- ( I) (nl, π2 is an integer of 1 or more). At least one terminal of the polymer chain shown is preferably a crystalline olefin polymer block (I). Such a block copolymer (Β1-3) is exemplified by Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Specifically, a polymer obtained by synthesizing a polybutadiene polymer block having a low 1,2-ethylene bond content (for example, 25% or less) and a conjugated diene compound as a main component can be used. a copolymer comprising a 1,2- and 3,4-bonded polymer having a high content (for example, 50% or more), and hydrogenating the copolymer by 201033322 to form the polybutadiene portion. A structure similar to polyethylene is used to form a crystalline polymer block or the like. The conjugated suspicion compound used as a raw material of the block copolymer (B1-3) can be exemplified by any of the above copolymers (B1-1) or the styrenic block copolymer (B1-2). The conjugated diene compound is similar to the 1,3-butadiene or isoprene from the viewpoint of ease of industrial availability. For example, the copolymer (B1 -1 ) of the commercially available product may be a styrene-butadiene random copolymer hydrogenated product (hereinafter abbreviated as HSBR), which is manufactured by JSR AG, "Dinalonl 320P"; The block copolymer (B1-2): styrene-isoprene-styrene block copolymer (hereinafter abbreviated as SIS), "SIS5200" manufactured by JSR AG, styrene-ethylene/butyl "Dinalon 8600P, Dinalon 8601 P" manufactured by JSR Corporation, which is an styrene-styrene block copolymer (hereinafter abbreviated as SEBS), and a styrene-ethylene/propylene-styrene block copolymer (hereinafter, abbreviated as S EPS) </ br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br> (hereinafter, referred to as CEBC.) "Dinalon 6200P" manufactured by JSR Corporation. The non-crystalline α-olefin-based block copolymer (B2) used for the surface protective film adhesive layer (B) of the present invention is a polymer containing a monomer unit based on an α-olefin having 3 to 20 carbon atoms. In the measurement range of -100 to 200 ° C of the differential scanning calorimeter (DSC), any of the crystallization peaks in which the melting heat of the crystallization is 1 J/g or more and the crystallization heat is 1 J/g or more Unobserved polymer. The α-olefin having 3 to 20 carbon atoms may be linear or branched, and may be exemplified by propylene, 1-butene, 1-pentene, and 1-hexene. , 1-heptene, 1-octene, 1-decene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1 a linear alpha-olefin such as a fifteen carbonene, a 1-hexadecene, a 1-hexadecene, a 1-octadecene, a 1-nonadecene or a 1-eicosene; -methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1 a branched α-olefin such as pentene. Further, the amorphous α-olefin polymer (Β2) is preferably a polymer containing two or more kinds of such α-olefins, more preferably one type of propylene-based monomer unit and φ on carbon. A polymer of 4 to 20 alpha-olefin monomer units. Further, the monomer other than the above olefin may be contained in the amorphous α-olefin polymer (Β2). Examples of such a monomer include ethylene, a polyene compound, a cyclic olefin, and a vinyl aromatic compound. Among the amorphous α-olefin polymers (Β2), a non-crystalline propylene-1-butene copolymer and an amorphous propylene-ethylene-oxime-butene copolymer are preferred. These copolymers may be used alone or in combination of two or more. Φ When the total monomer unit of the amorphous propylene-1-butene copolymer is 100% by mass, the amorphous propylene-i-butyl The monomer unit based on the susceptibility of the olefin copolymer is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. If the monomer unit based on propylene is in this range, the heat resistance will be improved. When the total monomer unit of the amorphous propylene-ethylene-oxime-butene copolymer is 100% by mass, the monomer unit based on the suspicion of the non-crystalline propylene-ethylene-1-butene copolymer is Preferably, it is 5 〇 mass% or more, more preferably 60 mass% or more. If the propylene-based monomer unit is in this range, the heat resistance will be improved. Further, the monomeric unit based on ethylene in the amorphous propylene-ethylene-butene copolymer -11-201033322 is preferably 10% by mass or more, more preferably 2% by mass or more. If the monomer unit based on ethylene is in this range, the adhesive layer will become softer. Even in the case where the surface of the adhesive has irregularities, it adheres closely to the shape of the unevenness, and the adhesion is sufficient. Will be available. Further, the ultimate viscosity [η] of the amorphous α-olefin polymer (B2) is preferably in the range of 0.1 to 1 Torr, 〇 dl / g, more preferably 0.7 to 7.0 dl / g. Further, the molecular weight distribution (Mw/Mn) represented by a ratio 0 of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably larger than 1, and not more than 4, more preferably 2 to 3. When the ultimate viscosity and molecular weight distribution of the amorphous α-olefin polymer (B2) are in this range, heat resistance, transparency, and adhesion are improved, and even if the adherend of the surface protective film is adhered for a long period of time, it is exposed. In a high-temperature environment, the low molecular weight component in the amorphous α-olefin polymer (Β 2 ) is not transferred to the surface of the adherend to contaminate the adherend. In addition, since the amorphous α-olefin polymer (Β2) is an olefin polymer, for example, when an ethylene-vinyl acetate copolymer is used for the adhesive layer, adhesion due to deterioration of the resin such as deacetic acid is not caused. As time goes by, after a long period of time, it can maintain the stability of stability. The method for producing the amorphous α-olefin polymer (B2) is, for example, a gas phase polymerization method, a solution polymerization method, a paste polymerization method, or a bulk polymerization method, which is carried out by a metallocene catalyst. The method of polymerization. A more preferable production method is the production method disclosed in Japanese Laid-Open Patent Publication No. 2002-348417. The crystalline olefin-based polymer (Β3) used for the adhesive layer of the surface protective film of the present invention may, for example, be a propylene homopolymer, a propylene-ethylene copolymer or a propylene-ethylene-1-butene copolymer. The propylene polymer; low density -12- 201033322 Polyethylene, medium density polyethylene, high density polyethylene, linear low density B, etc. Further, the above propylene-based polymer is preferably 230 t: the MFR is 〜3〇_og/io minutes' melting point is 12〇~i65-c, more preferably 230〇C2 is 2.0~15.0g/l〇 minute . Further, the above ethylene-based polymer is preferably 190. (The MFR is 〜3 0.0g/10 minutes' makes extrusion molding easy and preferable; more preferably, °CiMFR is 2.0 to 15. 〇g/l〇 minutes. The adhesive layer (B) of the present invention is mixed. 50 to 85% by mass of the total (B1-1), the styrene block copolymer (B1-2), or the interpolymer (B1-3); 5 to 45% by mass of the amorphous α- Olefin-based poly(Β2); blended with 5 to 45% by mass of a crystalline olefin-based polymer (Β3) if the composition (Bl-1), (Β1-2) or (Β1-3) is 50 mass When % is used, the adhesion of the protective film will be insufficient; if it exceeds 85%, the adhesion of the protective film is too strong, and there is a problem that the operation will become trapped and the residue will occur. In addition, if the composition (Β2) is blended, When the blending ratio is less than 5% by mass or more than 45% by mass, the surface is an uneven-shaped adherend, and the adhesive force is insufficient, and the component (Β3) is adjusted within the above range. The blending ratio is adjusted to the desired adhesive strength. The surface protective film of the present invention is composed of at least two layers of a substrate layer as described above, and may further The surface layer is provided on the base material layer (the resin having the surface opposite to the surface having the adhesive layer for the surface layer (C) is not particularly limited', based on the viewpoint of good affinity with the base (Α), For example, a low-density polyethylene, a linear low-density polyethylene, a 0.5 GFR, a 0.5 190 polymer segment, a low-mass, a low-quality, and a ratio-to-table are used. Energy and adhesion (C)) 0 layer, in the case of dense-13- ❹ 201033322 degree polyethylene, high density polyethylene, propylene homopolymer, f polymer, propylene-ethylene-1-butene copolymer, propylene -1-butene-etc. Among these olefin-based polymers, the film formation by the laminated film is preferably low-density polyethylene, linear low-density polyethylene, olefin, high-density polyethylene, and propylene homopolymerization. In addition, the resin used for the surface layer (C) is used as a main component of the mixed resin of the above-mentioned propylene-ethylene block copolymer, and the surface of the surface layer is modified into a pear-skin pattern. Skin pattern, which is easy to cause strong adhesion at the time of design. Here, propylene-ethylene is a block-polymerized propylene and ethylene resin, which is used for the surface, and the surface of the resin layer is preferably limited to a pear-skin pattern. For example, it can be exemplified by polymerization of polypropylene in the same manner. The material is subjected to polymerization of ethylene or polymerization of ethylene and propylene to obtain a β block copolymer, etc. Among these copolymers, propylene which is derived from the content of ethylene component is preferably used because it is easily formed into a pattern. - an ethylene block copolymer, more preferably a propylene-ethylene block copolymer derived from a vinyl group of 10 to 15% by mass in terms of easy extrusion processing, and a propylene-ethylene block copolymerized grease of 23 ° C The MFR is preferably 4 to 12 g/min, more preferably minutes. The density is preferably 0.890 to 0.91 Og/cm3, more preferably 0.905 g/cm3. The surface protective film of the present invention has a total film thickness of preferably 20 to 20%. If the film thickness is in this range, the protective property of the adherend is preserved. During the transfer, etc., workability such as floating or peeling does not occur, and adhesion/peeling is good. In addition, the viscous olefinic ethylene ethylene copolymer will be improved, and the medium-density polyethylene resin can also be used as a surface layer of the surface layer, which can block the copolymer ruthenium layer (C) without being present. Next, the β propylene-ethylene surface is made into a pear containing 8 to 20 olefin components. In addition, the mixed tree of the substrate: 6~1 0 g / 0.895~ - 1 2 Ο μ m ° If, the adhesion property of the adhesive J, the layer I (B)-14-201033322 The thickness is preferably 3~ 30 μιη, more preferably 5 to 25 μιη. When the thickness of the adhesive layer (B) is in this range, the adhesive property and the film forming property of the laminated film which are not caused by floating or peeling are good during storage and transportation of the adherend. Further, in the case where the surface layer (C) is provided on the surface protective film of the present invention, the thickness of the surface layer (C) is preferably from 3 to 30 μm, more preferably from 5 to 20 μm. When the thickness of the surface layer (C) is in this range, the heat resistance and the film formability of the laminated film are excellent. The method for producing the surface protective film of the present invention is not particularly limited as long as it is a co-extrusion lamination method, and for example, a resin for melting each resin layer by using two or more crucible extruders After laminating in a molten state by a co-extrusion method such as a co-extrusion extruder method or a feed block method, the film is processed into a film by a method such as blow molding, T-die/cooling roll method, or the like. The method. In the case of the T-die/cooling roll method, it is also possible to knead the melted laminated film between the rubber touch roll or the stainless steel belt and the like to cool the film. Further, the surface protective film of the present invention can be extended at least in a uniaxial direction. The stretching method can employ various methods such as uniaxial stretching in the longitudinal direction or in the transverse direction, sequential biaxial stretching, simultaneous biaxial stretching, or tubular biaxial stretching. In addition, the extension step can be either an in-line or an off-line. The extension method of the uniaxial extension may be a near roll extension method or a calendering method. The stretching ratio in the longitudinal direction or the transverse direction of the uniaxial stretching is preferably from 1.1 to 80 times, more preferably from 3 to 30 times. On the other hand, the stretching ratio of the biaxial stretching is preferably 1.2 to 70 times, more preferably 4 to 6 times in the longitudinal direction, 5 to 9 times in the lateral direction, and 20 to 54 times in the area ratio. In addition, the step of extending in the longitudinal direction or the lateral direction is not necessarily limited to one-stage extension, and may also be a plurality of-stage extension. In particular, in the longitudinal uniaxial stretching such as the longitudinal uniaxial roll extension and the longitudinal uniaxial rolling extension in the sequential biaxial stretching, the viewpoint of the thickness, the uniformity of the physical properties of -15 to 201033322, etc., is preferably a multi-stage extension. Furthermore, in the proximity roller extension, either the flat method or the cross method can be used, and it is more desirable to reduce the multi-section near-cross extension of the reduced width. In the case of uniaxial stretching, the elongation temperature of any of the stretching methods is preferably 80 to 160 ° C, and the uniaxial stretching and tenter stretching are preferably 90 to 1 65 ° C. In addition, the preferred extension temperatures are 1 1 〇 to 1 5 5 ° C and 1 20 to 1 60 ° C, respectively. On the other hand, in the case of biaxial stretching, either method is preferably the same extension temperature range as in the case of uniaxial stretching. Further, before the stretching step, φ may be appropriately provided after the preheating portion and the stretching step. In this case, the temperature of the preheating portion is preferably 60 to 140 ° C, and the temperature of the heat fixing portion is preferably in the range of 90 to 160 °C. The surface protective film of the present invention is formed by at least uniaxially extending, thermally stabilized, and desirably structurally stabilized, and is thermally aligned by the alignment of the base layer (A) having an olefin polymer as a main component, and heat resistance. It will be further improved because the change in adhesion over time will be smaller and better. Further, the φ adhesion-imparting agent may be added as appropriate within a range not impairing the effects of the present invention. There is no particular limitation, and a general-purpose adhesive such as an aliphatic copolymer, an aromatic copolymer, an aliphatic/aromatic copolymer or an alicyclic copolymer can be used; a rosin-based resin such as a coumarone-anthraquinone resin, an anthraquinone resin, a phenol resin, or a polymerized rosin; a phenol resin, a xylene resin, or a hydrogenated product thereof; Two or more types may be used alone or in combination. Further, a lubricant, an anti-caking agent, an ultraviolet absorber, a light stabilizer, an antistatic agent, an antifogging agent, or the like, a coloring agent, or the like may be added as appropriate within a range not impairing the effects of the present invention. These additives are preferably various additives for use in the olefin-based poly-16-201033322 compound. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples. (Synthesis example) [Synthesis of non-crystalline "-olefin-based polymer (non-crystalline propylene-1 -butene copolymer)] In a 100 L stainless steel polymerization vessel equipped with a stirrer, hydrogen was used as a molecular weight modifier. The propylene and 1-butene are continuously copolymerized to obtain a non-crystalline-1_butylene copolymer in which Q is a non-crystalline α-anhydrocarbon polymer. Specifically, 'from the lower part of the polymerizer', hexane was used as a polymerization solvent, and propylene and 1-butene were continuously supplied at a supply rate of 1001 ^ / hour, respectively, at 24.00 μm / hour, 1.811 ° / hour, from the polymerizer. In the upper portion, the reaction mixture was continuously withdrawn by maintaining the reaction mixture in the polymerization vessel at 100 L. In addition, from the lower part of the polymerizer, the dimethyl sulfonium dichloride (tetramethylcyclopentane) as a catalyst component was continuously supplied at a supply rate of 0_005 g/hr, 〇.298 g/hr, and 2.315 g/hr, respectively. Bismuth) (3-tert-butyl-5-methyl-2-phenoxy)titanium, triphenylmethyltetrakis(pentafluorophenyl)borate, triisobutylaluminum. The co-polymerization reaction was carried out at 45 ° C by circulating cooling water in a jacket installed outside the polymerization vessel. A small amount of ethanol is added to the reaction mixture continuously withdrawn from the upper portion of the polymerization vessel. After the polymerization reaction is stopped, the monomer removal, water washing, and solvent removal steps are carried out to obtain a non-crystalline propylene-1-butene copolymer. Then, the obtained copolymer was dried under reduced pressure at 80 ° C for 24 hours. The content of the propylene monomer unit in the amorphous propylene-1-butene copolymer was 94.5% by mass, and the content of the 1-butene monomer unit was 5.5% by mass. Further, the melting peak in the DSC of the copolymer was not observed, and the ultimate viscosity [η] was 2 - 3 dl / g and the molecular weight distribution (Mw / Mn ) was 2.2. -17- 201033322 (Adjustment) [Preparation of non-crystalline α-olefin polymer] Non-crystalline propylene-1-butene copolymer / crystalline propylene-1-butene copolymer = 95/5 (Quality) Crystalline propylene-1-butene copolymer [density: 0.900 g/cm3, MFR (230 °C, 21.18 Ν): 10.〇g/i〇 minutes, maximum melting peak in DSC 126 °C] blended with the amorphous propylene-1-butene copolymer obtained in the soil, and further blended with 2000 ppm of an aromatic phosphite-based antioxidant (Irgafos 168, manufactured by Ciba Specialty φ Chemicals Co., Ltd.) And a hindered phenol-based antioxidant ("Irganox 1010" manufactured by Ciba Specialty Chemicals Co., Ltd.)" was melt-mixed by a twin-screw extruder, and then a non-crystalline ?-olefin-based polymer composition was obtained by a granulator. Nine of the things. (Example 1) The resin for the surface layer was mixed with low-density polyethylene so that the mass ratio became 15/85 [density: 0.902 g/cm3, MFR (19〇t:, 21.18Ν) · 4g/l〇 minute: Hereinafter referred to as "LDPE". And a propylene-ethylene block copolymer; a metallocene catalyst-based propylene-ethylene random copolymer for a resin for a base material layer [density: 0.900 g/cm3, MFR (230 ° C, 21.18 N): 7.0 g /10 minutes, the content of ethylene monomer units · 3.5% by mass; hereinafter referred to as "COPP". The resin for the adhesive layer is used in a hydride of a styrene/butadiene random copolymer ("Dinalon 1 320P" manufactured by JSR Corporation, hereinafter referred to as "HSBR"). 35 parts by mass of the amorphous α-olefin polymer composition and linear low-density polyethylene [density: 920.920 g/cm 3 , MFR (19 (TC, 21.18 N): 3 g/10 min; hereinafter referred to as " LLDPE". 10 parts by mass of the resin composition, 10 parts by mass of the alicyclic petroleum resin (Japanese -18 - 201033322 "ARKON P-125" manufactured by Arakawa Chemical Co., Ltd.) The group was supplied to a surface layer extruder (caliber 50 mm), a substrate layer machine (caliber 50 mm), and an adhesive layer extruder (caliber 40 mm) coextrusion method at an extrusion temperature of 250 ° C from T - The die was extruded so that the surface degree was 12 μm, the thickness of the base material layer was 36 μm, and the adhesive layer was 12 μm, and it was cooled by a water-cooled metal at 40° C., and then wound up on a roll to obtain a surface protective film. The resulting matured room at 35 °C in order to stabilize the physical properties (Example 2) A mixture of HSBR, a non-crystalline α-olefin polymer and LLDPE is mixed at 65/25/10 with respect to 100 parts by mass of the resin for the adhesive layer. A surface protective film obtained in the same manner as in Example 1 was obtained except that the ARKON®-125 10 composition was blended. (Example 3) The resin layer of the adhesive layer was used in an amount of 100 parts by mass. A mixture of HSBR and a non-crystalline α-olefin-based polymer group LLDPE was mixed at /10/5, and a surface protective film was obtained in the same manner as in Example 1 except that a mixture of ARKON®-125 10 mass was used. (Example 4) A styrene-ethylene/propylene-styrene block ("septon 2063" manufactured by Kuraray Co., Ltd.) was mixed at 5 5/3 5/10 with respect to 100 parts by mass of the resin for the adhesive layer. - "SEPS".), non-crystalline α-olefin polymer composition and product, by extrusion, by the thick thickness of the layer into a roll, cold film system, hourly mass ratio, composition amount 2 mass ratio of components and parts of group 3

The mass ratio copolymer F was referred to as a mixture of LLDPE -19-201033322, and a film of Example 4 was obtained in the same manner as in Example 1 except that a mixture of 1.0 parts by mass of ARKON P-125 was blended. (Example 5) A mixture of SEPS and a non-crystalline α-olefin-based polymer group LLDPE was mixed at 65/2 5/10 with respect to 100 parts by mass of the resin for the adhesive layer, and blended ARKON® was used. A surface protection film was obtained in the same manner as in Example 1 except that the amount of the product was 125. (Example 6) A styrene-isoprene block copolymer ("SR5200" manufactured by JSR Division; below) was mixed with 5 5/3 5 / 10 in addition to 100 parts by mass of the resin for the adhesive layer. The surface protective film of Example 6 was obtained by the same formula as the mixture of the amorphous hydrocarbon polymer composition and the LLDPE, except that 10 parts by mass of the P-125 was blended. . (Example 7)

In addition, the styrene-isobutadiene block copolymer ("SIBSTAR 072T", manufactured by Kaneka Co., Ltd.) is mixed with 5 5/3 5 / 10 in addition to 100 parts by mass of the resin for the adhesive layer. "SIBS".) A mixture of a non-crystalline α-dilute-based polymer composition and a mixture of 10 parts by mass of ARKON®-125 was blended, and Example 7 was obtained in the same manner as in Example 1. Protective film. (Example 8) The mass ratio of the product to the surface mass ratio of the composition and the mass of the group 5 is equal to the mass ratio of the shareholding α-ene ARKON 1 , and the hydride is referred to as the LLDPE product. 201033322 In addition to 100 parts by mass of the resin for the adhesive layer, styrene-ethylene/butylene-styrene copolymer (Dinalon 88601P manufactured by JSR AG) is mixed at a mass ratio of 55/3 5/10; SEBS"), a mixture of a non-crystalline a-olefin polymer composition and LLDPE, which was obtained in the same manner as in Example 1 except that a composition of 10 parts by mass of ARKON P-125 was blended was used. Surface protection film. (Example 9) The crystalline olefin-ethylene/butene copolymer was mixed at a mass ratio of 5 5/40/5 in terms of a mass ratio of 1 part by mass, based on 1 part by mass of the resin for the adhesive layer. A crystalline olefin block copolymer (Dinalon 6200P, manufactured by JSR Corporation; hereinafter referred to as "CEBC"), a mixture of an amorphous α-olefin polymer composition and LLDPE, blended with ARKON®-125 10 A surface protective film of Example 9 was obtained in the same manner as in Example 1 except for the composition of parts by mass. (Example 1 〇) 高 High-density polyethylene was mixed in the resin for the base layer at a mass ratio of 50/50 [density: 〇96 g/cm3, MFR (190 ° C, 21.18 Ν): 138 The surface protective film of Example 10 was obtained in the same manner as in Example 1 except that it was used in the same manner as in Example 1 except that it was used in the following manner. (Example 1 1) A surface protective film of Example 11 was obtained in the same manner as in Example 5 except that the resin for the base layer was mixed with HDPE and LDPE in a mass ratio of 50/50. -21 - 201033322 (Example 1 2) Example 1 was obtained in the same manner as in Example 6 except that the resin for the base layer was mixed with HDPE and LDPE in a mass ratio of 5 0/5 0. 2 surface protection film. (Comparative Example 1) The same procedure as in the Example was carried out except that a mixture of HSBR and LLDPE was mixed at a mass ratio of 85/15 with respect to 100 parts by mass of the resin for the adhesive layer, and a composition of 10 parts by mass of ARKONP-125 was blended. The surface protective film of Comparative Example 1 was obtained in the manner of 1. (Comparative Example 2) A mixture of HSBR, a non-crystalline α-olefin-based polymer composition and LLDPE was mixed at a mass ratio of 40/50/10, in addition to 100 parts by mass of the resin for the adhesive layer. A surface protective film of Comparative Example 2 was obtained in the same manner as in Example 1 except that 10 parts by mass of the composition of ARKONP-125 was used. (Comparative Example 3) 混合物 A mixture of HSBR, a non-crystalline α-olefin polymer composition and LLDPE is mixed at a mass ratio of 90/3/7, in addition to 100 parts by mass of the resin for the adhesive layer. A surface protective film of Comparative Example 3 was obtained in the same manner as in Example 1 except that a composition of 10 parts by mass of ARKON®-125 was blended. (Comparative Example 4)

The mixture of SEPS and LLDPE was mixed at a mass ratio of 85/15 with respect to 100 parts by mass of the resin for the adhesive layer, and the same was carried out except that a composition of 10 parts by mass of ARKON-22-201033322 P-125 was blended. The surface protective film of Comparative Example 4 was obtained in the same manner as in Example 1. (Comparative Example 5) The resin for the adhesive layer was mixed with HDPE and LDPE in a mass ratio of 5 0/5 0, and the resin layer for the adhesive layer was HSBR/LLDPE = 85 with respect to 100 parts by mass. A surface protective film of Comparative Example 5 was obtained in the same manner as in Example 1 except that a mixture of 10 parts by mass of ARKON P-125 was blended. Using the surface protective films obtained in the above Examples 1 to 11 and Comparative Examples 1 to 5, the following measurements and evaluations were carried out: (1) The adhesion was measured in a constant temperature chamber at 23 ° C and 50% RH, according to Jis Z0237: 2000 adhesion evaluation method, the surface protective film is adhered to the surface of the convex shape (convex pitch 25 μιη, tip angle 90 °) of the adherend. After being allowed to stand for 30 minutes in a constant temperature room at 23 ° C for 30 minutes, the film was allowed to stand for 30 minutes, and then subjected to a tensile tester (manufactured by A&amp;D Co., Ltd., Japan) at 300 mm/min. The speed was peeled off in the 180° direction to measure the initial adhesion. (2) Evaluation of paste residue In a constant temperature chamber of 23 ° C and 50% RH, the surface protective film was adhered to an acrylic plate of 15 cm in length and 5 cm in width according to the method of JIS Z0237: 2000 (mirror finish, Mitsubishi 1 of Japan) ^丫〇11 The whole company of the company "eight €11丫1^1丁£"). The film was placed in a dryer at 60 ° C for 3 days, and then cooled in a constant temperature room at 23 ° C for 1 hour. From the cooled test piece, the film was quickly peeled off by hand in the direction of 180 °, and the contamination state of the surface of the propylene-23-201033322 acid plate was visually confirmed, and the residual residue was evaluated on the following basis: ◦: There is no blur on the surface of the acrylic plate, white streaks, foreign matter and the like. X: There is any one of blurring, white streaks, foreign matter, and the like on the surface of the acrylic plate. (3) Evaluation of anti-caking property The surface protective film obtained was cut in the size of A4 (longitudinal 297 mm x transverse 210 mm). At this time, the extrusion direction (MD direction) when the film was formed was cut so as to coincide with the longitudinal direction of the ® A4. After the 1 piece of the film was overlaid, the plate was clamped with a plate of vinyl chloride having a size of A4 and a thickness of 3 mm, and a hammer of 5 kg was placed and stored in a dryer at 40 ° C for 14 days, at 23 Store in a constant temperature room at °C and 50% RH for 1 hour. Next, the film was cut in a width of 25 mm in the MD direction, and a tensile tester (manufactured by A&M Co., Ltd., Japan) was used at a speed of 300 mm/min. The direction was peeled off and the anti-caking force was measured. From the obtained anti-caking force, it was evaluated according to the following criteria. ^ Anti-caking property: 〇: The anti-caking force was lower than 〇.8N/25 mm. X: The anti-caking force is 〇_8N/25mm or more. The results obtained by using the layer structure of the surface protective film produced above and the surface protective film of these were shown in Tables 1 to 4. -24- 201033322 [Table 1]

Example 1 Example 2 Example 3 Example 4 LDPE 15 15 15 1 5 Surface layer resin group propylene-ethylene block co-formation (% by mass) Polymer 8 5 8 5 8 5 8 5 Thickness of surface layer (&quot; m) 12 12 12 12 Table base layer resin group COPP 1 00 10 0 10 0 10 0 Surface formation (trade volume %) Thickness of the substrate layer (//m) 3 6 3 6 3 6 3 6 HSBR 5 5 6 5 8 5 Film SEPS 5 5 Amorphous propylene - 3 3.25 2 3.75 9.5 3 3.2 5 Adhesive layer resin group 1-butene cohesion (% by mass) Crystalline propylene - 1.7 5 1.2 5 0.5 1.7 5 1-butene co-cohesive LLDPE 10 10 5 10 P-1 2 5 10 10 10 10 Thickness of the adhesive layer Um) 12 12 12 12 Thickness of all films (&quot;m) 6 0 6 0 6 0 6 0 Adhesion (N/2 5 mm) 0.0 3 5 0.0 3 5 0.0 2 0 0·0 3 5 Paste residue 〇〇〇〇 Anti-caking property 〇〇〇〇-25- 201033322

[Table 2] Example 5 Example 6 Example 7 Example 8 LDPE 15 15 15 15 Surface layer resin composition (% by mass) Propylene-acetamethylene segment copolymer 8 5 8 5 8 5 8 5 Thickness of surface layer (&quot ;m) 12 12 1 2 12 Surface base layer resin composition valence %) COPP 100 10 0 100 1 00 Thickness of the surface substrate layer Um) 3 6 3 6 3 6 3 6 Guarantee SEPS 6 5 SIS 55 film SIBS 5 5 SEBS 5 5 constitutes the adhesive layer resin composition (% by mass) Amorphous propylene-1-butene cohesion 2 3.75 3 3.25 3 3-2 5 3 3.25 Crystalline propylene-1-butene cohesion 1.2 5 1-7 5 1.7 5 1.7 5 LLDPE 1 0 10 10 10 P-1 2 5 10 10 10 10 Thickness of the adhesive layer Um) 12 12 12 12 Thickness of all films Um) 6 0 6 0 6 0 6 0 Initial adhesion Force (N/2 5 mm) 0.040 0.0 5 5 0.0 2 0 0.0 2 5 Paste residue 〇〇〇〇 Anti-caking property 〇〇〇〇-26- 201033322 [Table 3]

Example 9 Example 1 0 Example 1 1 Example 1 2 Surface layer Resin composition (% by mass) LDP E 15 15 15 15 Propylene-ethylene block copolymer 8 5 8 5 8 5 8 5 Thickness of surface layer (Aim 12 12 12 12 HDP E 5 0 5 0 5 0 New layer resin LDPE 5 0 5 0 5 0 Table composition (% by mass) COPP 10 0 Thickness of the base material layer (&quot;m) 3 6 3 6 3 6 3 6 Guaranteed HSBR 5 5 Protected SEPS 6 5 Membrane SIS 5 5 CEBS 5 5 Weighed as Adhesive Layer Group Speckle Quality %) Amorphous Propylene-1-butene Cohesive Complex 3 8.0 0 3 3.2 5 2 3.7 5 3 3.2 5 Crystalline propylene-1-butene co-cohesive 2-0 0 1.7 5 1.2 5 1.75 L LDP E 5 10 10 10 P-1 2 5 10 10 10 10 Thickness of the adhesive layer ((4)) 12 12 12 12 All films Thickness Um) 6 0 6 0 6 0 6 0 Initial adhesion (N/2 5 mm) 0.0 2 0 0.0 3 5 0.0 4 5 0.0 5 5 Paste residue 〇〇〇〇 Anti-caking property 〇〇〇〇-27 - 201033322 [Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Surface layer LDP E 15 15 15 15 15 Resin composition (% by mass) Propylene-ethylene block copolymer 8 5 8 5 8 5 8 5 8 5 Thickness of surface layer (ym) 12 12 12 12 12 Substrate layer HDPE 5 0 Surface resin composition LDPE 5 0 surface (% by mass) COPP 100 10 0 10 0 10 0 Thickness (# m) 3 6 3 6 3 6 3 6 3 6 Guard HSBR 8 5 40 9 0 8 5 SEPS of the film 85 Adhesive layer Non-crystalline propylene-1-butene co-coincidence 47.5 2.8 5 Composition (% by mass) crystalline propylene-1-butene co-coincidence 2.5 0.15 LLDP E 15 10 7 15 15 P-1 2 5 10 1 0 10 10 10 Thickness of the adhesive layer (Am) 12 12 12 12 12 All films Thickness (&quot;m) 6 0 6 0 6 0 60 6 0 Initial adhesion (N/25mm) 0.0 1 0-0 1 5 0 0.0 1 0 Paste residue 〇〇〇〇〇 块 〇〇 X 〇〇

As is apparent from the results of Examples 1 to 12, the surface protective film of the present invention has an adhesive force for the adherend of the surface uneven shape, and has a practically slightly adhesive adhesion as a surface protective film. In addition, it was also found that when the film was peeled off from the acrylic sheet, the paste residue on the surface of the adherend was not visually recognized, and the contamination of the foreign matter was not confirmed. Further, it is also known that a good surface operation is possible without performing agglomeration. Comparative Example 1 is an example of a surface protective film which is the same as the surface layer 'base material layer of Example 1, a mixture of H SBR and LLDPE of 85/15 for the adhesive layer, and no synthetic component (Β2). In the surface protective film of Comparative Example 1, it was found that the adhesive force was low on the surface unevenness of the adherend. Comparative Example 2 is the same as the surface layer and the substrate layer of Example 1, and the blending ratio of the component (Β3) of the adhesive layer is 1 part by mass, and the blending ratio of the component is set to be less than 50 parts by mass of the lower limit. 40 parts by mass, and the blending ratio of the component (B2) ❹ is set to 50 parts by mass of the surface protective film exceeding 45 parts by mass of the upper limit. In the surface protective film of Comparative Example 2, it was found that the adhesion to the surface unevenness of the surface was low. In Comparative Example 3, the surface layer and the base material layer of Example 1 were the same, and the blending ratio of the component (B1-1) of the adhesive layer was 90 parts by mass or more, and the blending of the component (B) was carried out. The ratio is set to be 3 parts by mass of the surface protective film of 50 parts by mass or less. In the surface protective film of Comparative Example 3, it was found that the adhesive force was low φ to the adherend of the surface uneven shape, and the blocking strength was large, and the blocking resistance was deteriorated. Comparative Example 4 is an example of a surface protective film which is the same as the surface layer and the substrate layer of Example 1, which is a mixture of SEP S and LLDPE of 85/15 for the adhesive layer, and which is not doped with the synthetic component (B2). In the surface protective film of Comparative Example 1, it was found that the adhesive force was low on the surface unevenness of the adherend. Comparative Example 5 is an example in which a mixture of HDPE/LDPE = 50/50 was used for the substrate layer, and a surface protective film of the compound (B2) was not blended. In the surface protective film of Comparative Example 1, it was found that the adhesive force was low on the surface unevenness of the adherend. -29- 201033322 Industrial Applicability The surface protective film of the present invention is useful as a film for protecting various surfaces such as a resin plate, a glass plate, and a metal plate. It is particularly suitable for use as a protective film for a crucible or a diffusing plate having irregularities in the surface shape of the adherend. [Simple description of the diagram] Μ 〇 [Description of main component symbols]

-30-

Claims (1)

201033322 VII. Patent application scope: 1. A surface protective film characterized by a surface protective film having a substrate layer (A) and an adhesive layer (B), and the adhesive layer (B) is mixed with the following components As a main component: 50 to 85% by mass of a copolymer of a hydrogenated styrene-based polymer block and a styrene-based random copolymer block having a double bond portion of a random copolymer of styrene and a conjugated diene compound Olefin polymerization of the compound (B1-1), a hydrogenated formula aba or ab (a styrene polymer block, a b-based conjugated diene polymer block or a double bond in a conjugated diene polymer) Block of the styrene block copolymer (B1-2), or a crystalline olefin polymer block of a hydrogenated conjugated diene polymer block and a conjugated diene polymer block The block copolymer (B1-3); 5 to 45 mass% of the amorphous α-olefin polymer (B2); and 5 to 45 mass% of the crystalline olefin polymer (Β3). 2. The surface protective film of claim 1, wherein the substrate layer (Α) is an olefin polymer (Α1) as a main component. 3. The surface protective film according to claim 1 or 2, wherein the block 〇 copolymer (Β1-3) is a crystalline olefin block-ethylene/butylene copolymer block-crystalline olefin block structure Block copolymer. 4. The surface protective film according to any one of claims 1 to 3, wherein the surface layer (C) having an olefin polymer as a main component is provided on the opposite side of the adhesive layer (Β) On the layer (Α). 5. The surface protective film of claim 4, wherein the olefin-based polymer of the main component of the surface layer (C) is an ethylene-based polymer or a propylene-based polymer and a propylene-ethylene block copolymer. A mixed resin is used as a main component. -31- 201033322 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: 4E 〇 j\\\ ❹ 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: Μ 〇 〇