Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
  • C09J7/22—Plastics; Metallised plastics
  • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/241—Polyolefin, e.g.rubber
  • C09J7/243—Ethylene or propylene polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/04—Thermoplastic elastomer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2423/00—Presence of polyolefin
  • C09J2423/16—Presence of ethen-propene or ethene-propene-diene copolymers
  • C09J2423/166—Presence of ethen-propene or ethene-propene-diene copolymers in the substrate

Definitions

• the present invention relates to a surface protective film and a propylene copolymer composition for the surface protective film. Specifically, the present invention relates to a propylene copolymer composition suitable for producing a surface layer of a surface protective film, and a surface protective film comprising the composition.
• the surface protective film is usually a laminated film having a surface layer on one surface and an adhesive layer on the other surface, and the adhesive layer is attached to an adherend for use.
• the surface protective film has uses such as a building material use and an optical member use.
• a surface protective film may be pasted and stored on various optical films (for example, a diffusion film, a polarizing film, a retardation film, etc.) incorporated in a liquid crystal display or a plasma display.
• it is a transparent surface protection film, it may affix on the display surface of a display.
• a laminated film is produced by co-extrusion molding or by applying and forming an adhesive layer on a base film.
• a laminated film can be generally produced at low cost.
• the laminated film produced by coextrusion is usually wound and stored in a roll shape, and the film is fed out from the roll from which the film is wound when the film is used.
• Patent Document 2 discloses a surface protective film mainly composed of a polyethylene component.
• the method according to the publication can be applied to some use members, the adhesive strength is low and the transparency is insufficient, and the use of the adherend is limited.
• Patent Document 3 proposes a surface protective film made of a specific propylene random block copolymer obtained by a metallocene catalyst system, but further improvement is desired.
• An object of the present invention is to provide a surface protective film having a small amount of fish eyes and excellent in drawability (feeding out property and blocking resistance) of a winding film and having sufficient transparency.
• the present invention relates to the following [1] to [7].
• decalin of the part insoluble in room temperature n-decane (D insol ) is 1.5 dl / g or more and 2.5 dl / g or less.
• the intrinsic viscosity [ ⁇ ] sol in 135 ° C. decalin of the part soluble in room temperature n-decane (D sol ) is 2.5 dl / g or more and 4.5 dl / g or less.
• the content of the skeleton derived from ethylene in the portion soluble in n-decane at room temperature (D sol ) is 35% by weight to 50% by weight.
• (1 ′) A melt flow rate (MFR B ) under a load of 190 ° C.
• melt flow rate (MFR B ) satisfies the following relational expression (1) with respect to [ ⁇ ] sol of the propylene / ethylene block copolymer (A).
• a propylene copolymer composition for a surface protective film comprising (B) in an amount of 3% by weight to 25% by weight (provided that the total of (A) and (B) is 100% by weight).
• the intrinsic viscosity [ ⁇ ] insol in 135 ° C. decalin of the part insoluble in room temperature n-decane (D insol ) is 1.5 dl / g or more and 2.5 dl / g or less.
• the intrinsic viscosity [ ⁇ ] sol in 135 ° C. decalin of the part soluble in room temperature n-decane (D sol ) is 2.5 dl / g or more and 4.5 dl / g or less.
• the content of the skeleton derived from ethylene in the portion soluble in n-decane at room temperature (D sol ) is 35% by weight to 50% by weight.
• (1 ′) A melt flow rate (MFR B ) under a load of 190 ° C. and a load of 2.16 kg is 0.1 g / 10 min or more and 2 g / 10 min or less.
• Density is 860 kg / m 3 or more and 890 kg / m 3 or less.
• (3 ′) The melt flow rate (MFR B ) satisfies the following relational expression (1) with respect to [ ⁇ ] sol of the propylene / ethylene block copolymer (A).
• the propylene / ethylene block copolymer (A) has a content of skeleton derived from ethylene in a portion insoluble in room temperature n-decane (D insol ) of not less than 0% by weight and not more than 8% by weight.
• the propylene / ethylene block copolymer (A) polymerizes homopolypropylene or propylene / ethylene random copolymer in the first polymerization step, and polymerizes propylene / ethylene random copolymer in the second polymerization step.
• the propylene / ethylene block copolymer (A) is a portion insoluble in room temperature n-decane (D insol ) by controlling a polymerization amount ratio between the first polymerization step and the second polymerization step.
• the present invention less damage to the adherend due to less fisheye, sufficient transparency, excellent functionality as a surface protection film, and roll-like without using a release film Even when wound up and stored, it is possible to provide a surface protective film that is excellent in blocking resistance and excellent in pull-out properties when the wound film is used.
• the surface protective film according to the present invention can be used without limitation for various uses using the surface protective film, and also exhibits sufficient transparency, so that the surface of an optical film, an optical member, an electrical material, etc. is protected. Can be suitably used.
• the surface protective film of the present invention has a film formed from the propylene copolymer composition for a surface protective film according to the present invention as a surface layer.
• the surface protective film of the present invention may be formed singly, but as a preferred embodiment, it is a laminated film of at least two layers having a surface layer on one surface and an adhesive layer on the other surface.
• the propylene copolymer composition for a surface protective film of the present invention is a composition suitable for forming a surface layer of a surface protective film, and comprises a propylene / ethylene block copolymer (A), an ethylene elastomer ( B).
• Propylene / ethylene block copolymer (A) The propylene / ethylene block copolymer (A) according to the present invention is formed from a part insoluble in room temperature n-decane (D insol ) and a part soluble in room temperature n-decane (D sol ).
• the polymerization catalyst and polymerization conditions used in the production are not particularly limited. Moreover, it can also be used individually by 1 type, and can also be used in combination of 2 or more type.
• the intrinsic viscosity [ ⁇ ] insol in 135 ° C. decalin of the portion insoluble in room temperature n-decane (D insol ) is 1.5 dl / g or more and 2.5 dl / g or less.
• the lower limit is preferably 1.7 dl / g, more preferably 1.9 dl / g, and the upper limit is preferably 2.4 dl / g, more preferably 2.3 dl / g.
• the cast film moldability of the resulting propylene copolymer composition for a surface protective film tends to be inferior.
• homopolypropylene or propylene / ethylene random copolymer may be used in the first polymerization step, as described later in the method for producing the propylene / ethylene block copolymer (A).
• a portion insoluble in room temperature n-decane (D insol ) mainly composed of a polymer is polymerized, and a portion soluble in room temperature n-decane (mainly propylene / ethylene random copolymer elastomer) in the second polymerization step ( In the case of polymerizing D sol ), the intrinsic viscosity [ ⁇ ] insol in 135 ° C.
• decalin of the portion insoluble in room temperature n-decane (D insol ) is controlled by controlling the hydrogen feed amount in the first polymerization step. Can be controlled within.
• the intrinsic viscosity [ ⁇ ] sol in 135 ° C. decalin of a portion soluble in room temperature n-decane (D sol ) is 2.5 dl / g or more and 4.5 dl / g or less.
• the lower limit is preferably 3.0 dl / g, more preferably 3.5 dl / g, and the upper limit is preferably 4.4 dl / g, more preferably 4.3 dl / g.
• the resulting surface protective film is excellent in blocking resistance, and if it is at most the upper limit, the occurrence of fish eyes in the surface protective film is sufficiently suppressed.
• a portion insoluble in room temperature n-decane containing homopolypropylene or propylene / ethylene random copolymer as a main component in the first polymerization step ( D insol ) is polymerized, and in the second polymerization step, a portion soluble in room temperature n-decane (D sol ) mainly composed of a propylene / ethylene random copolymer elastomer is polymerized (D sol ).
• the intrinsic viscosity [ ⁇ ] sol in 135 ° C. decalin of the portion soluble in n-decane at room temperature (D sol ) can be controlled within the above range.
• the content of the skeleton derived from ethylene in the part (D sol ) soluble in room temperature n-decane is 35 wt% or more and 50 wt% or less.
• the lower limit is preferably 45% by weight, more preferably 40% by weight.
• homopolypropylene or propylene / ethylene random copolymer may be used in the first polymerization step as described later in the method of producing the propylene / ethylene block copolymer (A).
• a portion insoluble in room temperature n-decane (D insol ) mainly composed of a polymer is polymerized, and a portion soluble in room temperature n-decane (mainly propylene / ethylene random copolymer elastomer) in the second polymerization step (when polymerizing D sol), the second ethylene feed amount of the polymerization process and the like by controlling the, within the above range the content of skeletons derived from ethylene in the portion soluble (D sol) to room temperature n- decane Can be controlled.
• the propylene / ethylene block copolymer (A) according to the present invention preferably satisfies the following requirements (4) and (5) in addition to the above requirements (1) to (3).
• the mass fraction of the portion soluble in room temperature n-decane (D sol ) is 5 wt% or more and 40 wt% or less.
• the lower limit is more preferably 9% by weight, and the upper limit is more preferably 17% by weight.
• the resulting surface protective film is excellent in blocking resistance, and if it is at most the upper limit value, fish eyes of the surface protective film can be suitably suppressed.
• homopolypropylene or propylene / ethylene random copolymer may be used in the first polymerization step, as described later in the method for producing the propylene / ethylene block copolymer (A).
• a portion insoluble in room temperature n-decane (D insol ) mainly composed of a polymer is polymerized, and a portion soluble in room temperature n-decane (mainly propylene / ethylene random copolymer elastomer) in the second polymerization step (when polymerizing D sol), by controlling the polymerization amount ratio of the first polymerization step and the second polymerization step, the mass of the portion insoluble in room temperature n- decane (D insol) soluble portion (D sol) The fraction can be controlled within the above range.
• the content of the skeleton derived from ethylene in the portion (D insol ) insoluble in room temperature n-decane is 0 wt% or more and 8 wt% or less. More preferably, it is 0 to 1% by weight.
• the range to satisfy the above requirement (5) it is derived from ethylene in a part insoluble in D- sol at room temperature (D insol ) by adjusting the type of solid catalyst or electron donating compound used.
• the content of the skeleton can be controlled within the above range.
• the propylene / ethylene block copolymer (A) according to the present invention satisfying the above requirements (1) to (3), preferably further satisfying the above requirements (4) and (5), is as follows, for example: It can be manufactured by the method.
• the propylene / ethylene block copolymer (A) is not particularly limited in the polymerization catalyst and polymerization conditions used during production as described above, but is suitably known.
• the Ziegler catalyst or metallocene catalyst homopropylene or a propylene / ethylene random copolymer composed of propylene and a small amount of ethylene is produced in the first polymerization step ([Step 1]), and then the second polymerization step ( In [Step 2]), a propylene / ethylene copolymer elastomer is produced by copolymerizing propylene and a larger amount of ethylene than in the first step.
• polymerization catalyst used in the production of the propylene / ethylene block copolymer (A) examples include: (A1) a solid catalyst component having a magnesium atom, a titanium atom, and a halogen atom as essential components; and (B1). Examples thereof include highly stereoregular catalysts obtained using organoaluminum compounds. Examples of such a catalyst include a highly stereoregular catalyst obtained by using the following components (A1) and (B1). (A1) Solid catalyst component (B1) organoaluminum compound obtained by using (a) magnesium compound and (b) titanium compound. Preferably, the following (A1) component, (B1) component and (C1) component are also used. And a highly stereoregular catalyst obtained in the above manner.
• (A) Magnesium compound The magnesium compound is not particularly limited, and includes magnesium oxide, magnesium hydroxide, dialkylmagnesium, alkylmagnesium halide, magnesium halide, magnesium dialkoxide, specifically magnesium chloride, magnesium diethoxide, A magnesium dimethoxide etc. can be mentioned.
• a magnesium compound the well-known solid product obtained by making metal magnesium, a halogen, and alcohol react can be used conveniently.
• examples of the alcohol include methanol and ethanol, and those having a water content of 200 ppm or less are easy to obtain a solid product having a good morphology.
• halogen chlorine, bromine, iodine, particularly iodine is preferably used.
• TiB Titanium compound
• arbitrary titanium compounds can be used, for example, the titanium compound represented by General formula (1) is mentioned.
• X 1 is a halogen atom, particularly a chlorine atom
• R 1 is a hydrocarbon group having 1 to 10 carbon atoms, particularly a linear or branched alkyl group, and a plurality of groups R 1 are present.
• n is an integer from 0 to 4.
• Electron-donating compound For the preparation of the solid catalyst component (A1), any electron-donating compound (c) can be used as necessary. These electron donating compounds (c) are usually organic compounds containing oxygen, nitrogen, phosphorus or sulfur.
• amines, amides, ketones, nitriles, phosphines, esters, ethers Mention may be made of thioethers, alcohols, thioesters, acid anhydrides, acid halides, aldehydes, organic acids, and organosilicon compounds having a Si—O—C bond.
• aromatic phthalic acid diesters such as diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dimethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, di-
• organosilicon compounds such as t-butyldimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, dicyclohexyldimethoxysilane, and dicyclopentyldimethoxysilane.
• the solid catalyst component (A1) can be prepared by a known method using the magnesium compound (a), the titanium compound (b), and, if necessary, the electron donating compound (c).
• the magnesium compound (a) and the electron donating compound (c) are contacted and then contacted with the titanium compound (b).
• the contact conditions are not particularly limited, and usually 0.01 to 10 mol, preferably 0.05 to 5 mol of an electron donating compound (c) is added to 1 mol of the magnesium compound (a) in terms of magnesium atom.
• the contact is performed at 0 to 200 ° C. for 5 minutes to 10 hours, preferably at 30 to 150 ° C. for 30 minutes to 3 hours.
• inert hydrocarbons such as pentane, hexane, and heptane can be added to this preparation.
• the conditions for contacting the titanium compound (b) with the magnesium compound (a) or the contact product of the electron donor compound (c) with the magnesium compound (a) are not particularly limited.
• the titanium compound (b) is added in an amount of 1 to 50 mol, preferably 2 to 20 mol, and contacted at 0 to 200 ° C. for 5 minutes to 10 hours, preferably at 30 to 150 ° C. for 30 minutes to 5 hours.
• the contact with the titanium compound (b) can be performed in a state where the liquid titanium compound (for example, titanium tetrachloride) is used alone and the other titanium compounds are dissolved in an arbitrary inert hydrocarbon.
• the electron donating compound (c) for example, halogenated hydrocarbon, halogen-containing silicon compound, halogen gas, hydrogen chloride, hydrogen iodide Etc. can be brought into contact with the magnesium compound (a).
• the electron donating compound (c) for example, halogenated hydrocarbon, halogen-containing silicon compound, halogen gas, hydrogen chloride, hydrogen iodide Etc.
• Organoaluminum compound (B1) there is no limitation in particular as an organoaluminum compound (B1), For example, the compound represented by following General formula (2) is mentioned.
• R 2 is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or an aryl group, m is an integer of 1 to 3, and X 2 is a halogen atom (chlorine or bromine atom).
• Specific examples include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, and triisobutylaluminum, and dialkylaluminum monochlorides such as diethylaluminum monochloride and dipropylaluminum monochloride.
• Electron donating compound (C1) In the catalyst used for the production of the propylene / ethylene block copolymer (A) according to the present invention, an electron donating compound (C1) can be used in combination as required.
• the electron donating compound (C1) in this case, the same electron donating compound (c) used in the preparation of the solid catalyst component (A1) can be used. In this case, it may be the same as or different from that used in the preparation of the solid catalyst component.
• a preferred electron donating compound (C1) is a silane compound having a SiO—C bond, particularly a compound represented by the following general formula (3).
• R 3 p Si (OR 4 ) 4-p (3) (In the formula (3), R 3 represents a linear or branched hydrocarbon group, an aromatic hydrocarbon group, a cyclic saturated hydrocarbon group or a nitrogen atom-containing hydrocarbon group. R 4 is a linear hydrocarbon group or a branched hydrocarbon group, and p is an integer of 0 to 3.) Specific examples of the compound of the formula (3) include t-butylcyclohexyldimethoxysilane, methylcyclohexyldimethoxysilane, di-t-butyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxy.
• Silane trimethylethoxysilane, methylphenyldimethoxysilane, diethylaminotriethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, ethyl (perhydroquinolino) dimethoxysilane, ethyl (perhydroiso) Quinolino) dimethoxysilane, and the like.
• the propylene / ethylene block copolymer (A) uses a polymerization apparatus in which two or more reaction apparatuses are connected in series, and comprises the following two steps ([Step 1] and [Step 2]. ) Is preferably carried out continuously.
• propylene is polymerized alone or copolymerized with propylene and ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure.
• the amount of ethylene fed relative to propylene is made small so that the polypropylene or the propylene / ethylene random copolymer produced in [Step 1] becomes the main component of D insol .
• [Step 2] copolymerizes propylene and ethylene at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of normal pressure to 5 MPa gauge pressure.
• the propylene / ethylene copolymer elastomer produced in [Step 2] becomes the main component of D sol by increasing the amount of ethylene fed to propylene than in [Step 1]. To do.
• requirements (1) and (5) concerning D insol are adjusted by adjusting the polymerization conditions in [Step 1], and requirements (2) and (3) concerning D sol are [Step 2]. It can be satisfied by adjusting the polymerization conditions.
• the requirement (4) relating to the composition ratio between D insol and D sol can be controlled by adjusting the amount ratio of the polymer produced in [Step 1] and [Step 2].
• the intrinsic viscosity [ ⁇ ] in 135 ° C. decalin of D insol of requirement (1) can be adjusted by the feed amount of a molecular weight regulator such as hydrogen in [Step 1].
• the intrinsic viscosity [ ⁇ ] in 135 ° C. decalin of D sol of requirement (2) can be adjusted by the feed amount of a molecular weight regulator such as hydrogen in [Step 2].
• the content of the skeleton derived from ethylene in D sol of requirement (3) can be adjusted by the amount of ethylene feed in [Step 2].
• composition ratio between D insol and D sol of requirement (4) and the melt flow rate of the propylene / ethylene block copolymer (A) are the ratios of the polymers produced in [Step 1] and [Step 2]. It is possible to adjust appropriately by adjusting.
• the content of the skeleton derived from ethylene in D insol of requirement (5) can also be adjusted by adjusting the type of solid catalyst or electron donating compound used. It is also possible to adjust by the amount of ethylene feed in [Step 1].
• the propylene / ethylene block copolymer (A) used in the present invention is produced by the propylene / ethylene random copolymer produced in [Step 1] of the above method and [Step 2] of the above method.
• Propylene / ethylene random copolymer elastomers may be produced individually in the presence of a polymerization catalyst and then blended using these physical means.
• Ethylene elastomer (B) The ethylene-based elastomer is a random copolymer of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms of a comonomer type.
• the polymerization catalyst and polymerization conditions to be used are not particularly limited. Moreover, it can also be used individually by 1 type, and can also be used in combination of 2 or more type.
• the ethylene-based elastomer (B) according to the present invention satisfies the following requirements (1 ′) to (3 ′).
• (1 ′) The melt flow rate (MFR B ) under a load of 190 ° C. and a load of 2.16 kg is 0.1 g / 10 min or more and 2 g / 10 min or less.
• the lower limit is preferably 0.3 g / 10 minutes, more preferably 0.4 g / 10 minutes, and the upper limit is preferably 1.5 g / 10 minutes, more preferably 1.0 g / 10 minutes.
• the propylene copolymer composition obtained has excellent extrusion characteristics and surface protective film fish eye and blocking resistance, and if the upper limit value or less, the resulting protective eye fish eye and blocking resistance are obtained. Excellent.
• the density is 860 kg / m 3 or more and 890 kg / m 3 or less.
• the lower limit is preferably 870 kg / m 3 , more preferably 875 kg / m 3
• the upper limit is preferably 889 kg / m 3 , more preferably 888 kg / m 3 .
• melt flow rate (MFR B ) satisfies the following relational expression (1) with respect to [ ⁇ ] sol of the propylene / ethylene block copolymer (A).
• the relational expression (1) of the requirement (3 ′) indicates the magnitude relationship between the molecular weights of the propylene / ethylene block copolymer (A) and the ethylene-based elastomer (B).
• [ ⁇ ] sol of the propylene / ethylene block copolymer (A) it is found that the fish-eye improvement effect cannot be obtained unless the molecular weight of the ethylene-based elastomer (B) is larger than a certain level. This is specified in the relational expression (1).
• the propylene / ethylene block copolymer (A) by blending a high-viscosity ethylene-based elastomer (B) that does not become the core of fisheye, It is considered that the domain size (dispersed particle size) of the ethylene-based elastomer (B) component is large, and forming this makes the surface roughness of the film rough and significantly improves the blocking resistance.
• melt flow rate (MFR B ) of the ethylene-based elastomer (B) satisfies the requirement (3 ′) in addition to the requirement (1 ′)
• fish eyes of the resulting surface protective film are suppressed, and anti-blocking property Excellent in properties.
• the propylene copolymer composition for a surface protective film of the present invention has the object of the present invention for the purpose of imparting functions such as impact resistance, transparency, dimensional stability, and high-speed extrusion sheet formability. As long as it is not necessary, it may contain a polyethylene resin (C) or other thermoplastic resin as necessary. That is, the surface layer of the surface protective film of the present invention may contain a polyethylene resin (C) or other thermoplastic resin as necessary, as long as the object of the present invention is not impaired.
• the amount of the polyethylene resin (C) is determined by the amount of the propylene / ethylene block copolymer.
• the amount is usually 0 to 30 parts by mass, preferably 1 to 20 parts by mass with respect to 100 parts by mass.
• the ratio of ethylene-type elastomer (B) and polyethylene resin (C) can be arbitrarily adjusted according to the objective.
• the propylene copolymer composition for a surface protective film of the present invention is a range that does not impair the object of the present invention, and if necessary, vitamins, antioxidants, heat stabilizers, weathering stabilizers, slip agents, An additive such as an anti-blocking agent and mineral oil may be included. That is, the surface layer of the surface protective film of the present invention may contain the various additives as necessary within a range not impairing the object of the present invention.
• Propylene copolymer composition for surface protective film comprises the propylene / ethylene block copolymer (A) and the ethylene elastomer (B). If necessary, the above-mentioned other components are contained.
• the propylene copolymer composition for a surface protective film of the present invention comprises a propylene / ethylene block copolymer (A) of 75% by weight to 97% by weight and an ethylene elastomer (B) of 3% by weight to 25% by weight.
• the lower limit of the content of the propylene / ethylene block copolymer (A) is preferably 76% by weight, more preferably 77% by weight, and the upper limit is preferably 96% by weight, more preferably 95% by weight, still more preferably 93% by weight. It is.
• the blending amount of the ethylene-based elastomer (B) is not less than the above lower limit value, the resulting film has excellent blocking resistance, fish eyes are suppressed, and when it is not more than the above upper limit value, the moldability is excellent.
• the surface protective film propylene copolymer composition of the present invention 230 ° C., under a 2.16kg load melt flow rate (MFR E) is preferably 0.5 g / 10 min or more 50 g / 10 min or less, The lower limit is more preferably 3 g / 10 minutes, and the upper limit is more preferably 6 g / 10 minutes. The above range is preferable because cast film moldability is excellent.
• the propylene copolymer composition for a surface protective film of the present invention can be produced by melt-kneading the above-mentioned propylene / ethylene block copolymer (A) and ethylene elastomer (B), or propylene. -It can manufacture also by dry blending the pellet which granulated the ethylene block copolymer (A), and the pellet of ethylene-type elastomer (B).
• a method of production by melt kneading can be used, and at this time, a continuous extruder or a closed kneader can be used.
• apparatuses such as a single screw extruder, a twin screw extruder, a mixing roll, a Banbury mixer, a kneader, can be mentioned.
• a single screw extruder and / or a twin screw extruder from the viewpoints of economy, processing efficiency, and the like.
• the propylene copolymer composition for a surface protective film of the present invention is suitably used as a composition for forming a surface layer of a surface protective film having a surface layer and an adhesive layer.
• the surface protective film of the present invention includes at least two layers of a surface layer and an adhesive layer.
• the surface layer of the surface protective film of the present invention is formed from the propylene copolymer composition for a surface protective film of the present invention.
• Adhesive layer The material for forming the adhesive layer of the surface protective film of the present invention is not particularly limited as long as the surface protective film can be attached to an adherend.
• EVA, SBR, SIS, SBS examples thereof include SEBS-based, butyl elastomer-based, natural elastomer-based, and acrylic pressure-sensitive adhesives.
• linear low density polyethylene (LLDPE) having a density of 0.900 kg / m 3 or less can be used.
• a propylene-based random block copolymer described in JP-A-2009-185239, which is polymerized with a metallocene catalyst system can also be used.
• EVA EVA
• SEBS linear low density polyethylene
• LLDPE linear low density polyethylene
• an acrylic adhesive can be used preferably.
• the pressure-sensitive adhesive layer in the surface protective film of the present invention includes additives such as vitamins, antioxidants, heat stabilizers, weather stabilizers, mineral oils, etc., as necessary, as long as the purpose of the present invention is not impaired. May be.
• the surface protective film of the present invention has at least two layers of a surface layer and an adhesive layer, and may be formed of only two layers of a surface layer and an adhesive layer. One or more intermediate layers may be provided therebetween.
• the intermediate layer may be provided for the purpose of controlling the mechanical strength and transparency of the film. If the adhesive strength between the surface layer and the adhesive layer is insufficient, the intermediate layer may be made of a polyolefin resin, an adhesive resin, or an adhesive. It may be a layer having adhesiveness.
• the intermediate layer is not particularly limited as long as it does not hinder the functions of the surface layer and the adhesive layer, but generally, a crystalline polyolefin such as polypropylene or polyethylene having a melting point of 100 ° C. or higher, polyester, polyamide, polyolefin elastomer, etc. are used. it can.
• a crystalline polyolefin such as polypropylene or polyethylene having a melting point of 100 ° C. or higher, polyester, polyamide, polyolefin elastomer, etc. are used. it can.
• modified polyolefin, polyolefin elastomer, styrene elastomer, polyester elastomer or the like is used.
• polypropylene or polyolefin elastomer as the intermediate layer.
• the thickness of the surface protective film of the present invention can be appropriately determined according to the purpose, and can be, for example, 10 to 200 ⁇ m.
• the thickness of the surface layer can be 8 to 150 ⁇ m, and the thickness of the adhesive layer can be 2 to 50 ⁇ m.
• the surface layer of the surface protective film of the present invention is formed by using the propylene copolymer composition for a surface protective film of the present invention, so that fish eyes are effectively suppressed and usually has good transparency.
• the surface protective film of the present invention having such a surface layer is less likely to cause blocking with the adhesive layer that comes into contact when the surface protective film is rolled up, has excellent blocking resistance, and is a roll-shaped film. Excellent feedability.
• the exposed surface of the surface layer to be the surface of the surface protective film, that is, the surface opposite to the adhesive layer side preferably has a certain unevenness, and the average surface is a parameter indicating the surface state
• the roughness Ra (arithmetic mean roughness) is preferably 0.20 to 2.00 ⁇ m, more preferably 0.3 to 0.8 ⁇ m.
• a surface layer having such an average surface roughness can be easily obtained when the propylene / ethylene block copolymer according to the present invention is formed into a film by a conventional method.
• the surface layer of the surface protective film of the present invention exhibits such average surface roughness, is excellent in anti-blocking properties, and the fisheye is suppressed, the present inventor is not sure, By blending the propylene / ethylene block copolymer (A) with a high-viscosity ethylene elastomer (B) that does not become the core of fish eye, the ethylene elastomer in the propylene copolymer composition for surface protective film It is considered that the domain size (dispersed particle size) of the component (B) is large, and by molding this, the surface roughness of the film becomes rough and the blocking resistance is remarkably improved.
• a fish eye nucleus is a high-viscosity component resulting from an especially high molecular weight thing among the elastomer components which exist in a propylene ethylene block copolymer (A).
• the unevenness of the film surface for improving the blocking resistance is on the order of several ⁇ m, for example, about 1 to 3 ⁇ m
• the FE nucleus has an order of size that is on the order of several tens of ⁇ m, for example, about 10 to 50 ⁇ m. .
• the above-described propylene copolymer composition for a surface protective film of the present invention is formed into a film form from a T die together with a resin for forming an intermediate layer as necessary, and formed into a tube form from a circular die.
• a single layer / multilayer substrate film can be obtained.
• the base film containing the surface layer formed by these methods can be multilayered by a dry lamination method or an extrusion lamination method.
• the film formed by the above method can be used by appropriately stretching.
• the adhesive layer is formed by various known methods. For example, a method of coating a pressure-sensitive adhesive on a substrate including a surface layer with a coating machine, a co-extrusion method in which a substrate and a pressure-sensitive adhesive are formed into a multilayer film form from a T die or a circular die, and the like.
• the measuring method of the physical property in an Example and a comparative example is as follows.
• MFR melting flow rate
• MFR was measured according to ASTM D1238 (230 ° C or 190 ° C, load 2.16 kg).
• D sol room temperature n-decane soluble part 200 ml of n-decane was added to 5 g of a sample of the final product (that is, the propylene random block polymer of the present invention) and dissolved by heating at 145 ° C. for 30 minutes. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate (hereinafter, n-decane insoluble portion: D insol ) was filtered off.
• the filtrate was put in about 3 times the amount of acetone to precipitate the components dissolved in n-decane (precipitate (A)).
• the precipitate (A) and acetone were separated by filtration, and the precipitate was dried. Even when the filtrate side was concentrated to dryness, no residue was observed.
• the amount of n-decane soluble part was determined by the following formula.
• n-decane soluble part amount (wt%) [precipitate (A) weight / sample weight] ⁇ 100 (3) Content of skeleton derived from ethylene
• 20 to 30 mg of sample was subjected to 1,2,4-trichlorobenzene / heavy benzene (2: 1 )
• carbon nuclear magnetic resonance analysis ( 13 C-NMR) was performed. Propylene, ethylene, and ⁇ -olefin were quantitatively determined from the dyad chain distribution.
• PP S ⁇
• EP S ⁇ + S ⁇
• EE 1/2 (S ⁇ + S ⁇ ) + 1 / 4S ⁇
• Propylene (mol%) (PP + 1 / 2EP) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)] ...
• Ethylene (mol%) (1 / 2EP + EE) x 100 / [(PP + 1 / 2EP) + (1 / 2EP + EE)] ...
• homopolymerization was performed by supplying propylene at 45 kg / h and hydrogen at 380 Nl / h to a polymerization tank (homopolymerization tank) with a stirring blade having an internal volume of 200 liters.
• the pre-polymerized solid catalyst component was supplied so that the polymerization rate was 30 kg / hour, triethylaluminum was supplied at 120 mmol / hour, and dicyclopentyldimethoxysilane was supplied at 12 mmol / hour, and the polymerization temperature was 83 ° C.
• the reaction was carried out at a polymerization tank pressure of 3.0 MPa (Gauge). At this time, it adjusted so that it might become a predetermined molecular weight using hydrogen. Subsequently, powder was continuously extracted from the former polymerization tank and transferred to the latter stage (block polymerization tank).
• Heat stabilizer IRGANOX 1010 (Ciba Geigy Co., Ltd.) 0.1 parts by mass
• heat stabilizer IRGAFOS168 (Ciba Geigy Co., Ltd.) 0.1 parts by mass
• calcium stearate 0.1 parts by mass in a tumbler
• melt-kneading at 190 ° C using a twin-screw extruder manufactured by Nakatani Machinery Co., Ltd. (same direction twin-screw kneader) to prepare a propylene copolymer composition for a surface protective film in the form of pellets did.
• the peeling force from the adhesive layer was evaluated by the measurement method described above.
• As the evaluation adhesive layer a commercially available olefin-based adhesive film (A2450, manufactured by Hitachi Chemical Co., Ltd.) was used. The results are shown in Table 3 and Table 4 together.
• a laminate was manufactured by laminating a single layer film corresponding to the surface layer and an adhesive layer by a dry laminating method.
• Two laminated bodies having the same size are prepared (referred to as laminated bodies 1 and 2), the surface layers of the laminated body 1 and the adhesive layer of the laminated body 2 are opposed to each other, and the laminated bodies are overlapped with each other.
• a 2 kg rubber roller from above it was attached at a speed of 2 m / min. This was left at room temperature of 23 ° C. ⁇ 2 ° C. for 30 minutes.
• Examples 1 to 9 have excellent characteristics such as a large surface roughness and a small fish eye (FE) compared with Comparative Examples 1 to 3 compared with the Examples. Show. Further, as the amount of the elastomer component added increases, the surface roughness and FE improve, that is, the surface roughness increases and the FE tends to decrease. On the other hand, in Comparative Examples 4 to 6, the surface roughness is not so improved as compared with Comparative Examples 1 to 3 which are the respective references, and the improvement (suppression) effect of FE is not seen.
• FE small fish eye
• the surface protective film of the present invention can be widely used as a surface protective film for optical films, electronic component materials, building members and the like. Moreover, the propylene copolymer composition for surface protection films of this invention can be used suitably for manufacture of such a surface protection film.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Graft Or Block Polymers (AREA)
• Laminated Bodies (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Adhesive Tapes (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=50149903

Family Applications (1)

Country Status (5)

Cited By (4)

Families Citing this family (2)

Citations (4)

Family Cites Families (5)

• 2013
  • 2013-08-16 CN CN201380044173.7A patent/CN104583307B/zh active Active
  • 2013-08-16 JP JP2014531608A patent/JP5872048B2/ja active Active
  • 2013-08-16 WO PCT/JP2013/071998 patent/WO2014030594A1/ja active Application Filing
  • 2013-08-16 KR KR1020157005402A patent/KR101671654B1/ko active IP Right Grant
  • 2013-08-22 TW TW102129990A patent/TWI552872B/zh active

Patent Citations (4)

Also Published As

Similar Documents

Legal Events