JP2009255525A - Surface protective film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface protective film made of polyolefin-based resin which has extremely few fish eyes, is excellent in size stability and surface hardness, has improved performances with respect to peeling force control and delivery and is suitable as the surface protective film. <P>SOLUTION: The surface protective film comprises: a substrate made of propylene-based resin; a pressure-sensitive adhesive layer formed on one-side surface of the substrate; and a peeling treatment layer formed on the other side surface of the substrate, wherein the propylene-based resin of the substrate layer is a propylene single polymer or a propylene-α-olefin random copolymer which is polymerized by using a metallocene catalyst and has a specified MFR, a fusion peak temperature, a molecular weight distribution and a TREF value, the pressure-sensitive adhesive layer is a layer principally comprising an ethylene-α-olefin copolymer which is polymerized by using a metallocene catalyst and has a specified density, a TREF value and a molecular weight distribution, and the peeling treatment layer has a peeling treatment layer surface of which the center surface average roughness (Ra) falls into the range of 0.2 to 1.5 μm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a surface protective film, and more specifically, to protect a surface of a building member such as a synthetic resin plate, a decorative plate, a metal plate, and a glass plate, and to protect a surface of a constituent member of a liquid crystal display such as a polarizing plate and a retardation plate. The present invention relates to a film for protecting a surface which is preferably used as an application.

  Surface protection films are affixed to building materials such as synthetic resin plates and liquid crystal display parts of optical equipment members from the viewpoint of preventing scratches and dirt on the surface during processing, transportation and transportation, and after processing or transportation and transportation. It is common to peel off and use the surface protection film which concerns later.

  Conventionally, as the surface protective film, there is a surface protective film mainly composed of an ethylene-based resin. For example, a surface protective film made of an ethylene-based resin that is polymerized from a metallocene catalyst, has a narrow composition distribution and molecular weight distribution, and does not have fish eye is described (for example, see Patent Document 1). Further, a polyethylene comprising 50 to 90% by weight of a specific low density polyethylene and 10 to 50% by weight of a specific high density polyethylene having a weight average molecular weight / number average molecular weight ratio of 9 to 15, and an ethylene-unsaturated ester A laminated film obtained by coextruding a pressure-sensitive adhesive layer made of a copolymer is described (for example, see Patent Document 2).

However, in the surface protective film described in the above patent document, since polyethylene is the main component, retention occurs inside the molding machine extruder during film formation, gelation occurs due to deterioration of the ethylene component, Since the fish eye is generated, when the product is attached to the object to be protected and stacked and stored as it is, the object to be protected is dented due to the presence of the fish eye. Therefore, for example, even if an attempt is made to use the laminated film as a polarizing plate or a retardation plate used as a liquid crystal display material, there is a problem that the image is distorted due to the dents and cannot be applied.
In addition, in view of problems of heat resistance, scratch resistance, and rigidity of polyethylene, and having improved the point defects of the metal thin film layer due to the influence of chlorine ions, it is made of polypropylene having a chlorine content of 5 ppm by weight or less. A surface protective film containing a characteristic propylene-based resin as a main component has also been proposed (see, for example, Patent Document 3). However, even in the propylene-based resin described in the patent document, gelation like polyethylene does not occur, but the molecular weight distribution is wide, that is, low molecular weight having a low molecular weight and high molecular weight having a high molecular weight are mixed. Therefore, when the high molecular weight component is formed into a film, an unmelted fine lump becomes a fish eye and exists in the film, resulting in a dent in the protected object.

Further, both ethylene-based resins and propylene-based resins have a crystallinity distribution, but there is a problem that if the crystallinity distribution is wide and there are many low crystal components, the object to be protected is contaminated. In addition, in the process of producing the polymer, sticking of the low crystal component causes polymer adhesion in a polymerization tank or the like, resulting in deterioration of the polymer due to stagnation, and as a result, fish eyes derived from polymer degradation products exist in the film. As a result, the object to be protected is dented, and there is a problem that it cannot be applied as a surface protective film. In addition, if the crystallinity distribution is wide, the compatibility between the low crystallinity component and the high crystallinity component becomes non-uniform, and the high crystallinity component tends to exist as fish eyes in the form of a fine unmelted mass. Similarly, there is a problem that it cannot be applied as a surface protective film.
JP-A-9-111208 JP 54-133578 A JP 2006-282761 A

  In view of the problems of the above-described conventional technology, the present invention has a very small fish eye, excellent dimensional stability, surface hardness, improved peel force control and feeding performance, a synthetic resin board, a decorative board, To provide a surface protective film made of polyolefin resin suitable as a surface protective film for building members such as metal plates and glass plates, and as a surface protective film for liquid crystal display components such as polarizing plates and retardation plates. It is the purpose.

  As a result of repeating various studies in order to solve the above problems, the present inventors have obtained a specific melt flow rate, a melting peak temperature by a differential thermal scanning calorimeter, a weight average molecular weight and a number average determined by gel permeation chromatography. Propylene-based resin having a soluble fraction of 40 ° C. or less measured by the ratio of molecular weight and temperature rising elution fractionation method as a base material layer, and elution of 20 ° C. or less measured by specific density and temperature rising elution fractionation (TREF) An ethylene / α-olefin copolymer having a ratio of weight, weight average molecular weight and number average molecular weight is used for the pressure-sensitive adhesive layer, and the surface center plane average roughness (Ra) is in the range of 0.2 to 1.5 μm. By using a release treatment layer, a surface protective film with fewer fish eyes, excellent dimensional stability and surface hardness, improved peel force control and feeding performance can be obtained. To complete the present invention.

That is, according to the first invention of the present invention, in the surface protective film in which the pressure-sensitive adhesive layer is formed on one surface of the base material layer made of propylene-based resin and the release treatment layer is formed on the other surface, The propylene-based resin of the base material layer is polymerized using a metallocene catalyst and is a propylene homopolymer or propylene / α-olefin random copolymer having the following characteristics (A1) to (A4), and the pressure-sensitive adhesive layer is It is a layer mainly composed of an ethylene / α-olefin copolymer that is polymerized using a metallocene catalyst and has the following characteristics (B1) to (B3), and the release treatment layer has a center plane average of the release treatment layer surface: A film for surface protection is provided, wherein the roughness (Ra) is in the range of 0.2 to 1.5 μm under the following measurement conditions (C1) to (C6).
(A1) Melt flow rate (MFR: 230 ° C., 21.18 N load) is 1 to 50 g / 10 minutes (A2) Melting peak temperature (Tmp) by differential thermal scanning calorimeter (DSC) is 120 to 170 ° C.
(A3) Ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 1.5 to 3.5 (A4) temperature rising elution fractionation Soluble content (S ₄₀ ) measured by (TREF) method is 10% by weight or less (B1) Density is 0.860 to 0.915 g / cm ³
(B2) In temperature rising elution fractionation (TREF) measurement using orthodichlorobenzene as a solvent, the elution amount at 20 ° C. or less is 60% by weight or less. (B3) Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) is 3.5 or less (C1) The radius of curvature of the stylus tip is 5 mm
(C2) Cut-off wavelength is 0.80mm
(C3) Cutoff type is 2CR (phase compensation)
(C4) Measurement speed is 0.3 mm / second (C5) Measurement direction is MD direction of film (C6) Measurement length is 2 mm

According to the second invention of the present invention, in the first invention, the propylene-based resin further has the following property (A5): The surface protective film according to claim 1 is provided. Is done.
(A5) The range (T ₁₀₀ -T ₂₀ ) of the temperature (T ₁₀₀ ) at the end of elution by 100 wt% from the temperature (T ₂₀ ) at the elution of 20 wt% by the temperature rising elution fractionation (TREF) method is 30 ° C. Less than

  According to a third aspect of the present invention, there is provided the surface protecting film according to the first or second aspect, wherein the release treatment layer is made of a polyolefin resin.

  According to the fourth invention of the present invention, in any one of the first to third inventions, it is used for surface protection of building members such as a synthetic resin plate, a decorative plate, a metal plate, and a glass plate. A surface protective film is provided.

  According to a fifth aspect of the present invention, in any one of the first to third aspects, the surface is used for protecting a surface of a liquid crystal display component such as a polarizing plate or a retardation plate. A protective film is provided.

  The surface protective film of the present invention uses a specific propylene-based resin for the base material layer, which has a narrow resin crystallinity distribution, a small amount of low crystalline components to be eluted, a narrow molecular weight distribution, and a low molecular weight component. Therefore, there are very few unmelted fish eyes at the time of film forming. For this reason, even if a surface protection film is affixed on a to-be-protected object and stored in a stacked manner, the to-be-protected object does not dent. Moreover, the film for surface protection of this invention is excellent in blocking property, without using an antiblocking agent. Furthermore, when a specific ethylene / α-olefin copolymer polymerized using a metallocene catalyst is used as the pressure-sensitive adhesive layer, it is strong when at least one of the base material layer and the pressure-sensitive adhesive layer is laminated in a molten state. Bonds and has excellent delamination properties. Furthermore, by roughening the surface of the release treatment layer as the release treatment layer, the roll peels off when the roll is unwound from the roll wound state where both the pressure-sensitive adhesive layer and the release treatment layer are in contact with each other in a solid state. It can be set as the film for surface protection which has the characteristic of.

The present invention is a surface protection film having a pressure-sensitive adhesive layer formed on one surface of a base material layer and a base material layer, and having a release treatment layer on the pressure-sensitive adhesive layer and the other surface, Propylene resin polymerized using a metallocene catalyst and having characteristics (A1) to (A4) and, if necessary, further characteristics (A5) or a propylene / α-olefin random copolymer The pressure-sensitive adhesive layer is a propylene / α-olefin random copolymer which is polymerized using a metallocene catalyst and has characteristics (B1) to (B3) and, if necessary, characteristics (B4). The treatment layer is a film for surface protection made of a propylene-based resin whose center plane average roughness (Ra) on the surface of the release treatment layer is in the range of 0.2 to 1.5 μm in the measurement conditions (C1) to (C6). is there.
Hereinafter, the component of each layer of the film for surface protection of this invention and the manufacturing method of the film for surface protection are demonstrated in detail.

1. Base material layer The base material layer in the film for surface protection of the present invention is composed of a propylene-based resin. As the propylene-based resin, a propylene homopolymer or a propylene / α-olefin random copolymer of a copolymer of propylene and an α-olefin can be used. Here, examples of the α-olefin as the copolymer component include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and the like.

  Specific examples of the propylene / α-olefin random copolymer used in the present invention include propylene / ethylene random copolymer, propylene / 1-butene random copolymer, propylene / 1-hexene random copolymer, propylene / ethylene. -1-butene copolymer etc. are mentioned. Preferably, a propylene / ethylene random copolymer, a propylene / 1-butene random copolymer, a propylene / ethylene / 1-butene copolymer, and the like are used. More preferred is a propylene / ethylene random copolymer.

  The propylene-based resin used in the present invention has the following characteristics (A1) to (A4), and further has characteristics (A5) as necessary.

(A1) Melt flow rate The melt flow rate (MFR) of the propylene-based resin used in the present invention is 1 to 50 g / 10 minutes, preferably 2 to 30 g / 10 minutes, and more preferably 5 to 20 g / 10. Minutes, most preferably 7-15 g / 10 min.
If the MFR is less than 1 g / 10 minutes, the extrusion characteristics are deteriorated and the productivity is lowered, which is not preferable, and if the MFR exceeds 50 g / 10 minutes, the thickness accuracy at the time of film forming tends to be deteriorated.
MFR can be adjusted by the amount of hydrogen during polymerization. For example, increasing the amount of hydrogen increases the MFR.
In addition, the melt flow rate (MFR: unit g / 10min) employ | adopted in this invention is a value measured by 230 degreeC and a load of 21.18N load based on JISK-7210-1995.

(A2) Melting peak temperature The melting peak temperature (Tmp) of the propylene-based resin used in the present invention is 120 to 170 ° C, preferably 120 to 165 ° C, more preferably 120 to 160 ° C, and most preferably. Is 120 ° C to 150 ° C.
When the melting peak temperature is less than 120 ° C., the heat resistance is inferior, and the surface protection film is likely to be deformed during the processing step of applying heat to the surface protection film on the object to be protected. When the melting peak temperature is higher than 170 ° C., the impact strength is inferior, and there is a possibility that tearing may occur when the surface protection film is attached to an object to be protected.
The melting peak temperature (Tmp) can be adjusted by the amount of α-olefin used. For example, as the amount of α-olefin increases, the melting peak temperature (Tmp) decreases.
In addition, the melting peak temperature (Tmp: unit ° C) employed in the present invention is a differential scanning calorimeter (DSC), a sample amount of 5.0 mg is taken and held at 200 ° C for 5 minutes, and then 40 ° C. This is a value for measuring the melting peak temperature (Tmp) when crystallization is performed at a temperature lowering speed of 10 ° C./min until further melting at a temperature rising speed of 10 ° C./min.

(A3) Ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) Ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn) of the propylene-based resin used in the present invention is It is 1.5-3.5, Preferably it is 1.7-3.2, More preferably, it is 2.0-3.0, Most preferably, it is 2.3-2.8. When (Mw / Mn) is less than 1.5, the viscosity of the molten resin becomes high, the melt fluidity becomes poor, and extrusion molding becomes difficult. On the other hand, when (Mw / Mn) exceeds 3.5, the abundance ratio of molecules having a low molecular weight and molecules having a high molecular weight becomes high, and the high molecular weight component becomes an unmelted fish eye at the time of film formation and is stuck on a protected object. After that, if the products are stacked and stored as they are, the objects to be protected will be dented.
(Mw / Mn) can be adjusted by changing the polymerization conditions (polymerization temperature, polymerization pressure) during production and the type of catalyst used.

The weight average molecular weight (Mw) / number average molecular weight (Mn) used in the present invention is measured by gel permeation chromatography (GPC). The measurement conditions are as follows.
Apparatus: GPC 150C type manufactured by Waters Inc. Detector: 1A infrared spectrophotometer manufactured by MIRAN (measurement wavelength: 3.42 μm)
Column: Showa Denko Co., Ltd. AD806M / S 3 (column calibration is Tosoh monodisperse polystyrene (A500, A2500, F1, F2, F4, F10, F20, F40, F288 each 0.5 mg / ml solution) The logarithm of the elution volume and molecular weight was approximated by a quadratic equation, and the molecular weight of the sample was converted to polypropylene using the viscosity equation of polystyrene and polypropylene, where the coefficient of the viscosity equation of polystyrene was α = 0. .723, log K = −3.967, and polypropylene has α = 0.707 and log K = −3.616.)
Measurement temperature: 140 ° C
Concentration: 20 mg / 10 mL
Injection volume: 0.2ml
Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min Viscosity formula: log [η] = log K + α × log M

(A4) Soluble content of 40 ° C. or less by temperature rising elution fractionation (TREF) method (S ₄₀ )
The soluble content (S ₄₀ ) of 40 ° C. or less measured by the temperature rising elution fractionation (TREF) method of the propylene resin used in the present invention is 10% by weight or less, preferably 8% by weight or less, more preferably Is 6% by weight or less, and most preferably 4% by weight or less.
When the soluble content (S ₄₀ ) of 40 ° C. or less measured by the temperature rising elution fractionation (TREF) method is more than 10% by weight, there is a problem that the protected material is contaminated by the low crystalline component sticky component. In addition, in the process of producing the polymer, sticking of the low crystal component causes polymer adhesion in a polymerization tank or the like, resulting in deterioration of the polymer due to stagnation, and as a result, fish eyes derived from polymer degradation products exist in the film. End up.
The soluble content (S ₄₀ ) of 40 ° C. or lower can be adjusted by changing the polymerization conditions (polymerization temperature, polymerization pressure) during production, the type and amount of the catalyst and α-olefin used, and the composition.

(A5) by Atsushi Nobori elution fractionation _(T 100 _{-T 20)}
Width (T ₁₀₀ -T) of temperature (T ₁₀₀ ) when 100 wt% elution is completed from temperature (T ₂₀ ) when 20 wt% is eluted by the temperature rising elution fractionation (TREF) method of the propylene resin used in the present invention. ₂₀ ) is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, further preferably 20 ° C. or lower, and most preferably 15 ° C. or lower. When (T ₁₀₀ -T ₂₀ ) exceeds 30 ° C., a component having high crystallinity and a component having low crystallinity are simultaneously present in the propylene-based resin, and the size and quality of the crystal component are not uniform. As a result, there is unevenness in the viscosity of the molten resin, and an unmelted fine lump becomes a fish eye and exists in the film.
Using a Atsushi Nobori elution fractionation (T _{100 -T 20),} the polymerization conditions at the time of production (polymerization temperature, polymerization pressure), the type of catalyst and α- olefin used and the amount can be adjusted by changing the composition.

The temperature rising elution fractionation (TREF) method employed in the present invention is the method shown below.
That is, a sample is dissolved in orthodichlorobenzene at 140 ° C. to obtain a solution. This is introduced into a 140 ° C. TREF column, cooled to 100 ° C. at a rate of 8 ° C./min, subsequently cooled to 40 ° C. at a rate of 4 ° C./min, and held for 10 minutes. Thereafter, orthodichlorobenzene as a solvent is allowed to flow through the column at a flow rate of 1 mL / min, and components dissolved in the orthodichlorobenzene at 40 ° C. are eluted in the TREF column for 10 minutes, and then the heating rate is 100 ° C./hour. The column is linearly heated to 140 ° C. to obtain an elution curve.
From the elution curve obtained according to the above conditions, the ratio (% by weight) to the total amount of components eluted at 40 ° C. is calculated. Moreover, to calculate the width of the temperature at which eluted 20% by weight temperature upon 100 wt% elution-ending from _{(T 20) (T 100)} (T 100 -T 20). Conditions such as a column to be used, a solvent, and a temperature are as follows.
Column size: 4.3mmφ × 150mm
Column packing material: 100 μm surface inert treatment glass beads Solvent: Orthodichlorobenzene Sample concentration: 5 mg / mL
Sample injection volume: 0.2 mL
Solvent flow rate: 1 mL / min Detector: Fixed wavelength infrared detector MIOX 1A manufactured by FOXBORO
Measurement wavelength: 3.42 μm

Such a propylene resin is required to be polymerized using a metallocene catalyst. A propylene homopolymer or propylene / α-olefin random copolymer polymerized with a metallocene catalyst has a narrow crystallinity distribution and molecular weight distribution, and therefore, as described above, has few components that become fish eye.
On the other hand, when a propylene homopolymer polymerized with a catalyst other than a metallocene catalyst such as a so-called Ziegler-Natta catalyst containing magnesium, titanium, halogen, and an electron donor as an essential component, or a propylene / α-olefin random copolymer is used, Wide molecular weight distribution and high content of high molecular weight component, wide crystal distribution, many low crystal components, and non-uniform crystallinity distribution, resulting in unmelted fine lump in the film And it becomes easy to exist as fish eyes.

  The metallocene catalyst used in the present invention is (i) a group 4 transition metal compound containing a ligand having a cyclopentadienyl skeleton (so-called metallocene compound) and (ii) a metallocene compound. It is a catalyst comprising a cocatalyst that can be activated to a stable ionic state and, if necessary, (iii) an organoaluminum compound, and any known catalyst can be used. The metallocene compound is preferably a bridged metallocene compound capable of stereoregular polymerization of propylene, and more preferably a bridged metallocene compound capable of isoregular polymerization of propylene. Each component will be described.

  Examples of (i) metallocene compounds include JP-A-60-35007, JP-A-63-130314, JP-A-63-295607, JP-A-1-275609, JP-A-2-41303, and JP-A-2-41303. JP-A-2-131488, JP-A-2-76887, JP-A-3-163088, JP-A-4-300787, JP-A-4-21694, JP-A-5-43616, JP-A-5-209913, JP-A-6 No. 239914, JP-A-7-504934, and JP-A-8-85708.

More specifically, methylene bis (2-methylindenyl) zirconium dichloride, ethylenebis (2-methylindenyl) zirconium dichloride, ethylene 1,2- (4-phenylindenyl) (2-methyl-4-phenyl) -4H-azulenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (4-methylcyclopentadienyl) (3-t-butylindenyl) zirconium dichloride, dimethylsilylene (2- Methyl-4-t-butyl-cyclopentadienyl) (3′-t-butyl-5′-methyl-cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (4,5 , , 7-tetrahydroindenyl) zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenylindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-phenylindenyl)] zirconium Dichloride, dimethylsilylenebis [4- (1-phenyl-3-methylindenyl)] zirconium dichloride, dimethylsilylene (fluorenyl) t-butylamidozirconium dichloride, methylphenylsilylenebis [1- (2-methyl-4, ( 1-naphthyl) -indenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4,5-benzoindenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-methyl-4-phenyl-4H) -Azulenyl) ] Zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylsilylenebis [1- (2-ethyl-4-naphthyl-4H-azurenyl)] Zirconium dichloride, diphenylsilylene bis [1- (2-methyl-4- (4-chlorophenyl) -4H-azulenyl)] zirconium dichloride, dimethylsilylene bis [1- (2-ethyl-4- (3-fluorobiphenylyl) ) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-4- (4-chlorophenyl) -4H-azurenyl)] zirconium dichloride, dimethylgermylenebis [1- (2-ethyl-) 4-phenylindenyl)] zirconium Zirconium compounds such as chloride can be exemplified. In the above, compounds in which zirconium is replaced with titanium or hafnium can be used in the same manner. In some cases, a mixture of a zirconium compound and a hafnium compound can be used. Further, the chloride can be replaced with other halogen compounds, hydrocarbon groups such as methyl, isobutyl and benzyl, amide groups such as dimethylamide and diethylamide, alkoxide groups such as methoxy group and phenoxy group, hydride groups and the like.
Among these, a metallocene compound in which an indenyl group or an azulenyl group is crosslinked with silicon or a germyl group is preferable. In particular, a polymer obtained by a catalyst in which a metallocene compound having an azulenyl group and a clay mineral are combined has excellent balance of film forming property and low fish eye.

The metallocene compound may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably an inorganic or organic porous compound. Specifically, ion-exchange layered silicate, zeolite, SiO ₂ , Al ₂ O ₃ , silica alumina, MgO, ZrO ₂ , TiO ₂ , B Examples include inorganic compounds such as ₂ O ₃ , CaO, ZnO, BaO, and ThO ₂ , organic compounds composed of porous polyolefins, styrene / divinylbenzene copolymers, olefin / acrylic acid copolymers, and the like, or mixtures thereof. It is done.

  (Ii) As a co-catalyst that can be activated to a stable ionic state by reacting with a metallocene compound, an organoaluminum oxy compound (for example, an aluminoxane compound), an ion-exchange layered silicate, a Lewis acid, a boron-containing compound, an ionic compound And fluorine-containing organic compounds.

  (Iii) Examples of the organoaluminum compound include trialkylaluminum such as triethylaluminum, triisopropylaluminum, triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, organoaluminum alkoxide. Can be mentioned.

Examples of the polymerization method include a slurry method using an inert solvent in the presence of the catalyst, a solution method, a gas phase method substantially using no solvent, or a bulk polymerization method using a polymerization monomer as a solvent. . As a method for obtaining propylene used in the present invention, for example, a desired polymer can be obtained by adjusting the polymerization temperature and the comonomer amount and appropriately controlling the molecular weight and crystallinity distribution.
Such polypropylene can be appropriately selected from those commercially available as metallocene polypropylene. Examples of commercially available products include “Wintech” manufactured by Nippon Polypro.
The propylene resin of the present invention may be composed of one type or a combination of two or more types as long as the above properties are satisfied.

2. Pressure-sensitive adhesive layer In the surface protective film of the present invention, a pressure-sensitive adhesive layer is formed on one surface of the base material layer made of the propylene-based resin.
As the pressure-sensitive adhesive, an ethylene / α-olefin copolymer having the following characteristics (B1) to (B3) polymerized with a metallocene catalyst and (B4) as required is used.
By using a specific ethylene / α-olefin copolymer layer polymerized with a metallocene catalyst in the pressure-sensitive adhesive layer, at least one of the base material layer and the pressure-sensitive adhesive layer made of a propylene resin polymerized with the metallocene catalyst is in a molten state. When laminated with, it adheres firmly and has excellent delamination properties.
Since the adhesive layer and the base material layer are firmly bonded, for example, after the surface protective film of the present invention is attached to the adherend, the adhesive layer does not remain on the adherend even if it is peeled off again. It can also be used as a surface protective film that can be repeatedly applied.

The α-olefin copolymerized with ethylene is preferably an α-olefin having 3 to 20 carbon atoms, and examples thereof include propylene, butene-1, hexene-1, octene-1, and the like. In particular, propylene, butene- 1 or hexene-1 is preferred. Further, the α-olefin copolymerized with ethylene may be one type or two or more types.
The ethylene content in the ethylene / α-olefin random copolymer is preferably 50% by weight or more. If the ethylene content is low, the viscosity tends to be weak, so the effect as an adhesive layer may be inferior. The content of α-olefin is appropriately adjusted according to the required density.

(B1) the density of the density ethylene · alpha-olefin copolymer is 0.860~0.915g / cm ^3, preferably 0.870~0.910g / cm ^3, more preferably 0.880 to 0 908 g / cm ³ . The density is adjusted by the strength of the adhesive force. However, if the density is less than 0.860 g / cm ³ , the adhesive strength becomes too high, and there is a problem that the substrate film peels off and a mark remains on the protected object. If it exceeds / cm ³ , the adhesive strength becomes too weak and the effect as an adhesive layer cannot be obtained.
In addition, a density is a value measured based on JIS-K6922-2: 1997 appendix (23 degreeC).

(B2) Elution amount of 20 ° C. or less by temperature rising elution fractionation The elution amount of 20 ° C. or less in temperature elevation elution fractionation (TREF) measurement using orthodichlorobenzene of ethylene / α-olefin copolymer as a solvent is 60% by weight. Or less, preferably 50% by weight or less, particularly preferably 15% by weight or less. If the amount of elution at 20 ° C. or less by TREF exceeds 60% by weight, it is not preferable because the peeling strength at the time of feeding is large and the feeding cannot be smoothly performed.
In addition, the elution amount of 65 ° C. or more by temperature rising elution fractionation (TREF) of the ethylene / α-olefin copolymer is 0.3 wt% or more, preferably 1.0 wt% or more, more preferably 2.0 wt%. % Or more, and more preferably 5.0% by weight or more. If it is the said range, since favorable adhesive strength can be maintained, it is preferable.

Here, the amount of elution by TREF is measured by the following cross-fractionation chromatograph (CFC) comprising a temperature rising elution fractionation (TREF) portion for performing crystalline fractionation and a gel permeation chromatography (GPC) portion for performing molecular weight fractionation. Depending on the method.
First, a polymer sample was completely dissolved in orthodichlorobenzene (ODCB) containing 0.5 mg / mL BHT at 140 ° C., and this solution was passed through a sample loop of the apparatus, and a TREF column (inert) maintained at 140 ° C. The polymer sample is crystallized by slowly cooling to a predetermined first elution temperature. After maintaining at a predetermined temperature for 30 minutes, ODCB is passed through a TREF column, whereby the eluted component is injected into the GPC section to perform molecular weight fractionation, and an infrared detector (MIRAN 1A IR detector manufactured by FOXBORO, A chromatogram is obtained with a measuring wavelength of 3.42 μm). Meanwhile, in the TREF part, the temperature is raised to the next elution temperature, and after obtaining the chromatogram of the first elution temperature, the elution component at the second elution temperature is injected into the GPC part. Thereafter, the same operation is repeated to obtain a chromatogram of the eluted components at each elution temperature.
The measurement conditions are shown below.
Equipment: CFC-T102L manufactured by Dia Instruments
GPC column: Showa Denko AD-806MS (3 connected in series)
Solvent: ODCB
Sample concentration: 3 mg / mL
Injection volume: 0.4mL
Crystallization rate: 1 ° C / min Solvent flow rate: 1 mL / min GPC measurement time: 34 minutes Stabilization time after GPC measurement: 5 minutes Elution temperature: 0, 5, 10, 15, 20, 25, 30, 35, 40, 45 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 102, 120, 140
Data analysis: The chromatograms of the elution components obtained at each elution temperature obtained by measurement are processed by the data processing program attached to the instrument, and the elution amount is standardized so that the total is 100% (proportional to the area of the chromatogram) ) Is required. In addition, an integrated elution curve for the elution temperature is calculated. An elution amount of 20 ° C. or lower and an elution amount of 65 ° C. or higher are determined from the obtained elution curve.

(B3) Ratio (Mw / Mn) of weight average molecular weight (Mw) and number average molecular weight (Mn)
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene / α-olefin copolymer is 3.5 or less, preferably 3.0 to 1.5. Especially preferably, it is 2.5-2.0. If Mw / Mn exceeds 3.5, stickiness may occur.
Here, Mw / Mn is defined by the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). The measuring method of Mw / Mn is as follows.
Apparatus: Waters GPC 150C type Detector: MIRAN 1A infrared spectrophotometer (measurement wavelength, 3.42 μm)
Column: AD806M / S manufactured by Showa Denko Co., Ltd. (column calibration was performed by Tosoh monodisperse polystyrene (0.5 mg / ml solution of each of A500, A2500, F1, F2, F4, F10, F20, F40, and F288) Measurement was performed, and the logarithm of the elution volume and molecular weight was approximated by a quadratic equation. The molecular weight of the sample was converted to polyethylene using the viscosity formula of polystyrene and polyethylene. Here, the coefficients of the viscosity formula of polystyrene are α = 0.723 and log K = −3.767, and polyethylene has α = 0.723 and log K = −3.407.
Measurement temperature: 140 ° C
Injection volume: 0.2ml
Concentration: 20 mg / 10 mL
Solvent: Orthodichlorobenzene Flow rate: 1.0 ml / min

(B4) MFR
The melt flow rate (MFR: 190 ° C., 21.18N load) of the ethylene / α-olefin copolymer is preferably from 0.1 to 50 g / 10 minutes, more preferably from 1 to 30 g / 10 minutes, particularly preferably. Is 2 to 15 g / 10 min. When the MFR is less than 0.1 g / 10 min, the extrusion characteristics are likely to deteriorate, and there is a problem in that the interface with the base film made of the propylene resin of the present invention is roughened. If it exceeds 50 g / 10 min, it causes thickness unevenness.
In addition, MFR of an ethylene polymer is a value measured based on JIS-K6922-2: 1997 appendix (190 degreeC, 21.18N load).

  The ethylene / α-olefin copolymer is produced by using a metallocene catalyst in a process such as a gas phase method, a solution method, a high pressure method, or a slurry method, and ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1 Although it can be produced by copolymerization with an α-olefin such as -pentene and 1-octene, those produced by a high-pressure method or a solution method are particularly preferable because both the molecular weight distribution and the crystallinity distribution are narrow.

In the above ethylene / α-olefin copolymer, MFR, density, elution amount of TREF 20 ° C. or less, Mw / Mn change polymerization temperature, polymerization pressure, catalyst used, and type and composition of ethylene and α-olefin. By doing so, it can be adjusted easily.
For example, the density tends to increase as the polymerization temperature is increased, reducing the α-olefin feed rate. In addition, the amount of elution below TREF of 20 ° C. tends to increase as the α-olefin supply amount is increased or the polymerization temperature is lowered. Furthermore, the MFR tends to decrease with increasing polymerization pressure.

  The pressure-sensitive adhesive layer is mainly composed of an ethylene / α-olefin copolymer polymerized using the metallocene catalyst, but only the ethylene / α-olefin copolymer may be used and may contain other components. You can leave. Examples of other components include low density polyethylene. The pressure-sensitive adhesive layer can be used as a pressure-sensitive adhesive layer in consideration of adhesion to the base material layer by blending a pressure-sensitive adhesive with the propylene-based resin used in the present invention. When the above-mentioned pressure-sensitive adhesive is blended and used in the propylene-based resin used in the present invention, when the total amount of the propylene-based resin and the pressure-sensitive adhesive used in the present invention is 100% by weight, the content of the propylene-based resin is 1 to 1%. 99% by weight, and the pressure-sensitive adhesive content is 99 to 1% by weight.

Commercially available ethylene / α-olefin copolymers polymerized using a metallocene catalyst include Harmolex series, Kernel series, Prime polymer Evolue series, Sumitomo Chemical (Japan Polyethylene Co., Ltd.) Exelen GMH series, Exelen FX series, etc. manufactured by Co., Ltd. can be exemplified.
These pressure-sensitive adhesives can be used singly or in combination of two or more, as long as the effects of this object are not impaired.

3. Release treatment layer
As for the surface protection film of this invention, a peeling process layer is formed in the other surface of the adhesive layer formed in one side of the base material layer which consists of said propylene-type resin. As a peeling process layer, the layer which roughened the peeling process layer side surface of a film, formed the unevenness | corrugation, and improved peelability can be mentioned. Roughening the surface of the release treatment layer is for surface protection that has the characteristics that both the pressure-sensitive adhesive layer and the release treatment layer come into contact with each other in a solid state, and when the roll is unwound, it peels off smoothly, and when used, the feeding property improves. It can be a film.

In the layer where the release treatment layer side surface of the film is roughened to form unevenness and the peelability is improved, the center plane average roughness (Ra) of the release treatment layer surface is 0 in the following measurement conditions (C1) to (C6). The resin used is not particularly limited as long as it is within the range of 2 to 1.5 μm, and may be a known thermoplastic resin or thermosetting resin, or a mixture thereof. A layer made of a polyolefin resin is preferable. Specifically, the propylene / α-olefin block copolymer alone, or the propylene homopolymer blended with the propylene / α-olefin block copolymer, or the propylene / α-olefin random copolymer with propylene・ A blend of an α-olefin block copolymer, a low density polyethylene alone, a high density polyethylene alone, a blend of a high density polyethylene in a low density polyethylene, or a low density polyethylene in a propylene homopolymer, Or blended with high density polyethylene, or blended with propylene / α-olefin random copolymer with low density polyethylene, or blended with high density polyethylene, or propylene / α-olefin block copolymer with low density polyethylene, Or Those blended with density polyethylene, or may include those in which these things polyolefin resin blended two or more, or blended with such different thermoplastic resin compatible with these polyolefin resins. More preferably, a propylene / α-olefin block copolymer, low density polyethylene, or high density polyethylene blended with the propylene resin used in the base material layer of the present invention is from the viewpoint of fish eye and delamination. Also good.
(C1) The radius of curvature of the stylus tip is 5 mm
(C2) Cut-off wavelength is 0.80mm
(C3) Cutoff type is 2CR (phase compensation)
(C4) Measurement speed is 0.3 mm / second (C5) Measurement direction is MD direction of film (C6) Measurement length is 2 mm

In order to roughen the film surface to form irregularities and improve the peelability, the irregularities on the film surface have a center plane average roughness (Ra) of 0.2 to 1.5 μm. Preferably it is 0.3-1.2 micrometers, More preferably, it is 0.5-1.0 micrometer, Most preferably, it is 0.8-1.0 micrometer.
Here, since the value obtained by the measurement method of the center plane average roughness (Ra) differs depending on the measurement method and measurement conditions, in the present invention, the stylus type surface defined in JIS-B-0651 (1976). Measure with a roughness meter. The measurement conditions of the measuring instrument are: the radius of curvature of the stylus tip is 5 μm, the cutoff wavelength is 0.80 mm, the cutoff type is 2CR (phase compensation), the measurement speed is 0.3 mm / second, the measurement direction is the film MD direction, and the measurement The length was 2 mm, and the range of surface roughness was defined by the obtained value. The MD direction, which is the measurement direction, refers to the film feed direction during extrusion molding, that is, the direction parallel to the longitudinal direction of the film.

Polyolefin resins used for the release treatment layer include propylene homopolymers (homopolypropylene), propylene / α-olefin random copolymers, propylene resins made of propylene / α-olefin block copolymers, high density polyethylene, and high pressure. Radical polymerization method Polyethylene resin composed of low density polyethylene such as low density polyethylene and linear low density polyethylene.
Propylene-based resins consisting of propylene homopolymer (homopolypropylene), propylene / α-olefin random copolymer, propylene / α-olefin block copolymer generally use known catalysts such as Ziegler catalysts and metallocene catalysts. In the presence of the catalyst, a known polymerization method such as a slurry method using an inert solvent, a solution method, a gas phase method substantially using no solvent, or a bulk polymerization method using a polymerization monomer as a solvent. Manufactured by. Moreover, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene etc. are mentioned as an alpha olefin of a copolymerization component. The α-olefin may be used alone or in combination of two or more.

High-density polyethylene generally uses a catalyst such as a Ziegler catalyst, a Phillips catalyst, or a metallocene catalyst, and is a process such as a gas phase method, a solution method, a high-pressure method, or a slurry method. It is produced by (co) polymerizing with α-olefins such as -butene, 1-hexene, 4-methyl-1-pentene, 1-octene.
High-pressure radical polymerization method Low-density polyethylene uses ethylene or ethylene and a small amount of propylene, 1-butene, 1-hexene, 4-methyl in a process such as a high-pressure radical polymerization method using a radical generator such as peroxide as a polymerization initiator. It is produced by (co) polymerizing α-olefins such as -1-pentene and 1-octene.
Linear low-density polyethylene generally uses a catalyst such as a Ziegler catalyst, a Phillips catalyst, or a metallocene catalyst, and processes such as a gas phase method, a solution method, a high-pressure method, and a slurry method with ethylene and propylene, 1-butene. , 1-hexene, 4-methyl-1-pentene, 1-octene and other α-olefins are copolymerized. The α-olefin may be used alone or in combination of two or more.
The low density polyethylene is preferably a high pressure radical polymerization method low density polyethylene from the viewpoint of moldability.

Moreover, the polyolefin resin used for a peeling process layer can use the resin composition which combined single or 2 types or more of polyolefin resin.
The blending amount and the basic physical properties of the resin are not particularly limited as long as the center plane average surface roughness (Ra) of the surface of the release treatment layer of the film of the present invention is in the range of 0.2 to 1.5 μm. In the combination of polyethylene and high density polyethylene, preferably low density polyethylene 95-50% by weight, high density polyethylene 5-50% by weight, more preferably low density polyethylene 90-60% by weight, high density polyethylene 10-40% by weight. %, More preferably, a polyethylene resin composition containing 80 to 70% by weight of low density polyethylene and 20 to 30% by weight of high density polyethylene. The melt flow rate (MFR; based on JIS-K6922-2: 1997, measured at 190 ° C. and 21.18 N load) of the polyethylene-based resin is 0.1 to 40 g / 10 minutes, preferably 0.3. -25 g / 10 min, more preferably 1.0-10 g / 10 min.

Propylene homopolymer (homopolypropylene), propylene / α-olefin random copolymer, propylene resin and high density polyethylene, propylene / α-olefin block copolymer, high pressure radical polymerization method low density polyethylene, straight chain When a polyethylene-based resin composed of a low-density polyethylene such as a low-density polyethylene is used as a release treatment layer, the propylene-based resin is preferably 99 to 50% by weight, the polyethylene-based resin 1 to 50% by weight, more preferably And a resin composition containing 95 to 70% by weight of propylene resin and 5 to 30% by weight of polyethylene resin.
Moreover, in the combination of propylene-type resin which consists of a propylene homopolymer (homopolypropylene), a propylene alpha-olefin random copolymer, a propylene alpha-olefin block copolymer, Preferably, propylene homopolymer 95-5 Resin composition comprising 5% by weight, 5 to 95% by weight of propylene / α-olefin block copolymer, more preferably 95 to 50% by weight of propylene homopolymer, and 5 to 50% by weight of propylene / α-olefin block copolymer It is a thing. Also, the propylene / α-olefin random copolymer is 95 to 5% by weight, the propylene / α-olefin block copolymer is 5 to 95% by weight, and more preferably, the propylene / α-olefin random copolymer is 95 to 50% by weight. And a resin composition containing 5 to 50% by weight of a propylene / α-olefin block copolymer.

  Propylene resin melt flow rate (MFR; JIS K-7210) composed of a propylene homopolymer (homopolypropylene), a propylene / α-olefin random copolymer, and a propylene / α-olefin block copolymer used in the release treatment layer -The value measured at 230 ° C. under a load of 21.18 N in accordance with 1995) is a melt flow rate (MFR) close to the propylene-based resin used for the base material layer in order to suppress interface roughness with the base material layer. Is preferably 1 to 50 g / 10 minutes, preferably 2 to 30 g / 10 minutes, more preferably 5 to 20 g / 10 minutes, and most preferably 7 to 15 g / 10 minutes. Propylene homopolymer (homopolypropylene), propylene / α-olefin random copolymer, propylene resin and high-density polyethylene made of propylene / α-olefin block copolymer, high-pressure radical polymerization method In the case of a combination of polyethylene resins composed of low density polyethylene such as low density polyethylene and linear low density polyethylene, the melt flow rate (MFR) of propylene resin and the melt flow rate (MFR of polyethylene resin) (JIS-K6922-2). : According to 1997, the value measured at 190 ° C. and a load of 21.18 N) is extremely poor in compatibility if the MFR is too large, and causes fish eyes. Late (MFR) is 0.1 to 40 g / 1 0 minutes, preferably 0.3 to 25 g / 10 minutes, more preferably 1.0 to 10 g / 10 minutes.

  The low density polyethylene used for the release treatment layer has a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) determined by gel permeation chromatography (GPC) of 4.0 to 4.0. It is preferably 8.0. When Mw / Mn is 4.0 to 8.0, the outer layer (release treatment layer) -adhesive delamination property is excellent.

In particular, the polyolefin resin used for the release treatment layer preferably has a D hardness of 50 or more in order to prevent the film surface from being damaged during transportation and transportation.
Here, the D hardness is a value measured in accordance with JIS K7215.

  Since the D hardness of the polyolefin resin is listed in a product pamphlet created by a polyolefin resin manufacturer or a polyolefin resin sales company, it can be selected from those commercially available products. The D hardness of a resin composition in which two or more polyolefin resins are combined can be predicted by an addition rule calculation from the D hardness and composition ratio of each polyolefin resin. In general, the D hardness is considered to change according to the crystallinity of the polyolefin resin. Among the polyolefin-based resins, the polyethylene-based resin has a high density polyethylene and tends to decrease as the density decreases. Moreover, propylene homopolymer is high in a propylene-type resin, and it becomes low as the quantity of a copolymerization component increases.

In the present invention, it is preferable to select in consideration of other performances (transparency, moldability, interlayer strength with the intermediate layer, etc.) within a range where D hardness is 50 or more.
From the viewpoint of the outer layer having high hardness, a resin composition comprising a propylene homopolymer (homopolypropylene) having a high D hardness, a propylene / α-olefin random copolymer, a propylene / α-olefin block copolymer, and a high density polyethylene It is desirable that

4). Resin compounding agent that can be used in each layer The base material layer, the pressure-sensitive adhesive layer, and the release treatment layer that is used as necessary in the present invention include film-forming stability of the film, and handling during secondary processing. And various additives used as a known resin compounding agent, for example, an antioxidant, an antiblocking agent, a slip agent, and a nucleating agent as long as the purpose of the present invention is not impaired from the maintenance of quality as a surface protective film. , Neutralizers, light stabilizers, antistatic agents, tackifiers and the like may be contained. Various additives are described in detail below.

(1) Antioxidants As antioxidants, specific examples of phenolic antioxidants include tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10- Examples thereof include tetraoxaspiro [5,5] undecane, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid and the like.

Specific examples of phosphorus antioxidants include tris (mixed, mono and dinonylphenyl phosphite), tris (2,4-di-t-butylphenyl) phosphite, 4,4′-butylidenebis (3- Methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl) butane, bis (2, 4-di-t-butylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-t -Butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phos Or the like can be mentioned a fight.
Specific examples of the sulfur-based antioxidant include di-stearyl-thio-di-propionate, di-myristyl-thio-di-propionate, pentaerythritol-tetrakis- (3-lauryl-thio-propionate), and the like. it can.
These antioxidants can be used singly or in combination of two or more as long as the effects of the present object are not impaired.

  The compounding quantity of antioxidant is 0.01-1.0 weight part with respect to 100 weight part of each resin used for each layer of a base material layer, an adhesive layer, and a peeling process layer, Preferably it is 0.02-0. 0.5 part by weight, more preferably 0.05 to 0.1 part by weight. When the blending amount of the antioxidant is within the above range, the thermal stability is improved and the deterioration of the resin causing fish eyes is suppressed.

(2) Antiblocking agent The antiblocking agent has an average particle diameter of 1 to 7 μm, preferably 1 to 5 μm, and more preferably 1 to 4 μm. If the average particle diameter is less than 1 μm, the slipperiness and openability of the resulting film are inferior. On the other hand, if it exceeds 7 μm, the transparency and scratching property are remarkably inferior. Here, the average particle diameter is a value obtained by Coulter counter measurement.

Specific examples of the anti-blocking agent include, for example, inorganic or synthetic silica (silicon dioxide), magnesium silicate, aluminosilicate, talc, zeolite, aluminum borate, calcium carbonate, calcium sulfate, barium sulfate, calcium phosphate. Etc. are used.
Moreover, as an organic type, polymethyl methacrylate, polymethylsilyltosesquioxane (silicone), polyamide, polytetrafluoroethylene, epoxy resin, polyester resin, benzoguanamine / formaldehyde (urea resin), phenol resin, or the like may be used. it can.
In particular, synthetic silica and polymethyl methacrylate are preferable from the balance of dispersibility, transparency, blocking resistance, and scratch resistance.
The anti-blocking agent may be surface-treated, and as the surface treating agent, surfactant, metal soap, acrylic acid, oxalic acid, citric acid, tartaric acid and other organic acids, higher alcohols, esters, Condensed phosphates such as silicone, fluorine resin, silane coupling agent, sodium hexametaphosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium trimetaphosphate, etc. can be used, especially those treated with citric acid among organic acids Is preferred. The treatment method is not particularly limited, and a known method such as surface spraying or dipping can be employed.
The anti-blocking agent may have any shape, and can be any shape such as a spherical shape, a square shape, a columnar shape, a needle shape, a plate shape, and an indefinite shape.
These antiblocking agents can be used singly or in combination of two or more in a range that does not impair the effects of the present object.

  The compounding amount of the anti-blocking agent is 0.01 to 1.0 part by weight, preferably 0.05 to 0 with respect to 100 parts by weight of each resin used in each layer of the base material layer, the pressure-sensitive adhesive layer and the release treatment layer. 0.7 parts by weight, more preferably 0.1 to 0.5 parts by weight. When the blending amount of the anti-blocking agent is within the above range, the blocking property is improved and the feeding property is improved.

(3) Slip agent Examples of the slip agent include monoamides and bisamides, which may be substituted, and can be used alone or in combination of two or more.
Specific examples of monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide and the like as saturated fatty acid monoamides.
Examples of the unsaturated fatty acid monoamide include oleic acid amide, erucic acid amide, ricinoleic acid amide and the like.
Specific examples of substituted amides include N-stearyl stearic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide Etc.
Specific examples of bisamides include, as saturated fatty acid bisamides, methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bisisostearic acid amide, ethylene bishydroxystearic acid amide, Ethylene bis behenic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bishydroxy stearic acid amide, N, N'-distearyl adipic acid amide, N, N'-distearyl Sepacic acid amide and the like can be mentioned.
Examples of the unsaturated fatty acid bisamide include ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasin acid amide and the like.
Examples of the aromatic bisamide include m-xylylene bis stearic acid amide and N, N′-distearylisophthalic acid amide.
Among these, oleic acid amide, erucic acid amide, and behenic acid amide are particularly preferably used among the fatty acid amides.

  As a compounding quantity of a slip agent, 0.01-1.0 weight part with respect to 100 weight part of each resin used for each layer of a base material layer, an adhesive layer, and a peeling process layer, Preferably 0.05- When the blending amount of the slip agent is 0.7 parts by weight, more preferably 0.1 to 0.4 parts by weight, the slipping property is improved and the feeding property is improved.

(4) Nucleating agent Specific examples of the nucleating agent include sodium 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphate, talc, 1,3,2,4-di (p-methyl). Benzyl compounds such as benzylidene) sorbitol, hydroxy-di (t-butylaluminum benzoate), 2,2-methylene-bis (4,6-di-t-butylphenyl) phosphoric acid and an aliphatic monocarbon having 8 to 20 carbon atoms Examples thereof include a carboxylic acid lithium salt mixture (manufactured by ADEKA, trade name NA21).
As a compounding quantity of the said nucleating agent, 0.0005-0.5 weight part with respect to 100 weight part of each resin used for each layer of a base material layer, an adhesive layer, and a peeling process layer, Preferably it is 0.001. It is -0.1 weight part, More preferably, it is 0.005-0.05 weight part. When the blending amount of the nucleating agent is within the above range, the crystallization speed is increased and the transparency is improved.

Moreover, a high density polyethylene resin can be mentioned as a nucleating agent other than the above. The density of the high-density polyethylene resin is 0.94 to 0.98 g / cm ³ , preferably 0.95 to 0.97 g / 10 cm ³ . If the density is outside this range, the effect of improving transparency cannot be obtained. The 190 degreeC melt flow rate (MFR) of a high density polyethylene resin is 5 g / 10min or more, Preferably it is 7-500 g / 10min, More preferably, it is 10-100 g / 10min. When the MFR is less than 5 g / 10 min, the dispersion diameter of the high-density polyethylene resin is not sufficiently small, and it itself becomes a foreign matter and causes fish eyes. In order to finely disperse the high-density polyethylene resin, the MFR of the high-density polyethylene resin is preferably larger than the MFR of the propylene-based resin of the present invention.

  The production of the high-density polyethylene resin used as the nucleating agent is not particularly limited with respect to the polymerization method and catalyst as long as a polymer having the desired physical properties can be produced. For catalysts, Ziegler type catalysts (ie, based on a combination of supported or unsupported halogen-containing titanium compounds and organoaluminum compounds), Kaminsky type catalysts (ie, supported or unsupported metallocene compounds and organoaluminum compounds, especially alumoxanes). Based on the combination). There is no restriction | limiting about the shape of a high density polyethylene-type resin, A pellet form may be sufficient and a powder form may be sufficient.

  The blending amount of the high density polyethylene used as the nucleating agent is 0.01 to 5 parts by weight, preferably 100 parts by weight of each resin used in each layer of the base material layer, the pressure-sensitive adhesive layer and the release treatment layer. 0.05 to 3 parts by weight, more preferably 0.1 to 1 part by weight. When the blending amount of the high density polyethylene is within the above range, the crystallization speed is increased and the transparency is improved. Further, in the case of coextrusion molding, there is no transfer of the sweeper roll.

(5) Neutralizing agent Specific examples of the neutralizing agent include calcium stearate, zinc stearate, hydrotalcite, Mizukarak (manufactured by Mizusawa Chemical Co., Ltd.), and the like.
The blending amount of the neutralizing agent is 0.01 to 1.0 parts by weight, preferably 0.02 to 0 parts per 100 parts by weight of each resin used in each of the base layer, the pressure-sensitive adhesive layer and the release treatment layer. 0.5 part by weight, more preferably 0.05 to 0.1 part by weight. When the blending amount of the neutralizing agent is within the above range, the effect as an internal lubricant is improved, and scraping of deteriorated materials inside the extruder is suppressed.

(6) Light Stabilizer As the light stabilizer, a hindered amine stabilizer is preferably used, and a structure in which all hydrogen bonded to carbons at the 2-position and 6-position of a conventionally known piperidine is substituted with a methyl group. Although the compound which has this is used without being specifically limited, the following compounds are specifically used.
Specific examples include polycondensates of dimethyl oxalate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6). -Pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, N, N-bis (3-aminopropyl) ) Ethylenediamine · 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4- Jil} {(2,2, , 6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl} imino], poly [(6-morpholino-s-triazine-2,4-diyl) And [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}].
These hindered amine stabilizers can be used singly or in combination of two or more in a range not impairing the effect of the present object.

The blending amount of the hindered amine stabilizer is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of each resin used in the base layer, the pressure-sensitive adhesive layer and the release treatment layer. Parts, more preferably 0.05 to 0.5 parts by weight.
When the content of the hindered amine stabilizer is less than 0.005 parts by weight, there is no effect of improving the stability such as heat resistance and aging resistance, and when it exceeds 2 parts by weight, the fish eye itself becomes a foreign substance. This is not preferable.

(7) Antistatic agent The antistatic agent can be used without particular limitation as long as it is a known antistatic agent or antistatic agent conventionally used, and examples thereof include anionic surfactants and cations. Ionic surfactants, nonionic surfactants, amphoteric surfactants and the like.

  Examples of the anionic surfactant include fatty acid or rosin acid soap, N-acyl carboxylate, ether carboxylate, carboxylate such as fatty acid amine salt; sulfosuccinate, ester sulfonate, N-acyl sulfonate Sulfonates such as salts; sulfated oils, sulfate esters, alkyl sulfate salts, sulfate sulfate polyoxyethylene salts, sulfate ether salts, sulfate ester salts such as sulfate amide salts; alkyl phosphate salts, alkyl polyoxyethylene phosphates Examples thereof include phosphoric acid ester salts such as salts, phosphoric acid ether salts and phosphoric acid amide salts.

  Examples of the cationic surfactant include amine salts such as alkylamine salts; alkyltrimethylammonium chloride, alkylbenzyldimethylammonium chloride, alkyldihydroxyethylmethylammonium chloride, dialkyldimethylammonium chloride, tetraalkylammonium salt, N, N-di Quaternary ammonium salts such as (polyoxyethylene) dialkylammonium salts and N-alkylalkanamide ammonium salts; 1-hydroxyethyl-2-alkyl-2-imidazoline, 1-hydroxyethyl-1-alkyl-2-alkyl Examples include alkyl imidazoline derivatives such as -2-imidazoline; imidazolinium salts, pyridinium salts, isoquinolinium salts, and the like.

  Examples of the nonionic surfactant include ether forms such as alkyl polyoxyethylene ether and p-alkylphenyl polyoxyethylene ether; fatty acid sorbitan polyoxyethylene ether, fatty acid sorbitol polyoxyethylene ether, fatty acid glycerin polyoxyethylene ether, etc. Ether ester form of fatty acid polyoxyethylene ester, monoglyceride, diglyceride, sorbitan ester, sucrose ester, dihydric alcohol ester, boric acid ester, etc .; dialcohol alkylamine, dialcohol alkylamine ester, fatty acid alkanolamide, N, N-di (polyoxyethylene) alkanamide, alkanolamine ester, N, N-di (polyoxyethylene) alkaneamine, amine oxy De, a nitrogen-formed and fabricated and alkyl polyethylene imine.

  Examples of the amphoteric surfactant include amino acid forms such as monoaminocarboxylic acid and polyaminocarboxylic acid; N-alkyl-β-alanine such as N-alkylaminopropionate and N, N-di (carboxyethyl) alkylamine salt. Forms: Betaine forms such as N-alkylbetaines, N-alkylamidobetaines, N-alkylsulfobetaines, N, N-di (polyoxyethylene) alkylbetaines, imidazolinium betaines; 1-carboxymethyl-1-hydroxy- And alkyl imidazoline derivatives such as 1-hydroxyethyl-2-alkyl-2-imidazoline and 1-sulfoethyl-2-alkyl-2-imidazoline.

  Among these, nonionic surfactants and amphoteric surfactants are preferable. Among them, monoglycerides, diglycerides, boric acid esters, dialcohol alkylamines, dialcohol alkylamine esters, amides and the like or nitrogen-containing non-type surfactants are preferred. Ionic surfactants; betaine amphoteric surfactants are preferred.

  In addition, as an antistatic agent, a commercial item can be used, for example, electro stripper TS5 (trade name, glycerin monostearate manufactured by Kao Corporation), electro stripper TS6 (trade name, stearyl manufactured by Kao Corporation). Diethanolamine), electrostripper EA (trade name, lauryl diethanolamine, manufactured by Kao Corporation), electrostripper EA-7 (trade name, polyoxyethylene laurylamine capryl ester, manufactured by Kao Corporation), Denon 331P (maruhishi oil ( Co., Ltd., trademark, stearyl diethanolamine monostearate), Denon 310 (manufactured by Maruhishi Oil Chemical Co., Ltd., trademark, alkyldiethanolamine fatty acid monoester), Register PE-139 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trademark) , Stearic acid mono & diglyceride Ester), Chemistat 4700 (Sanyo Chemical Industries Co., Ltd., trademark, alkyl dimethyl betaine), rheostat S (Lion Co., Ltd., trademark, alkyl diethanolamide), and the like.

    The blending amount of the antistatic agent is 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of each of the base layer, the pressure-sensitive adhesive layer and the release treatment layer. Preferably it is 0.1-0.8 weight part, Most preferably, it is 0.2-0.5 weight part. These antistatic agents can be used singly or in combination of two or more in a range that does not impair the effects of this object. When the blending amount of the antistatic agent is within the above range, it is possible to prevent electrification and suppress deposits such as dust.

(8) Tackifier The tackifier includes, for example, aliphatic petroleum resins, alicyclic hydrogenated petroleum resins, aromatic petroleum resins, C5 petroleum resins, terpene resins, coumarone / indene resins, A phenol resin, a rosin resin, a tackifier, etc. are mentioned, These can be used 1 type or in combination of 2 or more types in the range which does not impair the effect of this invention remarkably.

  The compounding amount of the tackifier is not particularly limited as long as the effects of the present invention are not impaired, but with respect to 100 parts by weight of each resin used for each layer of the base material layer, the pressure-sensitive adhesive layer and the release treatment layer. 0.0001 to 200 parts by weight. Preferably it is 0.01-150 weight part, More preferably, it is 1-150 weight part, Most preferably, it is 10-100 weight part. When the compounding amount of the tackifier is within the above range, the adhesive strength is improved.

(9) Others Further, an elastomer is blended as a component for imparting flexibility, an ultraviolet absorber, a metal deactivator, a peroxide, a filler, an antibacterial and antifungal agent, as long as the effects of the present invention are not significantly impaired. Agents, fluorescent brighteners, antifogging agents, flame retardants, colorants, pigments, natural oils, synthetic oils, waxes and the like can be blended, and the blending ratio is an appropriate amount.

The blending of the above various additives can be directly added to the propylene resin of the present invention obtained by polymerization and melt kneaded for use, or may be added during melt kneading. Furthermore, it can be added directly after melt-kneading, or can be added as a masterbatch within a range that does not significantly impair the effects of the present invention. Moreover, you may add by these composite methods.
In general, additives such as an antioxidant and a neutralizing agent are blended, mixed, melted and kneaded, and then molded into a product for use. It is also possible to add and use other resins or other additional components (including a masterbatch) as long as the effects of the present invention are not significantly impaired during molding.

  For the above mixing, melting, and kneading, any conventionally known method can be used. Usually, Henschel mixer, super mixer, V blender, tumbler mixer, ribbon blender, Banbury mixer, kneader blender, uniaxial or biaxial kneading. It can be carried out in an extruder. Among these, it is preferable to perform mixing or melt-kneading with a uniaxial or biaxial kneading extruder.

5. Production of Surface Protection Film The surface protection film of the present invention can be produced by a known method for producing a laminated film.
For example, it manufactures by well-known techniques, such as a T die-cast method, a water cooling inflation method, an air cooling inflation method.
Among them, the T-die casting method in which a resin melted and kneaded by an extruder is extruded from a T-die and cooled by being brought into contact with a roll through a coolant such as water to produce a film generally has good transparency. A film with good thickness accuracy can be produced.

  Here, the thickness of the film for surface protection is not particularly limited, but is 10 to 500 μm, preferably 20 to 200 μm, more preferably 30 to 100 μm, and most preferably 40 to 80 μm. If the thickness is outside this range, processing becomes difficult.

As a means for providing the pressure-sensitive adhesive layer on one side of the base material layer, as a method obtained by coating by a solution coating method or the like, a pressure-sensitive adhesive dissolved in an organic solvent such as a toluene solution is applied to one side of the base material layer by a roll coater or the like. The method of drying after application | coating and forming an adhesive layer can be mentioned. At that time, in order to improve the affinity between the base material layer and the pressure-sensitive adhesive layer, conventionally known corona discharge treatment, plasma discharge treatment, primer treatment, etc. are performed on one side of the base material layer (the adhesive surface with the pressure-sensitive adhesive layer). May be.
Moreover, as a method for obtaining the pressure-sensitive adhesive layer by lamination, the pressure-sensitive adhesive is heated and melted by an extruder, extruded into a film form from a T die, and laminated on one side of the base material layer, or the substrate is obtained by an extruder. Examples thereof include a method in which the layer and the pressure-sensitive adhesive are heated and melted and coextruded into a film shape from a T-die together with the base material layer.

  The thickness of the pressure-sensitive adhesive layer is not particularly limited because the adhesive strength varies depending on the application, but is usually 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 5 to 30 μm, and most preferably 10 to 20 μm. .

Examples of the means for forming the release treatment layer provided on the other surface of the pressure-sensitive adhesive layer of the surface protective film of the present invention include known methods such as coating, curing, and lamination.
As a method for obtaining a release treatment layer by coating, a release treatment layer dissolved in an organic solvent such as a toluene solution is applied to one side of a base material layer with a roll coater or the like, and dried to cure the release treatment layer. The method of forming a process layer can be mentioned. At that time, in order to improve the affinity between the base material layer and the release treatment layer, conventionally known corona discharge treatment, plasma discharge treatment, primer treatment, etc. are performed on one side of the base material layer (adhesion surface with the release treatment layer). May be.
In addition, as a method for obtaining a release treatment layer by lamination, a method in which the release treatment layer is heated and melted by an extruder and laminated in a film shape from a T die on one side of a base material layer, or by an extruder, Examples thereof include a method in which the material layer and the release treatment layer are heated and melted and coextruded into a film shape from a T die together with the base material layer.
In the present invention, adopting a method of roughening the surface of the release treatment layer to form unevenness and imparting release properties is advantageous in terms of contamination problems and economical points, and is suitable for the production of the release treatment layer. In addition, a method of co-extrusion with a T die and lamination is preferable.

  Although the thickness of the said peeling process layer is not specifically limited, Usually, 0.1-100 micrometers, Preferably it is 1-50 micrometers, More preferably, it is 5-30 micrometers, Most preferably, it is 10-20 micrometers.

6). Use of surface protective film The surface protective film of the present invention is stuck so that the pressure-sensitive adhesive layer is in contact with the surface of the adherend. Examples of the adherend include building members and liquid crystal display components. Examples of the building member include a synthetic resin plate, a decorative plate, a metal plate, and a glass plate. Moreover, as a structural member of a liquid crystal display, a polarizing plate, a phase difference plate, etc. are mentioned.

  Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. The physical property measurement methods, characteristic evaluation methods, and resin materials used in Examples and Comparative Examples are as follows.

1. Physical property measurement method, characteristic evaluation method (1) MFR: Propylene resin is measured at 230 ° C. under a load of 21.18 N in accordance with JIS K-7210-1995, and ethylene / α-olefin copolymer is measured according to JIS K-6922-2: Measured at 190 ° C. under a load of 21.18 N in accordance with the appendix of 1997.
(2) Density: Measured according to JIS K-6922-2: 1997 appendix (23 ° C.).
(3) Melting peak temperature: Using a differential scanning calorimeter (Seiko DSC), a sample amount of 5.0 mg was taken, held at 200 ° C. for 5 minutes, and then crystallized at a rate of temperature decrease of 10 ° C./min to 40 ° C. And the melting peak temperature (Tmp) when melted at a heating rate of 10 ° C./min was measured.
(4) Weight average molecular weight (Mw) / Number average molecular weight (Mn): Measured by the method described above.
(5) Temperature rising elution fractionation method: Measured by the method described above.
(6) n-decane soluble content: 200 ml of n-decane was added to 5 g of the sample and heated while stirring to completely dissolve the sample. It was cooled to 20 ° C. over about 3 hours and left for 30 minutes. Thereafter, the precipitate was filtered off. The filtrate was put in 1000 ml of acetone to precipitate the components dissolved in n-decane. The precipitate and acetone were filtered off and the precipitate was dried. Even when the filtrate side was concentrated to dryness, no residue was observed. The amount of n-decane solubles was determined by the following formula.
n-decane soluble content (% by weight) = [precipitate weight / sample weight] × 100
(7) Haze: The film was conditioned at 23 ° C. and 50% RH for 24 hours, and then measured with a haze meter in accordance with JIS-K7136-2000.
The smaller the value obtained, the better the transparency.
(8) Tensile elastic modulus: The film was measured for tensile elastic modulus in the flow direction (MD) under the following conditions in accordance with ISO 527.
The higher the obtained numerical value, the higher the rigidity of the film and the easier it is to handle it as a surface protecting film.
Sample length: 150mm
Sample width: 10mm
Distance between chucks: 100mm
Crosshead speed: 25mm / min
(9) Fish eye: The appearance was visually evaluated at an area of 1 m ² of the film. A sample with very few fish eyes was marked with ○, and a sample with many fish eyes was marked with ×.
If the surface of the protective film is less, even if the surface protective film is attached to the object to be protected and stacked and stored, the object to be protected does not dent and is better as a surface protective film.
(10) Tackiness: Acrylic resin plate (mirror surface acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd. “Acrylic”), which has a longitudinal direction of the film, cut to a width of 25 mm and a length of 20 cm, and heated to 60 ° C. LIGHT L001 ”3 mm plate) After aging the pasted film at a temperature of 23 ° C. and a humidity of 50% for 12 hours, in accordance with JIS Z0237, at a pulling speed of 300 mm / min, at a peeling angle of 180 ° C. The adhesive strength per 25 mm width was measured.
The higher the value, the higher the adhesive strength. Although the target strength varies depending on the adherend, the adhesive strength is generally used in the range of 1 to 400 g / 25 mm. If the adhesive strength is too low, it cannot be bonded to a non-adherent body. If the adhesive strength is too high, it cannot be easily peeled off from the adherend.
(11) Surface hardness: measured in accordance with JIS K7215.
(12) Outer layer (peeling treatment layer)-adhesive delamination property: Usually, the surface protective film is wound around a paper tube in a form in which the peeling treatment layer and the pressure sensitive adhesive layer are in contact with each other. Is done. As an evaluation of unwinding property, the molded film is wound up in a form in which a release treatment layer and an adhesive layer are in contact with a 3 inch paper tube, and it is attached to the unwinding machine so that it does not wrinkle or sag when unwinding at 20 m / min. It was confirmed visually whether it could be drawn out smoothly, and ○ that could be drawn out smoothly was marked with ○ and that that could not be drawn out smoothly was marked with ×.
(13) Delamination (Punching impact strength): Using a “puncture tester” tester manufactured by Toyo Seiki, punching was performed using a 1/2 inch hemispherical head, visually confirmed, and those that did not peel Those with peeling were marked with x.

2. Resin material (1) Base layer resin As propylene-based resin of the base layer, the propylene-based resin (PP-1 to 4) obtained in Production Examples 1 to 4 using a metallocene catalyst, and propylene / ethylene random copolymer by metallocene catalyst Combined (Wintech WFX4 (manufactured by Nippon Polypro), Wintech WFW4 (manufactured by Nippon Polypro), Wintech WFX6 (manufactured by Nippon Polypro), Wintech WSX02 (manufactured by Nippon Polypro)) , Propylene / ethylene / butene random copolymer (Novatech PP FX4G (manufactured by Nippon Polypro Co., Ltd.), Novatec PP FW4B (manufactured by Nippon Polypro))), propylene / ethylene random copolymer (manufactured by Nippon Polypro Co., Ltd.) Novatec PP FX3A (Nippon Polypro Co., Ltd.)), Ziegler catalyst Propylene homopolymer (Novatech PP FB3C (manufactured by Nippon Polypro Co., Ltd.)) was used. Table 1 shows the physical properties.

(Production Example 1)
(I) Synthesis of metallocene compound Synthesis of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium is disclosed in JP-A-11-240909. It carried out according to the method as described in the gazette.
(Ii) Preparation of chemically treated ion-exchange layered silicate Slowly add 3.75 liters of distilled water followed by 2.5 kg of concentrated sulfuric acid (96%) to a 10-liter glass separable flask equipped with a stirring blade did. At 50 ° C., 1 kg of montmorillonite (Mizusawa Chemical Benclay SL) was further dispersed, the temperature was raised to 90 ° C., and the temperature was maintained for 6.5 hours. After cooling to 50 ° C., the slurry was filtered under reduced pressure to recover the cake. 7 liters of distilled water was added to this cake, and after reslurry, it was filtered. This washing operation was performed until the pH of the washing liquid (filtrate) exceeded 3.5.
The collected cake was dried at 110 ° C. overnight under a nitrogen atmosphere. The weight after drying was 705 g of chemically treated silicate.
The silicate previously chemically treated was further dried with a kiln dryer. The specifications and conditions of the dryer are as follows.
Rotating cylinder: cylindrical shape, inner diameter 50 mm, humidification zone 550 mm (electric furnace), rotation speed with lifting blade: 2 rpm, tilt angle: 20/520, silicate feed rate: 2.5 g / min, gas flow rate: nitrogen, 96 liters / hour, countercurrent drying temperature: 200 ° C. (powder temperature)
(Iii) Preparation of solid catalyst In a metal reactor equipped with a stirrer with an internal volume of 13 liters, 0.20 kg of the dried silicate obtained above and 0.74 liters of Nitsubishi Mitsubishi Corporation heptane (hereinafter referred to as heptane). In addition, 1.26 liters of a heptane solution of trinormal octyl aluminum (0.04M) was added, and the system temperature was maintained at 25 ° C. After the reaction for 1 hour, it was thoroughly washed with heptane to prepare 2.0 liters of a silicate slurry.
0.80 liters of heptane was added to 2.44 g (3.30 mmol) of (r) -dichloro [1,1′-dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) -4H-azulenyl}] hafnium, A mixture obtained by adding 33.1 ml of a heptane solution of triisobutylaluminum (0.71 M) and reacting at room temperature for 1 hour is added to the silicate slurry, and after stirring for 1 hour, 5.0 heptane is added and 5.0 liter is added. Adjusted.
Subsequently, at a temperature of 40 ° C., propylene was supplied at a rate of 100 g / hour, and prepolymerization was performed for 4 hours. After further polymerization for 1 hour.
After completion of the prepolymerization, the residual monomer was purged, and the catalyst was thoroughly washed with heptane. Subsequently, 0.17 L of heptane solution of triisobutylaluminum was added, followed by drying under reduced pressure at 45 ° C. By this operation, 0.60 kg of a dried prepolymerized catalyst was obtained.
(Iv) Polymerization After the inside of a stirring autoclave having an internal volume of 200 liters was sufficiently substituted with propylene, 24 g of triisobutylaluminum and 0.4 g of hydrogen were added, and 45 kg of sufficiently dehydrated liquefied propylene was introduced thereto. The temperature was raised to 40 ° C. Thereafter, 1.6 g of the prepolymerized catalyst was injected with argon, the temperature was raised to 75 ° C. over 40 minutes, and polymerization was performed for 3 hours. Thereafter, 100 ml of ethanol was injected to stop the reaction, the remaining gas was purged, and the product was dried to obtain a propylene homopolymer (PP1).
(V) Propylene-based resin Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) as an antioxidant with respect to 100 parts by weight of the obtained propylene homopolymer (PP1) Propionate] methane (manufactured by Ciba Specialty Chemicals, trade name Irganox 1010) 0.05 parts by weight, tris- (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals, 0.05 parts by weight of trade name Irgafos 168) was mixed, mixed at 750 rpm for 1 minute with a Henschel mixer, then pelletized at an extrusion temperature of 230 ° C. using a 50 mmφ single screw extruder, and propylene resin (PP-1) Got.

(Production Example 2)
After thoroughly replacing the inside of the stirring autoclave with an internal volume of 200 liters with propylene, 500 ml (0.12 mol) of triisobutylaluminum / n-hexane solution, 0.8 NL of hydrogen, and 1.94 kg of ethylene were added. 45 kg of sufficiently dehydrated liquefied propylene was introduced. The temperature was raised to 40 ° C., and 2.8 g of the prepolymerized catalyst prepared in Production Example 1 was injected with argon. The temperature was raised to 62 ° C. over 40 minutes, and polymerization was carried out for 2 hours under these conditions. Thereafter, 100 ml of ethanol was injected to stop the reaction, and the remaining gas was purged to obtain a propylene / ethylene random copolymer (PP2). The resulting propylene / ethylene random copolymer (PP2) was pelletized by the same additive formulation and method as in Production Example 1 to obtain a propylene-based resin (PP-2).

(Production Example 3)
After thoroughly replacing the inside of the stirred autoclave with an internal volume of 200 liters with propylene, 500 ml (0.12 mol) of triisobutylaluminum / n-hexane solution, 8.0 NL of hydrogen, and 1.92 kg of ethylene were added. 45 kg of sufficiently dehydrated liquefied propylene was introduced. The temperature was raised to 40 ° C., and 1.6 g of the prepolymerized catalyst prepared in Production Example 1 was injected with argon. The temperature was raised to 62 ° C. over 40 minutes, and polymerization was carried out for 2 hours under these conditions. During this time, hydrogen was introduced at a constant speed of 0.48 g / hr. Thereafter, 100 ml of ethanol was injected to stop the reaction, the remaining gas was purged, and the product was dried to obtain a propylene / ethylene random copolymer (PP3). The resulting propylene / ethylene random copolymer (PP3) was pelletized by the same additive formulation and method as in Production Example 1 to obtain a propylene-based resin (PP-3).

(Production Example 4)
After thoroughly replacing the inside of the stirred autoclave with an internal volume of 200 liters with propylene, 500 ml (0.12 mol) of triisobutylaluminum / n-hexane solution, 2.3 NL of hydrogen, and 1.94 kg of ethylene were added. 45 kg of sufficiently dehydrated liquefied propylene was introduced. The temperature was raised to 40 ° C., and 2.2 g of the prepolymerized catalyst prepared in Production Example 1 was injected with argon. The temperature was raised to 62 ° C. over 40 minutes, and polymerization was carried out for 2 hours under these conditions. Thereafter, 100 ml of ethanol was injected to stop the reaction, the remaining gas was purged, and the product was dried to obtain a propylene / ethylene random copolymer (PP4). The resulting propylene / ethylene random copolymer (PP4) was pelletized by the same additive formulation and method as in Production Example 1 to obtain a propylene-based resin (PP-4).

(2) Adhesive Layer Resin As the ethylene / α-olefin copolymer of the adhesive layer resin, the ethylene / α-olefin random copolymer (PE-1 to 2) obtained in Production Examples 5 to 6 using a metallocene catalyst. Low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., brand name: Novatec LD LF441B) was used. Table 2 shows the physical properties.

(Production Example 5)
The catalyst was prepared by the method described in JP-T-7-508545. That is, to the complex dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) hafnium dimethyl 2.0 mmol, tripentafluorophenyl boron was added in an equimolar amount to the above complex, and diluted to 10 liters with toluene. A catalyst solution was prepared.
A stirred autoclave type continuous reactor having an internal volume of 1.5 liters was maintained at a pressure of 130 MPa, and a mixture of ethylene and 1-hexene was 40 kg / hour so that the composition of 1-hexene was 64% by weight. Continuously. Further, the catalyst supply amount was adjusted so that the polymerization temperature was maintained at 150 ° C. The amount of polymer production per hour was about 3.0 kg. After completion of the reaction, an ethylene / 1-hexene copolymer (PE1) having a 1-hexene content of 15% by weight was obtained. The obtained ethylene / 1-hexene copolymer (PE1) was pelletized at an extrusion temperature of 230 ° C. using a 50 mmφ single screw extruder to obtain an adhesive resin (PE-1).

(Production Example 6)
In Production Example 5, the conditions were changed so that the polymerization temperature was 135 ° C., and the composition of 1-hexene in the mixture of ethylene and 1-hexene was 74% by weight, and an ethylene / 1-hexene copolymer (PE2 ) The obtained ethylene / 1-hexene copolymer (PE2) was pelletized at an extrusion temperature of 230 ° C. using a 50 mmφ single screw extruder to obtain an adhesive resin (PE-2).

(3) Release treatment layer resin A polyolefin resin was used as the release treatment layer resin. As propylene-based resin, propylene / ethylene random copolymer (manufactured by Nippon Polypro Co., Ltd., brand name: Wintech WFW4), propylene / ethylene block copolymer (manufactured by Nippon Polypro Co., Ltd., brand name: Novatec BC3HF), As a polyethylene resin, low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., brand name: Novatec LD LC600A, MFR: 7.0 g / 10 min, density: 0.918 g / cm ³ , Mw / Mn: 7.9), Low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., brand name: Novatec LD LF240, MFR: 0.7 g / 10 min, density: 0.924 g / cm ³ , Mw / Mn: 4.9), low density polyethylene (Japan) Product name manufactured by Polyethylene Co., Ltd .; Novatec LD LF441B, MFR: 2.0 g / 10 min, density ^{0.924g / cm 3, Mw / Mn} : 4.4), high density polyethylene (Nippon Polyethylene Co., Ltd., brand name: Novatec HD HJ560, MFR: 7g / 10 min, density: 0.964 g / ^cm 3) Was used.

Example 1
As a base material layer, WFX4 of a propylene-based resin polymerized using a metallocene catalyst, PE-1 as an adhesive layer, and LC600A as a release treatment layer were used.
Using a multilayer T die molding machine having a release agent layer extruder 20 mmφ, a substrate layer extruder 35 mmφ, and an adhesive layer extruder 20 mmφ, a release treatment layer thickness of 20 μm and a substrate layer thickness of 20 μm at a molding temperature of 230 ° C. A surface protective film made of a multilayer T-die film having a pressure-sensitive adhesive layer thickness of 10 μm was prepared. Table 3 shows the evaluation results of the obtained surface protective film.

(Example 2)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the base layer resin WFX4 used in Example 1 was replaced with WFW4. The results are shown in Table 3.

(Example 3)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the pressure-sensitive adhesive layer resin PE-1 used in Example 2 was replaced with PE-2. The results are shown in Table 3.

Example 4
The release treatment layer resin LC600A used in Example 2 was formed and evaluated in the same manner as in Example 1 except that the mixed composition of 80% by weight of LC600A and 20% by weight of HJ560 was replaced. The results are shown in Table 3.

(Example 5)
Except that the release treatment layer resin LC600A used in Example 2 was replaced with BC3HF, a film was formed in the same manner as in Example 1 and evaluated. The results are shown in Table 3.

(Example 6)
The release treatment layer resin LC600A used in Example 2 was formed and evaluated in the same manner as in Example 1 except that the mixed composition of BC3HF was changed to 60% by weight and LF240 was changed to 40% by weight. The results are shown in Table 3.

(Example 7)
The release treatment layer resin LC600A used in Example 2 was formed and evaluated in the same manner as in Example 1 except that the mixed composition was 80% by weight of WFW4 and 20% by weight of LF441B. The results are shown in Table 3.

(Example 8)
The release treatment layer resin LC600A used in Example 2 was formed and evaluated in the same manner as in Example 1 except that the mixed composition was 80% by weight of WFW4 and 20% by weight of HJ560. The results are shown in Table 3.

Example 9
Evaluation was performed by forming a film by the same method as in Example 1 except that the base material layer WFX4 used in Example 1 was replaced with PP-1. The results are shown in Table 3.

(Example 10)
A film was formed and evaluated in the same manner as in Example 1 except that the base material layer WFX4 used in Example 1 was replaced with WFX6. The results are shown in Table 3.

Example 11
Evaluation was performed by forming a film by the same method as in Example 1 except that the base material layer WFX4 used in Example 1 was replaced with WSX02. The results are shown in Table 3.

(Comparative Example 1)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the base material layer resin WFX4 used in Example 1 was replaced with FX4G. The results are shown in Table 4.

(Comparative Example 2)
Evaluation was performed by forming a film by the same method as in Example 1 except that the base material layer resin WFX4 used in Example 1 was replaced with FX3A. The results are shown in Table 4.

(Comparative Example 3)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the base layer resin WFX4 used in Example 1 was replaced with FW4B. The results are shown in Table 4.

(Comparative Example 4)
Evaluation was performed by forming a film by the same method as in Example 1 except that the base layer resin WFX4 used in Example 1 was replaced with FB3C. The results are shown in Table 4.

(Comparative Example 5)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the base material layer resin WFX4 used in Example 1 was replaced with PP-2. The results are shown in Table 4.

(Comparative Example 6)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the base material layer resin WFX4 used in Example 1 was replaced with PP-3. The results are shown in Table 4.

(Comparative Example 7)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the base material layer resin WFX4 used in Example 1 was replaced with PP-4. The results are shown in Table 4.

(Comparative Example 8)
Except that the release treatment layer resin LC600A used in Example 1 was replaced with WFX4, a film was formed in the same manner as in Example 1 and evaluated. The results are shown in Table 4.

(Comparative Example 9)
Evaluation was performed by forming a film in the same manner as in Example 2 except that the adhesive layer resin PE-1 used in Example 2 was replaced with LF441B. The results are shown in Table 4.

  From the results of Table 3 and Table 4, it can be seen that the surface protective film of the present invention has excellent rigidity and less fish eyes. In particular, it can be seen that by adjusting the density of the pressure-sensitive adhesive layer, the desired pressure-sensitive adhesive strength can be imparted, and further, it is excellent in pay-out property and has no or little delamination (Example 1 to Example 1). 11). On the other hand, the propylene homopolymer, propylene / ethylene random copolymer, and propylene / ethylene / butene random copolymer obtained with the Ziegler catalyst have too many fish eyes and are inferior in delamination (Comparative Examples 1 to 4). Moreover, the propylene / ethylene random copolymer having MFR and Mw / Mn obtained by using a metallocene catalyst outside the scope of the present invention cannot produce a film or has too many fish eyes (Comparative Examples 5 to 7). ). Moreover, when the average center surface roughness (Ra) of the release treatment layer is small, the peelability between the outer layer and the adhesive layer is inferior (Comparative Example 8). Furthermore, if a resin produced using a material other than the metallocene catalyst is used for the adhesive layer, the adhesive strength is poor (Comparative Example 9).

  The surface protective film of the present invention uses a specific propylene resin as a base material layer, uses a specific ethylene / α-olefin copolymer as an adhesive layer, and removes the propylene resin and / or polyethylene resin. Since it is used for a layer, there are very few unmelted fish eyes at the time of film formation, and even if a surface protection film is stuck on a to-be-protected object and stored in layers, the to-be-protected object will not be dented. Furthermore, when at least one of a base material layer and an adhesive layer is laminated | stacked in a molten state, it adhere | attaches firmly and is excellent in delamination property. Furthermore, by roughening the surface of the release treatment layer as the release treatment layer, the roll peels off when the roll is unwound from the roll wound state where both the pressure-sensitive adhesive layer and the release treatment layer are in contact with each other in a solid state. Surface protective film having the characteristics of, for protecting the surface of building materials such as synthetic resin plates, decorative plates, metal plates, glass plates, and the surface of liquid crystal display components such as polarizing plates and retardation plates It can be suitably used as a protective film.

Claims (5)

In a surface protective film in which a pressure-sensitive adhesive layer is formed on one surface of a base material layer made of a propylene-based resin and a release treatment layer is formed on the other surface, the propylene-based resin of the base material layer uses a metallocene catalyst. A propylene homopolymer or propylene / α-olefin random copolymer that is polymerized and has the following characteristics (A1) to (A4), the pressure-sensitive adhesive layer is polymerized using a metallocene catalyst, and the following (B1) ~ (B3) is a layer mainly composed of an ethylene / α-olefin copolymer, and the release treatment layer has a surface roughness average (Ra) on the surface of the release treatment layer of the following measurement condition (C1) The film for surface protection characterized by being in the range of 0.2 to 1.5 μm in (C6).
(A1) Melt flow rate (MFR: 230 ° C., 21.18 N load) is 1 to 50 g / 10 minutes (A2) Melting peak temperature (Tmp) by differential thermal scanning calorimeter (DSC) is 120 to 170 ° C.
(A3) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is 1.5 to 3.5.
(A4) Soluble content (S ₄₀ ) of 40 ° C. or less measured by the temperature rising elution fractionation (TREF) method is 10% by weight or less (B1) Density is 0.860 to 0.915 g / cm ³
(B2) In temperature rising elution fractionation (TREF) measurement using orthodichlorobenzene as a solvent, the elution amount at 20 ° C. or less is 60% by weight or less. (B3) Ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) is 3.5 or less (C1) The radius of curvature of the stylus tip is 5 mm
(C2) Cut-off wavelength is 0.80mm
(C3) Cutoff type is 2CR (phase compensation)
(C4) Measurement speed is 0.3 mm / second (C5) Measurement direction is MD direction of film (C6) Measurement length is 2 mm The film for surface protection according to claim 1, wherein the propylene-based resin further has the following property (A5).
(A5) The range (T ₁₀₀ -T ₂₀ ) of the temperature (T ₁₀₀ ) at the end of elution by 100 wt% from the temperature (T ₂₀ ) at the elution of 20 wt% by the temperature rising elution fractionation (TREF) method is 30 ° C. Less than   The film for surface protection according to claim 1, wherein the release treatment layer is made of a polyolefin resin.   The film for protecting a surface according to any one of claims 1 to 3, wherein the film is used for protecting a surface of a building member such as a synthetic resin plate, a decorative plate, a metal plate, and a glass plate.   The surface protecting film according to any one of claims 1 to 3, which is used for protecting a surface of a constituent member of a liquid crystal display such as a polarizing plate or a retardation plate.