JP5264571B2 - Propylene surface protective film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface protection film made of propylene based resin having very little fish eyes, and suitable for a surface protection film of construction members such as a synthetic resin plate, a decorative plate, a metallic plate, and a glass plate, and a surface protection film for a liquid crystal display constituent member such as a polarization plate and a retardation plate. <P>SOLUTION: In the surface protection film, an adhesive layer is formed on one surface of a base material layer made of the propylene based resin, and an exfoliation processing layer is formed on the other surface. The propylene based resin of the base material layer is polymerized by using a metallocene catalyst, and is a propylene monopolymer or a propylene_&alpha;-olefin random copolymer having specific MFR, peak melting temperature, molecular weight distribution, and a TREF value. The adhesive layer is a layer in which the principal component is a rubber based adhesive. The exfoliation processing layer has a central surface mean roughness (SRa) of in a range of 0.2 &mu;m to 1.5 &mu;m. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a film for protecting a propylene-based surface, and more specifically, for protecting a surface of a building member such as a synthetic resin plate, a decorative plate, a metal plate, and a glass plate, and a liquid crystal display component such as a polarizing plate and a retardation plate. The present invention relates to a propylene-based surface protective film that is suitably used for surface protection.

  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 composed of 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.

  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, Providing a surface protective film made of a propylene resin suitable for protecting a surface of a building member such as a metal plate or a glass plate, or as a surface protecting film for a liquid crystal display component such as a polarizing plate or a retardation plate. 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. The ratio of the molecular weight, the propylene resin having a soluble content of 40 ° C. or less measured by the temperature rising elution fractionation method is used for the base material layer, the rubber adhesive is used for the adhesive layer, and the surface center plane average roughness By using a release treatment layer in which (SRa) is in the range of 0.2 to 1.5 μm, the surface has less fish eyes, excellent dimensional stability and surface hardness, and improved peel force control and feeding performance. The inventors found that a protective film can be obtained and completed 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 formed of a rubber-based adhesive, and the release treatment layer has a center plane average roughness (SRa) of the release treatment layer surface within the range of 0.2 to 1.5 μm under the following measurement conditions (B1) to (B6). A surface protective film is provided.
(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 temperature rising elution fractionation (TREF) method is 10% by weight or less Release treatment layer measurement condition (B1) The radius of curvature of the stylus tip is 5 μm
(B2) Cut-off wavelength is 0.80 mm
(B3) Cutoff type is 2CR (phase compensation)
(B4) Measurement speed is 0.3 mm / second (B5) Measurement direction is MD direction of film (B6) Measurement length is 2 mm

According to a second aspect of the present invention, there is provided a surface protecting film according to the first aspect, 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

  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.

  Moreover, according to the 4th invention of this invention, in the 1st-3rd invention, it is used for the surface protection of a building member, The film for surface protection characterized by the above-mentioned is provided.

According to a fifth aspect of the present invention, there is provided a surface protecting film which is used in the first to third aspects of the invention to protect the surface of a liquid crystal display component.

  The film for surface protection of the present invention is made of a specific propylene resin, because the crystallinity distribution of the resin is narrow, the amount of low crystalline components eluted is small, the molecular weight distribution is narrow, and the high molecular weight component is small. There is very little unmelted fish eye during 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 surface protective film of this invention is excellent in blocking property, without using an antiblocking agent. Furthermore, by using a rubber-based adhesive as the adhesive layer, it is excellent in delamination and adhesion because at least one of the base material layer and the adhesive layer is firmly bonded when laminated in a molten state. Excellent resistance to body contamination. 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 protective 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 made of a rubber-based pressure-sensitive adhesive, and the release treatment layer has a center plane average roughness (SRa) of 0.2 to 1. in the measurement conditions (B1) to (B6). It is a film for surface protection which is a layer formed within a range of 5 μm.
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 caused to flow through the column at a flow rate of 1 mL / min, and components dissolved in 40 ° C orthodichlorobenzene 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-3-163888, JP-A-4-30087, 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 polyolefin, styrene / divinylbenzene copolymer, olefin / acrylic acid copolymer, and the like, or a mixture 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, and triisobutylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide, alkylaluminum hydride, and 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 adhesive, a rubber-based adhesive is used.
By using a rubber-based pressure-sensitive adhesive for the pressure-sensitive adhesive layer, when at least one of the base material layer and the pressure-sensitive adhesive layer is laminated in a molten state, it has excellent delamination because it adheres firmly to the adherend. Excellent stain resistance. For example, even if the surface protective film of the present invention is attached to an adherend and then peeled again, the adhesive layer does not remain on the adherend, and can be used as a surface protective film that can be repeatedly attached.
The rubber-based pressure-sensitive adhesive is not particularly limited as long as the effects of the present invention are not impaired, but a natural rubber-based pressure-sensitive adhesive or a synthetic rubber-based pressure-sensitive adhesive such as a thermoplastic styrene-diolefin copolymer hydrogenated product. Agents and the like. Examples of the natural rubber used in the pressure-sensitive adhesive layer of the present invention include a commercial product name: SMR (manufactured by Kasho Corporation). Moreover, the thermoplastic styrene-diolefin copolymer hydrogenated product used in the pressure-sensitive adhesive layer of the present invention has the following property (C1).

(C1) Styrene content [St]
The styrene content [St] of the thermoplastic styrene-diolefin copolymer hydrogenated product is not particularly limited, but is 5 to 60% by weight, preferably 10 to 50% by weight, more preferably 20 to 40% by weight. %. When the styrene content is within the above range, the transparency is good, the affinity with the propylene resin is good, the dispersibility is good, and the flexibility is small.

  The hydrogenated thermoplastic styrene-diolefin copolymer is obtained by hydrogenating a thermoplastic styrene-diolefin copolymer. The hydrogenated thermoplastic styrene-diolefin copolymer may be a block copolymer or a random copolymer. A block copolymer is preferred.

  In the thermoplastic styrene-diolefin block copolymer hydrogenated product, when the styrene block is represented by STY and the diolefin block hydrogenated product is represented by DEN, STY-DEN, STY-DEN-STY, DEN-STY-DEN- A copolymer having a structure such as STY or STY-DEN-STY-DEN-STY can be given.

  Examples of the monomer constituting the diolefin hydrogenated block include hydrogenated butadiene, isoprene, vinylated polyisoprene, etc., and these may be used alone or in admixture of two or more. it can.

  Specific examples of hydrogenated products of block copolymers of styrene blocks and diolefin blocks include, for example, hydrogenated products of styrene-butadiene block copolymers, hydrogenated products of styrene-isoprene block copolymers, styrene- Examples thereof include hydrogenated products of vinylated polyisoprene block copolymers. These can be used alone or in admixture of two or more.

  The hydrogenated styrene-butadiene block copolymer is sold as “Clayton G” by Clayton Polymer Japan Co., Ltd., and as “Tough Tech” by Asahi Kasei Kogyo Co., Ltd. The hydrogenated styrene-isoprene block copolymer is sold by Kuraray Co., Ltd. under the trade name “Septon”. A hydrogenated product of a styrene-vinylated polyisoprene block copolymer is sold by Kuraray Co., Ltd. under the trade name “Hibler”. You may select and use suitably from these goods groups.

  In the hydrogenated thermoplastic styrene-diolefin random copolymer, examples of the monomer constituting the diolefin hydrogenated block include butadiene, isoprene, vinylated polyisoprene, and the like. , Or a mixture of two or more.

  Specific examples of the hydrogenated random copolymer of styrene and diolefin include hydrogenated styrene butadiene random copolymer, hydrogenated styrene-isoprene random copolymer, and styrene-vinylated polyisoprene random. Examples include hydrogenated products of copolymerization, and these can be used alone or in admixture of two or more.

  A hydrogenated product of a styrene-butadiene random copolymer is sold under the trade name “Dynalon” by JSR Corporation.

  Furthermore, a hydrogenated product of a thermoplastic styrene-diolefin block copolymer and a hydrogenated product of a thermoplastic styrene-diolefin random copolymer can be mixed and used.

  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.

  In addition, when the pressure-sensitive adhesive layer is laminated by coextrusion molding with an extruder, the pressure-sensitive adhesive is mixed with the propylene-based resin used for the base material layer of the present invention in consideration of adhesion with the base material layer. It can be used as an agent layer. When the above-mentioned pressure-sensitive adhesive is blended and used in the propylene-based resin used in the present invention, when the total 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. Preferably, the content of the propylene-based resin is 5 to 75% by weight, the content of the pressure-sensitive adhesive is 95 to 25% by weight, more preferably the content of the propylene-based resin is 10 to 50% by weight, and the pressure-sensitive adhesive The content of is 50 to 90% by weight.

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 (SRa) of the release treatment layer surface is 0 under the following measurement conditions (B1) to (B6). 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.
(B1) The radius of curvature of the stylus tip is 5 μm
(B2) Cut-off wavelength is 0.80 mm
(B3) Cutoff type is 2CR (phase compensation)
(B4) Measurement speed is 0.3 mm / second (B5) Measurement direction is MD direction of film (B6) 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 are 0.2 to 1.5 μm in terms of center plane average roughness (SRa). 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 (SRa) differs depending on the measurement method and measurement conditions, in the present invention, the stylus type surface defined in JIS-B-0651 (2001). 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 0.8 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-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 surface average roughness (SRa) 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. And high density polyethylene, preferably low density polyethylene 95-50 wt%, high density polyethylene 5-50 wt%, more preferably low density polyethylene 90-60 wt%, high density polyethylene 10-40 wt% More preferably, it is 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. and a load of 21.18 N in accordance with 1995 is a melt flow rate (MFR) close to that of the propylene-based resin used for the base material layer in order to suppress interface roughness with the base material layer. Preferably, the melt flow rate (MFR) is from 1 to 50 g / 10 minutes, preferably from 2 to 30 g / 10 minutes, more preferably from 5 to 20 g / 10 minutes, most preferably from 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 21.18 N load) is too poor in compatibility with the MFR, and causes a fish eye, so the melt flow rate of polyethylene resin. (MFR) is 0.1 to 40 g / 10 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

  Further, when a release treatment agent such as a silicone type or a long chain alkyl type is used in combination with the release treatment layer, a smooth feeling when the roll is unwound is improved, and a further feeding effect is obtained.

  As the silicone release treatment agent, a commonly used silicone release treatment agent mainly composed of dimethylpolysiloxane can also be used. It is also possible to use a silicone release treatment agent containing a three-dimensional organopolysiloxane. Specifically, a silicone-based release treatment agent containing organopolysiloxane as a main component and blended with a cellulose derivative such as methyl cellulose, ethyl cellulose, acetyl cellulose, alkyd resin, or the like is preferably used. By incorporating a cellulose derivative, an alkyd resin, or the like, it is possible to control the release property of the silicone release agent. The cellulose derivative and alkyd resin are preferably blended in an amount of 5 to 50% by weight in the silicone-based release treatment agent.

Depending on the type of curing reaction (crosslinking reaction) of the organopolysiloxane, it is roughly divided into a condensation reaction type and an addition reaction type, but in the present invention, any reaction type may be used.
For example, as the condensation reaction type silicone release agent, for example, a silicone release agent in which a cellulose derivative or an alkyd resin is blended with an organopolysiloxane having a silanol group at a molecular terminal is mentioned. Here, as the organopolysiloxane having a silanol group at the molecular end, a polysiloxane in which an alkyl group such as a methyl group or an ethyl group or a phenyl group is introduced as a side chain functional group (for example, dimethyl diphenylpolysiloxane) is used. It is preferable that the release agent has a good compatibility with the cellulose derivative and the alkyd resin, and a stable release property. In addition, the organopolysiloxane having a silanol group at the molecular end is appropriately blended with a crosslinking agent such as an alkoxy group-containing organopolysiloxane, or a catalyst such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate, or zinc octylate. May be. Moreover, resin, such as an acrylic resin, can also be suitably mix | blended as a 3rd component as needed. In the silicone release agent, the crosslinking agent is preferably 4 to 20% by weight, the catalyst is preferably 5 to 10% by weight, and the resin as the third component is preferably 5 to 26% by weight.

  As an addition reaction type silicone release agent, for example, a silicone release agent in which a cellulose derivative or alkyd resin is blended with organopolysiloxane having at least two alkenyl groups such as vinyl groups bonded to silicon atoms in one molecule. Agents. Here, as the above-mentioned organopolysiloxane, it is preferable to use an organopolysiloxane having an alkyl group such as a methyl group or an ethyl group or a phenyl group introduced as a functional group of the side chain, whereby cellulose derivatives or alkyds are used. A release agent having good compatibility with the resin and stable release characteristics can be obtained. The organopolysiloxane may be appropriately blended with a crosslinking agent such as an organohydrodiene polysiloxane and a catalyst such as a platinum compound such as chloroplatinic acid.

  The silicone-based release treatment agent can be appropriately selected from commercially available products. For example, as a condensation reaction type silicone release agent, KS available from Shin-Etsu Chemical Co., Ltd., KS -723A / B (consisting of dimethyl diphenylpolysiloxane, methoxysilicone and ethylcellulose) is X-62-9201A / B available from Shin-Etsu Chemical Co., Ltd. as an addition reaction type silicone release agent. be able to.

Examples of the long-chain alkyl release agent include a polymer of a long-chain alkyl acrylate having 12 or more carbon atoms, a copolymer of a long-chain alkyl acrylate and another vinyl monomer, or a long-chain alkyl isocyanate to polyvinyl alcohol. And a release agent obtained from a reaction product obtained by reacting the long-chain alkyl component.
For example, BP type manufactured by Nitto Denko Corporation, ashioresin manufactured by Ashio Sangyo Co., Ltd., and Pyroleil manufactured by Yushi Co., Ltd. can be used.

As a means of using a release treatment agent such as a silicone type or a long chain alkyl type in combination with the release treatment layer, a method of applying and curing to the release treatment layer by a known method, blending in advance with a release treatment layer resin, etc. A method can be mentioned.
As a method of applying to the release treatment layer, on the surface of the release treatment layer, a silicone or long chain alkyl release agent dissolved in an organic solvent such as a toluene solution is applied with a roll coater and dried. A method of curing the release treatment agent to form a release treatment layer can be mentioned. At this time, in order to improve the affinity, the surface of the release treatment layer may be subjected to conventionally known corona discharge treatment, plasma discharge treatment, primer treatment, and the like.
In addition, as a method of blending in advance in the release treatment layer, by using an extruder, a release treatment agent such as silicone or long-chain alkyl is blended in the release treatment layer resin and heated and melted, and in a film form from the T die, Examples thereof include a method of laminating on one side of the base material layer, a method of heating and melting with an extruder, and coextruding into a film form from a T die together with the base material layer.

  In the present invention, when a silicone-based or long-chain alkyl-based release treatment agent is blended into a release treatment layer resin and a method of co-extrusion formation with a base layer from a T-die is adopted, there is a problem of contamination and economics. This is advantageous.

In the case of a method in which a silicone-based or long-chain alkyl-based release treatment agent is applied in a subsequent process to form a release treatment resin layer, the application amount of the release treatment agent is usually 0.01 to 10 g / m ² , preferably 0.5 to 0.7 g / m ² , more preferably 0.1 to 0.4 g / m ² . In the case of long-chain alkyl-based, 0.005~10g / ^{m 2,} preferably 0.02~0.3g / ^{m 2,} particularly preferably preferably 0.01 to 0.1 g / ^{m 2.}
In addition, in the case of a method of forming a release treatment layer obtained by blending a release treatment agent into a release treatment layer resin and heating and melting from an extruder, the blending amount of the release treatment agent is the sum of the release treatment layer resin and the release treatment agent. Is 100% by weight, the content of the release treatment layer resin is 90 to 99.95% by weight, and the content of the release treatment agent is 10 to 0.05% by weight. Preferably, the content of the release treatment layer resin is 95 to 99.9% by weight, and the content of the release treatment agent is 5 to 0.1% by weight.

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 You can list s fights.
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 0.01-2.0 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 average particle diameter of an antiblocking agent is 1-7 micrometers, Preferably it is 1-5 micrometers, More preferably, it is 1-4 micrometers. 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, etc. 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 with citric acid treatment among organic acid treatments 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 anti-blocking agents can be used singly or in combination of two or more in a range that does not impair the effects of this 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, and these may be substituted. Among these, it can be used 1 type or in combination of 2 or more types.
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 among monoamides 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 Examples include palmitic acid amide.
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 bisbehenic 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 unsaturated fatty acid bisamides include ethylene bisoleic acid amide and hexamethylene bisoleic acid amide.
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.
Specific examples of substituted amides among bisamides include N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin amide, and the like.

  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- 0.7 part by weight, more preferably 0.1 to 0.4 part by weight. When the blending amount of the slip agent is within the above range, 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 out of 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, as long as the effects of the present object are not impaired.

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 amount of the hindered amine stabilizer is within the above range, stability such as heat resistance and aging resistance is improved.

(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 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. More 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 within a range that does not significantly impair the effects of the present invention. 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 antioxidants and neutralizers are blended, mixed, melted and kneaded, and then molded into products 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, a Henschel mixer, a super mixer, a V blender, a tumbler mixer, a ribbon blender, a Banbury mixer, a kneader blender, a 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. Such a method is a preferable manufacturing method for the film.

  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.
In the present invention, adopting a method in which the pressure-sensitive adhesive layer is coextruded and formed from a T-die together with a base material layer is advantageous in terms of contamination problems and economical points.

  The thickness of the pressure-sensitive adhesive layer is not particularly limited because the pressure-sensitive adhesive strength varies depending on the application, but in the case of a method of forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive in a subsequent step, the thickness of the pressure-sensitive adhesive layer is also melted by heating from an extruder. Also in the method of forming the pressure-sensitive adhesive layer, it 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 the release treatment layer by coating, a release treatment agent dissolved in an organic solvent such as a toluene solution is applied to one side of the base material layer with a roll coater, and then dried to cure the release treatment agent and release. 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.
Moreover, as a method of obtaining the release treatment layer by lamination, it is heated and melted by an extruder, and is an extrusion laminating method in which a film is formed from a T-die and laminated on one side of the substrate layer, or the substrate layer is obtained by an extruder. And a method in which the release treatment layer is heated and melted and coextruded into a film shape from a T die together with the base material layer.

  In the present invention, when an extrusion laminating method for laminating on one side of a base material layer or a method of co-extrusion forming a release treatment layer together with a base material layer from a T-die is used, contamination problems and economic points Is advantageous.

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.

  The thickness of the release treatment layer is not particularly limited, but in the case of a method of forming a release treatment layer by applying a release treatment agent in a subsequent step, a method of forming a release treatment layer formed by heating and melting from an extruder. In some cases, the thickness 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 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 with respect to the flow direction (MD) of the film in accordance with ISO 527 under the following conditions.
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 film was cut into a size of 20 cm × 15 cm and visually evaluated. A sample with very few fish eyes was marked with ◯, a sample with slightly scattered eyes was marked with Δ, 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. 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, bonding to the adherend cannot be performed. If the adhesive strength is too high, it cannot be easily peeled off from the adherend.
(11) Exterior (peeling treatment layer) -adhesive delamination property: Usually, the surface protective film is wound around a paper tube in a form in which the outer layer (peeling treatment layer) and the pressure sensitive adhesive layer are in contact with each other, and is fed and adhered to the product. Used. As an evaluation of unwinding property, the formed film is wound up in a form in which the outer layer (peeling layer) and the adhesive layer are in contact with a 3 inch paper tube, attached to the unwinding machine, and wrinkled, sagging, etc. It was visually confirmed whether it could be smoothly fed out without entering, and the one that could be smoothly fed out was marked with ◯, and the one that could not be smoothly fed out was marked with X.
(12) Contamination resistance of adherend: In the above-described adhesion evaluation, when the film is peeled off from the acrylic plate, ○ indicates that no peeling trace remains, and the peeling trace or the adhesive layer resin remains on the acrylic plate. 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. For comparison, the base layer is made of low-density polyethylene (Novatech LD LC600A (manufactured by Nippon Polyethylene Co., Ltd.), MFR: 7.0 g / 10 min, density: 0.918 g / cm ³ , Mw / Mn: 7.9). 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. This was performed according to the method described in the publication.
(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 Co., Ltd. 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. Further polymerization was carried out 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).
(Vi) 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 powder) ) Propionate] 0.05 parts by weight of methane (manufactured by Ciba Specialty Chemicals, trade name Irganox 1010), tris- (2,4-di-t-butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals) , 0.05 parts by weight of trade name Irgaphos 168), mixed at 750 rpm with a Henschel mixer for 1 minute, pelletized at an extrusion temperature of 230 ° C. using a 50 mmφ single screw extruder, and propylene resin (PP-1 ) Table 1 summarizes the physical properties of the resulting propylene-based resin (PP-1).

(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, the remaining gas was purged, and the product was dried to obtain a propylene / ethylene random copolymer (PP2). The resulting propylene / ethylene random copolymer (PP2 powder) was pelletized by the same additive formulation and method as in Production Example 1 to obtain a propylene 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 powder) 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 powder) 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 The rubber adhesive used as the adhesive layer is SMR (manufactured by Kasho Co., Ltd.) as a natural rubber adhesive, and styrene-butadiene-styrene block copolymer as a synthetic rubber adhesive. Kraton G1657 (made by Kraton Polymer Japan Co., Ltd., styrene content: 13% by weight), Kraton G1652 (made by Kraton Polymer Japan Co., Ltd., styrene content: 29% by weight), Kraton G1726 (Clayton Polymer Japan Co., Ltd.) Styrene content: 30 wt%), Dynalon 1321P (manufactured by JSR Corporation, styrene content: 10 wt%), which is a hydrogenated product of styrene-butadiene random copolymer, and ethylene / vinyl acetate copolymer ( EVA), obtained by high pressure radical polymerization method Novatec EVA / LV342 (made by Nippon Polyethylene Co., Ltd.) having a vinyl acetate content (VAC) of 10% was used.

(3) Release treatment layer Polyolefin resin was used as the release treatment layer resin. As propylene-based resins, 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) Using. 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) Brand name: Novatec LD LF441B, MFR: 2.0 g / 10 min, density: 0.924 g / cm ³ , Mw / Mn: 4.4), high density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.) Brand name: Novatec HD HJ560, MFR: 7 g / 10 min, density: 0.964 g / cm ³ ).

Example 1
As the base material layer, WFX4 of a propylene-based resin polymerized using a metallocene catalyst, Kraton G1657 as an adhesive layer, and LC600A as a release treatment layer were used.
Extruder 35 mmφ for base material layer, 20 mmφ for pressure sensitive adhesive layer, 20 mmφ for exfoliation treatment layer, multilayer T-die molding machine with air knife and cooling roll, forming temperature 230 ° C., cooling roll temperature 30 A surface protective film made of a co-pressed three-layer T-die film having a base material layer thickness of 30 μm, a pressure-sensitive adhesive layer thickness of 10 μm, and a release treatment layer thickness of 10 μm was produced under the conditions of ° C. 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 2.

(Example 3)
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 2.

Example 4
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 2.

(Example 5)
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 2.

(Example 6)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the adhesive layer resin Kraton G1657 used in Example 2 was replaced with Kraton G1652. The results are shown in Table 2.

(Example 7)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the adhesive layer resin Kraton G1657 used in Example 2 was replaced with Kraton G1726. The results are shown in Table 2.

(Example 8)
Evaluation was performed by forming a film in the same manner as in Example 1 except that the adhesive layer resin Kraton G1657 used in Example 2 was replaced with Dynalon 1321P. The results are shown in Table 2.

Example 9
The same as Example 5 except that the pressure-sensitive adhesive resin Dynalon 1321P used in Example 8 was replaced with a pellet mixture in which WFX4 of propylene-based resin polymerized using a metallocene catalyst was 10 wt% and Dynalon 1321P was 90 wt%. The film was formed by the method and evaluated. The results are shown in Table 2.

(Example 10)
The pressure-sensitive adhesive resin used in Example 9 was changed in the same manner as in Example 5 except that the propylene-based resin polymerized using a metallocene catalyst was replaced with a pellet mixture containing 50% by weight of WFX4 and 50% by weight of Dynalon 1321P. A film was formed and evaluated. The results are shown in Table 2.

(Example 11)
Same as Example 5 except that the pressure-sensitive adhesive resin Dynalon 1321P used in Example 9 was replaced with a pellet mixture in which WFX4 of propylene-based resin polymerized using a metallocene catalyst was 90% by weight and Dynalon 1321P was 10% by weight. The film was formed by the method and evaluated. The results are shown in Table 2.

(Example 12)
As a base material layer, using a propylene-based resin WFW4 polymerized using a metallocene catalyst, a base material layer extruder 35 mmφ, a release treatment layer extruder 20 mmφ, a T-die molding machine having an air knife and a cooling roll A two-layer co-pressed film having a substrate layer thickness of 30 μm and a release treatment layer thickness of 10 μm was produced under the conditions of a molding temperature of 230 ° C. and a cooling roll temperature of 30 ° C.
Natural rubber (trade name: SMR, manufactured by Kasho Co., Ltd.) 100% by weight, alicyclic petroleum resin (trade name: Alcon P100, Arakawa Chemical Co., Ltd.) 50 parts by weight of a company), 10 parts by weight of a terpene phenol resin (trade name: PR-12603N, manufactured by Sumitomo Chemical Co., Ltd.), 1 part by weight of an antioxidant (trade name: Irganox 1010, manufactured by Ciba Specialty Chemicals) Is mixed in toluene to produce a rubber-based pressure-sensitive adhesive having a solid content concentration of 20%, and this rubber-based pressure-sensitive adhesive is applied to the surface opposite to the release treatment layer with a reverse coater. The surface protection film which dried for 10 minutes and formed the 10-micrometer-thick rubber-type adhesive layer was produced. Table 2 shows the evaluation results of the obtained surface protective film.

(Example 13)
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 14)
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 15)
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 16)
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 17)
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 18)
The exfoliation treatment layer resin LC600A used in Example 2 was melt extrusion mixed with 99.75% by weight of BC3HF and 0.25% by weight of polydimethylsiloxane SH200 (made by Toray Dow Corning Co., Ltd.) as a silicone release agent. Except having replaced with the composition, it formed into a film by the same method as Example 1, and evaluated. 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)
A film was formed and evaluated in the same manner as in Example 1 except that the pressure-sensitive adhesive Kraton G1657 used in Example 2 was replaced with LV342. The results are shown in Table 4.

(Comparative Example 9)
Evaluation was performed by forming a film in the same manner as in Example 1 except that LC600A of the release treatment layer resin used in Example 2 was replaced with WFW4. The results are shown in Table 4.

(Comparative Example 10)
The base material layer resin WFW4 used in Comparative Example 8 is LC600A (Novatec LD (low density polyethylene) manufactured by Nippon Polyethylene Co., Ltd.), MFR: 7.0 g / 10 min, density: 0.918 g / cm ³ , Mw / Mn : A film was formed and evaluated in the same manner as in Example 1 except that it was changed to 7.9). The results are shown in Table 4.

From the results of Table 2 and Table 3, it can be seen that the surface protective film of the present invention has excellent rigidity and little fish eye (Examples 1 to 18). 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 (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). ).
In addition, by using a rubber-based pressure-sensitive adhesive for the pressure-sensitive adhesive layer, it is possible to provide a surface protective film having high adhesive strength and excellent resistance to contamination to an adherend (Examples 1 to 8 and Example 12). To 18). Furthermore, adhesive strength can be easily adjusted by mix | blending propylene-type resin with an adhesive (Examples 9-11). On the other hand, a film using EVA instead of a rubber-based pressure-sensitive adhesive layer is inferior in stain resistance to the adherend due to the pressure-sensitive adhesive layer being peeled off from the adherend even though the adhesive strength is weak (comparison) Example 8).
Moreover, even if the adhesive force is strong, the peelability between the outer layer and the adhesive layer is improved by roughening the surface of the release treatment layer, and the payout property is improved (Examples 1 to 18). On the other hand, a film in which the surface of the release treatment layer is not rough has a poor feeding property (Comparative Example 9).
Moreover, the film using low-density polyethylene for the base material layer has lower rigidity and lower stiffness than the film using the propylene-based resin of the present invention (Comparative Example 10).

  The surface protective film of the present invention uses a specific propylene-based resin as a base material layer, a rubber-based adhesive as a pressure-sensitive adhesive layer, and a propylene-based resin within a specific center plane average roughness (SRa) and Also, because it uses a release layer of polyethylene resin, there are very few unmelted fish eyes when forming the film, and even if the surface protection film is stuck on the object to be stacked and stored in layers, it will dent in the object to be protected Will not occur. Furthermore, when at least one of the base material layer and the pressure-sensitive adhesive layer is laminated in a molten state, it is firmly bonded, so that the delamination property is excellent and the adherend is excellent in stain resistance. 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.

JP-A-9-111208 JP 54-133578 A JP 2006-282761 A

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. It is 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 formed of a rubber-based pressure-sensitive adhesive, and the release treatment layer is peeled off The surface protective film, wherein the center plane average roughness (SRa) of the treatment layer surface is in the range of 0.2 to 1.5 μm under the following measurement conditions (B1) to (B6).
(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 temperature rising elution fractionation (TREF) method is 10% by weight or less (B1) radius of curvature of stylus tip is 5 μm
(B2) Cut-off wavelength is 0.80 mm
(B3) Cutoff type is 2CR (phase compensation)
(B4) Measurement speed is 0.3 mm / second (B5) Measurement direction is MD direction of film (B6) 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.   It is used for the surface protection of a building member, The film for surface protection of any one of Claims 1-3 characterized by the above-mentioned.   It is used for the surface protection of the structural member of a liquid crystal display, The film for surface protection of any one of Claims 1-3 characterized by the above-mentioned.