TW201510035A - Surface protective film - Google Patents

Abstract

The purpose of the present invention is to provide a surface protective film in which, when affixed to various adherends that are flat or have concavities and convexities, self-releasing from an adherend is prevented and acceleration of adhesion in the adhesive layer can be prevented. The surface protective film of the present invention comprises a layered body having a substrate layer and at least one adhesive layer composed of a resin composition characterized in containing 2 to 50 parts by weight of a 4-methyl-1-pentene.[alpha]-olefin copolymer (A) that satisfies the conditions (a), (b), (c), and (d) below, and 50 to 98 parts by weight of a thermoplastic resin (B). The copolymer (A) satisfies the conditions of (a) comprising 65 to 90 mol% of a constituent element (i) derived from 4-methyl-1-pentene, and 35 to 10 mol% of a constituent element (ii) derived from [alpha]-olefin; (b) having an intrinsic viscosity [[eta]] in the range of 0.1 to 5.0 dL/g as measured at 135 DEG C in decalin; (c) having a molecular weight distribution (Mw/Mn) in the range of 1.0 to 3.5; and (d) having a density in the range of 870 to 830 kg/m3.

Description

Surface protection film

The present invention relates to a surface protective film comprising a laminate having an adhesive layer comprising a specific resin composition.

In order to protect a metal plate such as an aluminum plate, a steel plate, or a stainless steel plate, and such a coated plate, a glass or a synthetic resin plate, and a product and a component including the same, a surface protective film in which an adhesive layer and a base material layer are laminated is used. The surface protective film is peeled off at a predetermined period of time during or after the forming of the material.

The surface protective film is required to be adhered to the adherend and easily adhered, and is not easily peeled off during conveyance of the adherend, and can be easily peeled off during processing or peeling after processing. Therefore, the protective film is required to have a moderate degree of adhesion to the protected surface of the adherend, and the film itself is not moderately soft to the extent that the protected surface is damaged, and the stretched film is required to be processed during the forming of the adhered body. Various properties such as characteristics such as moderate mechanical properties and heat resistance. Further, it is necessary to have a good appearance, transparency, and color tone depending on the use, and it is required to have no film defects such as gel or fish eyes. Further, such a surface film is consumed in a large amount and is quickly discarded, and therefore it is required to be inexpensive to manufacture.

In the past, as an adhesive film, an acrylic or rubber-based adhesive is applied to one surface of a base film containing a polymer such as low-density polyethylene or polypropylene as a main component, or a poly-polymer is used. An olefin, a styrene-based elastomer, or the like is formed by extrusion molding of a base material layer in the form of particles for an adhesive.

For example, Patent Document 1 discloses an adhesive or an adhesive sheet containing a propylene-based polymer containing propylene, an α-olefin having 4 to 12 carbon atoms, and ethylene as a copolymer component, and having low contamination to the adherend.

Further, regarding electronic materials and optical products, there are a large number of members having required characteristics such as a polarizing plate, a phase difference plate, a light guide plate, a reflecting plate, and a seesaw, and it is desirable to provide a protective film which also maintains an appropriate adhesive force for the members. Since the adhered body having irregularities on the surface has a small contact area with the adhesive layer, a high adhesive force is required for the adhesive layer. However, due to the formation of high adhesion, there is a concern about the limitation of the molding method such as coating, the residue remaining on the adherend, and the like.

In view of the above, the electronic material and the optical product may have irregularities such as a polarizing plate, a phase difference plate, a light guide plate, a reflection plate, a ruthenium sheet, or a diffusion film. In order not to damage the unevenness, the uneven surface is protected by a protective film before use, and it is desirable to maintain a moderately protective surface protective film for the members. When such a surface protective film is attached to the surface of the adherend, there is a problem of so-called adhesion due to time, temperature, and the like. Adhesive adhesion, especially in the case of having a surface uneven shape, is caused by an increase in the contact area between the adherend and the adhesive layer, in the case of an adherend having a relatively small unevenness such as a diffusion film or a reflective film, The increase in the contact area is remarkable, so that adhesion is particularly likely to occur. As a result, it is difficult to carry out the work of peeling off from the surface of the adherend, or the adhesive portion partially remains on the adherend to cause paste residue.

Patent Documents 2 and 3 disclose a surface protective film containing an adhesive layer containing a styrene-based elastomer as an isobutylene-based block copolymer and an adhesion-imparting resin. However, in the case of adhering to the adherend of high irregularities by the method of the above publication, there is a case where the adhesive force is insufficient, the viscosity or the adhesion is poor, and the extrusion molding is poor. Productivity is defective.

Further, Patent Documents 4 and 5 disclose that a resin composition and a surface protective film which are not easily viscous in the adhesive layer using a styrene-based elastomer are present, but remain in polyethylene terephthalate (PET). The adhesion of a smooth substrate such as a substrate or an acrylic substrate is evaluated, and the adhesion is low, so that it is difficult to promote the substrate having the uneven shape.

Further, Patent Document 6 discloses a surface protective film in which an adhesive layer suppresses adhesion by a composition of a strong adhesive styrene elastomer and a specific fatty amide, but since a low molecular weight compound is used, it is feared that Contamination of the adherend.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. WO2008/099865

Patent Document 2: Japanese Patent Laid-Open Publication No. 2007-126512

Patent Document 3: Japanese Patent Laid-Open Publication No. 2012-255071

Patent Document 4: Japanese Patent Laid-Open Publication No. 2008-274213

Patent Document 5: Japanese Patent Laid-Open No. 2011-126169

Patent Document 6: Japanese Patent Laid-Open Publication No. 2013-121989

In order to solve the problem to be solved by the present invention, it is an object of the invention to provide a surface protection film which prevents natural peeling from an adherend when attached to a flat surface or various adherends having irregularities. Further, another object of the present invention is to provide a surface protection capable of suppressing adhesion of an adhesive layer when attached to various adherends. film.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the surface protective film having an adhesive layer containing a specific resin composition in which a thermoplastic resin is blended in a 4-methyl-1-pentene copolymer is expressed. A good bump follow-up, with sufficient adhesion strength and sufficient adhesion stability. That is, when a material having a higher adhesiveness is attached to an adherend having a small contact area as before, an adhesive having a sufficient adhesive force and good bump followability can be used to be attached to the adhesive. The contact area of various adherends having irregularities. As a result, it was found to have good adhesive stability, thereby completing the present invention.

Further, the inventors of the present invention have found that a specific resin composition obtained by blending a thermoplastic resin in a 4-methyl-1-pentene copolymer has sufficient adhesive strength and adhesion inhibition effect when used as an adhesive. Thus, the present invention has been completed.

The surface protection film of the present invention comprises a laminate comprising at least one adhesive layer comprising a resin composition and a substrate layer, the resin composition comprising: the following necessary conditions (a), (b), (c) and (d) 4-methyl-1-pentene ‧ α -olefin copolymer (A) 2 to 50 parts by weight, and the 4-methyl-1-pentene ‧ α - olefin copolymer ( 98 to 50 parts by weight of the thermoplastic resin (B) other than A) (wherein the total of the 4-methyl-1-pentene ‧ α - olefin copolymer (A) and the thermoplastic resin (B) is 100 parts by weight) : (a) comprises a constituent unit derived from 4-methyl-1-pentene (i) 65 to 90 mol% and a composition derived from olefin (excluding 4-methyl-1-pentene) Unit (ii) 35~10 mol%.

(b) The ultimate viscosity [η] measured at 135 ° C in decalin is in the range of 0.1 to 5.0 dL/g; (c) the weight average molecular weight measured by gel permeation chromatography (GPC) The ratio of (Mw) to the number average molecular weight (Mn) (molecular weight distribution, Mw/Mn) is in the range of 1.0 to 3.5; and (d) the density is in the range of 870 to 830 kg/m ³ .

The surface protection film of the present invention can exert sufficient adhesion not only when attached to the adherend of the flat plate, but also exerts sufficient adhesion when attached to various adherends having irregularities, and is excellent in unevenness. Follow-up increases the contact area to the adherend, thereby providing sufficient adhesion stability. Further, the surface protective film of the present invention exhibits sufficient adhesion not only when adhered to the adherend of the flat plate, but also exhibits sufficient adhesion when attached to various adherends, and has excellent adhesion inhibition. effect.

The surface protective film of the present invention will be described in further detail below.

The surface protection film of the present invention comprises a laminate having at least one layer of an adhesive layer and a substrate layer comprising the following resin composition.

[Resin composition]

The resin composition used in the present invention contains a 4-methyl-1-pentene‧ α -olefin copolymer (A) having a specific physical property in a specific ratio and copolymerized with the 4-methyl-1-pentene ‧ α -olefin A thermoplastic resin (B) other than the compound (A).

Further, in the present specification, the 4-methyl-1-pentene‧ α -olefin copolymer (A) may be simply referred to as "copolymer (A)", and sometimes 4-methyl-1- The thermoplastic resin (B) other than the pentene ‧ α -olefin copolymer (A) is simply referred to as "thermoplastic resin (B)".

<4-methyl-1-pentene‧ α -olefin copolymer (A)>

The 4-methyl-1-pentene‧ α -olefin copolymer (A) constituting the resin composition used in the present invention satisfies the following requirements (a), (b), (c) and (d).

Necessary condition (a):

The 4-methyl-1-pentene‧ α -olefin copolymer (A) used in the present invention comprises a constituent unit derived from 4-methyl-1-pentene (i) 65 to 90 mol % and α The constituent unit derived from an olefin (excluding 4-methyl-1-pentene) (ii) is 35 to 10 mol%. Here, the "mol%" is a value obtained by setting the total of the constituent units derived from all the constituent monomers to 100 mol%, for example, in the 4-methyl-1-pentene ‧ α -olefin copolymer (A) In the case where only the constituent unit (i) and the constituent unit (ii) are formed, the total value of the constituent unit (i) and the constituent unit (ii) is set to 100 mol%.

That is, the lower limit of the ratio of the constituent unit (i) is 65 mol%, preferably 80 mol%, more preferably 81 mol%. On the other hand, the upper limit of the ratio of the constituent unit (i) is 90 mol%, more preferably 86 mol%. In the present invention, the surface protective film obtained by the ratio of the above-mentioned constituent unit (i) in the 4-methyl-1-pentene‧ α -olefin copolymer (A) is at least the above lower limit value. It has excellent concavity and followability, and has moderate flexibility due to the upper limit or less. Further, in the case of 80 to 90 mol%, the surface protective film obtained is excellent in adhesion strength to the flat plate or the uneven surface, adhesive stability, and moderate softness which does not cause damage to the adherend, and The surface hardness is improved, whereby the formability of the film and the operation of the surface protective film before the film are easy and preferable, and more preferably 81 to 86 mol%.

Further, the ratio of the above constituent unit (ii) is 35 to 10 mol%, preferably 20 to 10 mol%, more preferably 19 to 14 mol%. That is, the upper limit of the ratio of the constituent unit (ii) is 35 mol%, preferably 20 mol%, more preferably 19 mol%. On the other hand, the lower limit of the ratio of the constituent unit (ii) is 10 mol%, more preferably 14 mol%.

Examples of the α-olefin from which the above structural unit (ii) is derived include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 1-tenth. The monoene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexene, etc. have 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms. More preferably, it is a linear α-olefin having 2 to 10 carbon atoms, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4 - dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1- A branched α-olefin having 5 to 20 carbon atoms such as hexene, preferably 5 to 15 carbon atoms. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferable, and ethylene and propylene are particularly preferable.

The α-olefin from which the above-mentioned constituent unit (ii) is derived may be used alone or in combination of two or more.

Here, in one aspect of the present invention, the 4-methyl-1-pentene‧ α -olefin copolymer (A) is composed only of the constituent unit (i) and the constituent unit (ii). In this case, the total of the constituent unit (i) and the constituent unit (ii) is 100% by mole.

However, in the 4-methyl-1-pentene ‧ α -olefin copolymer (A), a small amount, specifically 10 mol% or less, preferably 5 mol, which is not detrimental to the object of the present invention % or less, more preferably 3 mol% or less, may include, in addition to the constituent unit (i) and the constituent unit (ii), α which is not derived from 4-methyl-1-pentene and derived from the constituent unit (ii) a constituent unit derived from another polymerizable monomer of any of the olefins.

Preferred examples of such other polymerizable monomers include styrene, vinylcyclopentene, vinylcyclohexane, and vinyl halide. a vinyl compound having a cyclic structure such as an alkoxide; a vinyl ester such as vinyl acetate; an unsaturated organic acid such as maleic anhydride or a derivative thereof; butadiene, isoprene, pentadiene, 2, 3 a conjugated diene such as dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1, 5-heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, bicyclooctadiene, methylene drop Alkene, 5-vinyl-2-nor Alkene, 5-ethylidene-2-nor Alkene, 5-methylene-2-nor Alkene, 5-isopropylidene-2-lower Alkene, 6-chloromethyl-5-isopropenyl-2-lower Alkene, 2,3-diisopropylidene-5-lower Alkene, 2-ethylene-3-isopropylidene-5-lower Alkene, 2-propenyl-2,2-nor Non-conjugated polyenes such as dienes.

In other words, the 4-methyl-1-pentene‧ α -olefin copolymer (A) used in the present invention comprises the following constituent units: constituent units derived from 4-methyl-1-pentene (i) 65~ 90 mol %; constituent units derived from α-olefins (excluding 4-methyl-1-pentene) (ii) 35-10 mol%; and by 4-methyl-1-pentene and The constituent unit derived from the other polymerizable monomer other than the α-olefin constituting the above-mentioned structural unit (ii) is 0 to 10 mol%.

Here, in the case where a constituent unit derived from another polymerizable monomer is present, the total content of the constituent unit (ii) and the constituent unit derived from the other polymerizable monomer satisfies the above-mentioned "composition unit (ii) ratio". In this case, the total of the constituent units (i) and the constituent units (ii) and the constituent units derived from the other polymerizable monomers is 100 mol%.

Further, the other polymerizable monomers may be used in combination of two or more kinds.

Further, in the present specification, the term "constituting unit derived from X" (here, X is a compound having a carbon-carbon double bond) means that the (co)polymer obtained by using X as a monomer is The constituent unit corresponding to X, for example, when it is referred to as "a constituent unit derived from 4-methyl-1-pentene", means 4-a 4-methyl-1-pentene as a monomer. The constituent unit corresponding to 4-methyl-1-pentene in the methyl-1-pentene (co)polymer.

Necessary condition (b):

The 4-methyl-1-pentene ‧ α - olefin copolymer (A) used in the present invention has a limit viscosity [η] measured at 135 ° C in decalin of from 0.1 to 5.0 dL/g. In addition, the details of measurement conditions and the like are described in the column of the examples to be described later.

The above ultimate viscosity [η] is preferably from 0.5 to 4.0 dL/g, more preferably from 0.5 to 3.5 dL/g.

As will be described later, if hydrogen is used in combination in the polymerization, the molecular weight can be controlled, and the ultimate viscosity [η] can be adjusted.

If the above-mentioned ultimate viscosity [η] is less than 0.1 dL/g and is too small or larger than 5.0 dL/g, it is excessively formed, and when it is processed into a surface protective film, especially when forming an adhesive layer constituting the surface protective film, the formability is affected. The situation of damage.

Necessary condition (c):

The weight average molecular weight (Mw) and the number average molecular weight measured by gel permeation chromatography (GPC) of the 4-methyl-1-pentene‧ α -olefin copolymer (A) used in the present invention ( The ratio of Mn) (molecular weight distribution, Mw/Mn) is in the range of 1.0 to 3.5. In addition, the details of measurement conditions and the like are described in the column of the examples to be described later.

The above Mw/Mn is preferably from 1.2 to 3.0, more preferably from 1.5 to 2.8. If the above Mw/Mn is more than 3.5 and is too large, there is concern about the influence of the low molecular weight, low stereoregular polymer caused by the composition distribution, and the adhesion surface of the obtained surface protective film, that is, the surface of the adhesive layer constituting the surface protective film. It is sticky, so its touch is deteriorated, and it is easy to contaminate the adherend.

Here, in the present invention, if the catalyst described later is used, the above-described catalyst can be obtained. The above-mentioned copolymer (A) satisfying the necessary condition (c) within the range of the ultimate viscosity [η] represented by the necessary condition (b). In addition, the value of the above Mw/Mn and the following Mw is a value when measured by the method used in the examples described later.

Further, the weight average molecular weight (Mw) of the above 4-methyl-1-pentene‧ α -olefin copolymer (A) as measured by gel permeation chromatography (GPC) is in terms of polystyrene. It is preferably from 500 to 10,000,000, more preferably from 1,000 to 5,000,000, still more preferably from 1,000 to 2,500,000.

Necessary condition (d):

The density of the 4-methyl-1-pentene‧ α -olefin copolymer (A) used in the present invention (measured according to ASTM D 1505) is 870 to 830 kg/m ³ , preferably 865 to 830 kg/m ³ More preferably, it is 855~830kg/m ³ . In addition, the details of measurement conditions and the like are described in the column of the examples to be described later.

The density can be appropriately changed by the comonomer composition ratio of the 4-methyl-1-pentene ‧ α -olefin copolymer (A), and the above-mentioned copolymer (A) having a density within the above range is used for the manufacture of a lightweight adhesive. It is advantageous for the agent and the adhesive sheet.

The 4-methyl-1-pentene‧ α -olefin copolymer (A) used in the present invention is preferably a Shore A hardness after 15 seconds from the start of contact of the probe when the sheet is formed ( The value measured in the state of the pressed sheet having a thickness of 3 mm in accordance with JIS K6253 is in the range of 5 to 90, preferably 10 to 85, more preferably 15 to 80. The method for producing the pressed sheet is as shown in the examples.

The 4-methyl-1-pentene‧ α -olefin copolymer (A) used in the present invention is preferably a Shore A hardness defined by the following formula (in accordance with JIS K6253, in thickness) when formed into a sheet. The value ΔHS of the value measured in the state of the pressed sheet of 3 mm is in the range of 5 to 60, preferably 10 to 50, more preferably 10 to 45.

△HS=(While A hardness value immediately after the probe is contacted - Xiao A hardness value 15 seconds after the probe starts to contact)

△HS can be arbitrarily changed by constituting the comonomer type and comonomer composition of the 4-methyl-1-pentene‧ α -olefin copolymer (A), and if the ΔHS is within the above range, the unevenness followability Excellent.

In addition, when it is difficult to measure the Shore A hardness, the ΔHS'= can be similarly obtained by using the Shore D hardness value. (The Shore D hardness value immediately after the probe is first contacted - starting from the probe The Shore D hardness value after 15 seconds of contact). In this case, it is preferable that the ΔHS' is in the range of 5 to 50, preferably 5 to 25, more preferably 6 to 20. The ΔHS' can also be arbitrarily changed by the comonomer type and comonomer composition of the 4-methyl-1-pentene ‧ α -olefin copolymer (A), similarly to the above ΔHS, if ΔHS ' Within the above range, the bump followability is excellent.

<Method for producing 4-methyl-1-pentene ‧ α -olefin copolymer (A)>

Next, a method for producing the 4-methyl-1-pentene‧ α -olefin copolymer (A) will be described.

The method for producing the 4-methyl-1-pentene‧ α -olefin copolymer (A) used in the present invention is such that the above-mentioned requirements (a), (b), (c) and (d) are satisfied. The 4-methyl-1-pentene‧ α -olefin copolymer (A) is not particularly limited. Wherein, in the general aspect of the invention, the 4-methyl-1-pentene ‧ α -olefin copolymer (A) can be derived from the above-mentioned "derived constituent units" by using 4-methyl-1-pentene The ii) olefin is obtained by polymerization in the presence of a suitable polymerization catalyst. Here, as the polymerization catalyst which can be used in the present invention, a conventionally known catalyst such as a magnesium-supported titanium catalyst, International Publication No. 01/53369, International Publication No. 01/27124, is preferably used. It is more preferable to use a metallocene catalyst or the like described in Japanese Laid-Open Patent Publication No. Hei-3-193796 or Japanese Patent Application Laid-Open No. Hei 02-41303, and it is preferable to use the following formula (1) or (2). An olefin polymerization catalyst representing a metallocene compound.

(In the above formulae (1) and (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ And R ¹⁴ is selected from the group consisting of hydrogen, a hydrocarbon group and a hydrazine-containing hydrocarbon group, and may be the same or different, and the adjacent substituents of R ¹ to R ⁴ may be bonded to each other to form a ring, and the adjacent substituents of R ⁵ to R ¹² may be bonded. The ring may be bonded to each other to form a ring, and A is a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain a part of unsaturated bonds and/or an aromatic ring, and A may also include 2 rings including a ring formed together with Y. In the above ring structure, M is a metal selected from Group 4 of the periodic table, Y is carbon or ruthenium, Q is selected from a halogen, a hydrocarbon group, and an anionic ligand or may be a lone pair of electrons in a coordination neutral group. In the same or different combinations, j is an integer of 1 to 4) R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R of the above formula (1) or (2) ^8. R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are selected from the group consisting of hydrogen, a hydrocarbon group and a hydrazine-containing hydrocarbon group, and may be the same or different.

The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms. It may contain more than one ring structure. Further, part or all of the hydrogen of the hydrocarbon group may be substituted with a functional group such as a hydroxyl group, an amine group, a halogen group or a fluorine-containing hydrocarbon group. Specific examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, 2-methylpropyl group, 1,1-dimethylpropyl group, and 2,2-dimethylpropyl group. 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, second butyl, tert-butyl, 1,1- Dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, 1-adamantyl, 2-adamantane Base, 2-methyl-2-adamantyl, capping, descending Base, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, biphenyl, naphthyl, tolyl, chlorophenyl, chloro Phenyl, chloronaphthyl and the like.

The anthracene-containing hydrocarbon group is preferably an alkylalkylene group or an arylalkylalkyl group having 1 to 4 carbon atoms and 3 to 20 carbon atoms, and specific examples thereof include a trimethylsulfanyl group and a tert-butyldimethyl group. Alkylene, triphenylsulfanyl, and the like.

The adjacent substituents of R ⁵ to R ¹² on the anthracene ring may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, and an octamethyl octahydrodibenzofluorenyl group.

Further, the substituent of R ⁵ to R ¹² on the anthracene ring is preferably bilaterally symmetrical in terms of ease of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , and R ⁸ =R ⁹ , the anthracene ring is preferably an unsubstituted anthracene, a 3,6-disubstituted anthracene, a 2,7-disubstituted anthracene or a 2,3,6,7-tetrasubstituted anthracene. Here, the 3rd, 6th, 2nd, and 7th positions on the anthracene ring correspond to R ⁷ , R ¹⁰ , R ⁶ , and R ^{11 , respectively} .

R ¹³ and R ^{14 in the} above formula (1) are selected from hydrogen and a hydrocarbon group, and may be the same or different. Specific examples of the preferred hydrocarbon group include the same as described above.

Y is carbon or hydrazine. In the case of the formula (1), R ¹³ and R ^{14 are} bonded to Y to form a substituted methylene group or a substituted alkylene group as a crosslinking portion.

Preferred examples thereof include a methylene group, a dimethylmethylene group, a diisopropylmethylene group, a methyl tert-butylmethylene group, a dicyclohexylmethylene group, and a methylcyclohexyl group. Methyl, methylphenylmethylene, fluoromethylphenylmethylene, chloromethylphenylmethylene, diphenylmethylene, dichlorophenylmethylene, difluorophenyl methylene , methylnaphthylmethylene, diphenylmethylene, di-p-methylphenylmethylene, methyl-p-methylphenylmethylene, ethyl-p-methylphenylmethylene, Dinaphthylmethylene, or dimethylarylene, diisopropylarylene, methyl tertiary butyl sulfenyl, dicyclohexyl fluorenylene, methylcyclohexyl fluorenylene, methyl Phenylenealkylene, fluoromethylphenylarylene, chloromethylphenylarylene, diphenylalkylene, di-p-methylphenylarylene, methyl-p-methylphenylarylene A group, an ethyl p-methylphenyl fluorene alkyl group, a methylnaphthyl fluorenylene group, a dinaphthyl fluorenylene group, or the like.

In the case of the formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may contain a part of the unsaturated bond and/or the aromatic ring to constitute a cycloalkylene group or a cyclomethylene group.矽 alkyl and the like. Preferred examples thereof include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a bicyclo ring [3.3.1] fluorenyl group, and a sub-halogen. , adamantyl, tetrahydronaphthylene, dihydroindenylene, cyclodimethylene sulfenyl, cyclotrimethylene sulfenyl, cyclotetramethylene fluorenylene, cyclopentamethylene A decylene group, a cyclohexamethylene sulfenylene group, a cycloheptylene fluorene alkyl group, and the like.

M of the general formulae (1) and (2) is a metal selected from Group 4 of the periodic table, and examples of M include titanium, zirconium and hafnium.

Q is a combination of a halogen group, a hydrocarbon group having 1 to 20 carbon atoms, and an anionic ligand or the same or a different one of the ortho-electron pair-coordinating neutral ligands. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine, and specific examples of the hydrocarbon group include the same as described above. Specific examples of the anionic ligand include an alkoxy group such as a methoxy group, a third butoxy group, and a phenoxy group; a carboxylate group such as an acetate or a benzoate; and a mesylate or toluene; a sulfonate group or the like such as a sulfonate. Specific examples of the ortho-electron pair-coordinating neutral ligand include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and tetrahydrofuran and diethyl ether. ,two An ether such as an alkane or a 1,2-dimethoxyethane. Among these, Q may be the same or a combination of different ones, and preferably at least one of them is a halogen or an alkyl group.

Further, in the above formulae (1) and (2), j is preferably 2. The metallocene compound constituting the olefin polymerization catalyst which can be used in the present invention is preferably a metallocene compound represented by the above formula (1) or (2), but is not limited thereto. For example, as another preferable example of the metallocene compound which can be used in the present invention, a metallocene compound represented by the following formula [I] can also be mentioned.

[Chemical 3]

(In the formula [I], R ¹ , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently Is a hydrogen atom, a hydrocarbon group, a hetero atom-containing hydrocarbon group or a fluorenyl group, R ² is a hydrocarbon group, a hetero atom-containing hydrocarbon group or a fluorenyl group, and R ⁴ is a hydrogen atom, and a substituent of R ¹ to R ¹⁶ other than R ⁴ Any two substituents may be bonded to each other to form a ring, M is a Group 4 transition metal, Q is a halogen atom, a hydrocarbon group, an anionic ligand or a so-called l-electron pair coordination neutral ligand, j is 1~ An integer of 4, when j is an integer of 2 or more, Q may be the same or selected from a combination of different ones) In the general formula [I], R ¹ and R ^{3 are} preferably a hydrogen atom; and R ^{2 is} preferably carbon. a hydrocarbon group of 1 to 20, preferably a carbon bonded to the cyclopentadienyl ring is a substituent of a tertiary carbon; R ⁵ and R ^{7 are} preferably bonded to each other to form a ring; R ⁹ , R ¹² , R ¹³ and R ^{16 are} preferably a hydrogen atom; R ¹⁰ , R ¹¹ , R ¹⁴ and R ^{15 are} preferably a hydrocarbon group, or R ¹⁰ and R ¹¹ are bonded to each other to form a ring and R ¹⁴ and R ¹⁵ are bonded to each other to form a ring. ring.

<R ¹ to R ¹⁶ >

In the above formula [I], examples of the hydrocarbon group which may be R ¹ to R ¹⁶ (excluding R ⁴ ) include a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, and a cyclic unsaturated group. The hydrocarbon group is a group in which one or two or more hydrogen atoms of the saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group. The carbon number of the hydrocarbon group is usually from 1 to 20, preferably from 1 to 15, more preferably from 1 to 10.

Examples of the linear hydrocarbon group include a linear chain such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-decyl. An alkyl group; a linear alkenyl group such as an allyl group.

Examples of the branched hydrocarbon group include an isopropyl group, a tert-butyl group, a third amyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, and 1,1. - dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-propylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1- A branched alkyl group such as isopropyl-2-methylpropyl.

Examples of the cyclic saturated hydrocarbon group include a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a methylcyclohexyl group; A polycyclic group such as a benzyl group, an adamantyl group or a methyladamantyl group.

Examples of the cyclic unsaturated hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a phenanthryl group or a fluorenyl group; a cycloalkenyl group such as a cyclohexenyl group; and a 5-bicyclo ring [2.2.1]. a polycyclic unsaturated alicyclic group such as a hepta-2-enyl group.

The group in which one or two or more hydrogen atoms of the saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group is exemplified by a benzyl group. A group in which one or two or more hydrogen atoms of an alkyl group such as a 1,1-diphenylethyl group or a triphenylmethyl group are substituted with an aryl group.

Examples of the hetero atom-containing hydrocarbon group in R ¹ to R ¹⁶ (excluding R ⁴ ) include an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an oxygen atom such as a furyl group. a hydrocarbon group; an amine group such as an N-methylamino group, an N,N-dimethylamino group or an N-phenylamino group; a nitrogen atom-containing hydrocarbon group such as a pyrrolyl group; and a sulfur atom-containing hydrocarbon group such as a thienyl group. The carbon number of the hetero atom-containing hydrocarbon group is usually from 1 to 20, preferably from 2 to 18, more preferably from 2 to 15. Among them, the sulfhydryl group is excluded from the hetero atom-containing hydrocarbon group.

Examples of the mercapto group contained in R ¹ to R ¹⁶ (excluding R ⁴ ) include, for example, trimethyldecylalkyl group, triethylsulfonylalkyl group, dimethylphenylsulfanyl group, and diphenylmethyldecanealkyl group. And a triphenyldecyl group having the formula -SiR ₃ (wherein a plurality of R are each independently an alkyl group having 1 to 15 carbon atoms or a phenyl group).

Two adjacent substituents in the substituents of R ¹ to R ¹⁶ other than R ⁴ (for example, R ¹ and R ² , R ² and R ³ , R ⁵ and R ⁷ , R ⁶ and R ⁸ , R ⁷ and R ⁸ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁵ and R ¹⁶ ) may be bonded to each other to form a ring, R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ¹ and R ⁸ may be bonded to each other to form a ring, and R ³ and R ⁵ may be bonded to each other to form a ring. The above ring may be formed in the molecule in two or more places.

In the present specification, examples of the ring (addition ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a hetero ring. Specific examples thereof include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, a cyclopentene ring, a furan ring, a thiophene ring, and the like, and a hydrogenated hetero ring corresponding thereto; preferably a cyclohexane ring or a benzene; Ring and hydrogenated benzene ring. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

R ¹ and R ³ are preferably a hydrogen atom from the viewpoint of stereoregularity.

At least one selected from the group consisting of R ⁵ , R ⁶ and R ⁷ is preferably a hydrocarbon group, a hetero atom-containing hydrocarbon group or a mercapto group-containing group, R ^{5 is more} preferably a hydrocarbon group, and R ^{5 is} further preferably a linear alkyl group or a branched chain. An alkyl group having 2 or more carbon atoms, a cycloalkyl group or a cycloalkenyl group such as an alkyl group, and R ⁵ is preferably an alkyl group having 2 or more carbon atoms. Further, from the viewpoint of synthesis, it is also preferred that R ⁶ and R ⁷ are a hydrogen atom. Further, it is more preferred that R ⁵ and R ⁷ are bonded to each other to form a ring, and the ring is preferably a 6-membered ring such as a cyclohexane ring.

R ^{8 is} preferably a hydrocarbon group, and particularly preferably an alkyl group.

R ² is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably an aryl group, and more preferably a linear hydrocarbon group, a branched hydrocarbon group or a cyclic group. A saturated hydrocarbon group, particularly preferably a carbon having a free valence (carbon bonded to a cyclopentadienyl ring) is a substituent of a tertiary carbon.

Specific examples of R ² include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a third pentyl group, a third amyl group, and a 1-methylcyclohexyl group. -adamantyl, more preferably a substituent having a free valence carbon such as a third butyl group, a third pentyl group, a 1-methylcyclohexyl group or a 1-adamantyl group, and a third-order carbon, particularly preferably Third butyl, 1-adamantyl.

In the general formula [I], the anthracene ring moiety is not particularly limited as long as it is a structure obtained from a known anthracene derivative, and R ⁹ , R ¹² , R ¹³ and R ^{16 are in} terms of stereoregularity and molecular weight. It is preferably a hydrogen atom.

R ¹⁰ , R ¹¹ , R ¹⁴ and R ^{15 are} preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group, and further preferably a hydrocarbon group having 1 to 20 carbon atoms.

R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include a benzofluorenyl group, a dibenzofluorenyl group, an octahydrodibenzofluorenyl group, and a 1,1,4,4,7,7,10,10-octamethyl group. -2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]decyl, 1,1,3,3,6,6,8,8-eight Methyl-2,3,6,7,8,10-hexahydro-1H-bicyclopenta[b,h]decyl, 1',1',3',6',8',8'-six Methyl-1'H,8'H-bicyclopenta[b,h]fluorenyl, especially preferably 1,1,4,4,7,7,10,10-octamethyl-2,3,4 , 7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl.

<M, Q, j>

In the general formula [I], M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and particularly preferably Zr.

In the general formula [I], examples of the halogen atom which can be Q include fluorine, chlorine, bromine and iodine.

The hydrocarbon group which may be Q may be the same as the hydrocarbon group in R ¹ to R ¹⁶ (excluding R ⁴ ), and is preferably an alkyl group such as a linear alkyl group or a branched alkyl group.

Examples of the anionic ligand in Q include a methoxy group and a third group. Alkoxy group such as butoxy group; aryloxy group such as phenoxy group; carboxylate group such as acetate or benzoate; sulfonate group such as mesylate or tosylate; dimethyl decylamine An amidino group such as diisopropyl decylamine, methylaniline or diphenylguanamine.

Examples of the coordinating neutral ligand in the Q group of Q may include, for example, an organophosphorus compound such as trimethylphosphine, triethylphosphine, triphenylphosphine or diphenylmethylphosphine; tetrahydrofuran, Ether, two An ether such as an alkane or a 1,2-dimethoxyethane.

Preferably, at least one of Q is a halogen atom or an alkyl group.

Further, in the above formula [I], j is preferably 2.

Further, regarding the position number used for the naming of the above compound [I], [1-(1', 1', 4', 4', 7', 7', 10', 10'-octamethyl eight Hydrogen dibenzo[b,h]indole-12'-yl)(5-t-butyl-1-methyl-3-isopropyl-1,2,3,4-tetrahydrocyclopentadiene )] Zirconium dichloride, and [8-(1',1',4',4',7',7',10',10'-octamethyl octahydrodibenzo[b,h]茀-12'-yl)(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indole)]zirconium dichloride For example, an image isomer is shown in the formula [I-1] and the formula [I-2], respectively.

Specific examples of the above-mentioned metallocene compound in the present invention include compounds exemplified in International Publication No. 01/27124, International Publication No. 2006/025540, and International Publication No. 2014/050817. But does not put the scope of the invention It is limited to this.

In the case where a metallocene compound is used in the production of the above 4-methyl-1-pentene‧ α -olefin copolymer (A), the catalyst component is derived from (a) a metallocene compound (for example, the above formula) (1), (2) or a metallocene compound represented by [I], (b) is selected from (b-1) an organoaluminum oxy compound, (b-2) and a metallocene compound (a) Further, at least one of the compound of the ion pair and the (b-3) organoaluminum compound is formed, and further, if necessary, the (c) fine particle carrier is formed. As the production method, for example, the method described in the specification of International Publication No. 01/27124 can be employed.

Further, the organoaluminum oxy-compound (b-1) (hereinafter also referred to as "component (b-1)") and the metallocene compound (a) (hereinafter also referred to as "component (a)") are reacted. a compound forming an ion pair (hereinafter also referred to as "component (b-2)"), an organoaluminum compound (b-3) (hereinafter also referred to as "component (b-3)"), and a particulate carrier (c) Specific examples thereof include those conventionally known in the art of olefin polymerization as such compounds or carriers, and specific examples described in the specification of International Publication No. 01/27124, for example.

Here, in a preferred aspect of the present invention, the 4-methyl-1-pentene‧ α -olefin copolymer (A) can be formed by deriving 4-methyl-1-pentene with the above The α-olefin of the unit (ii) is obtained by polymerization in the presence of the above polymerization catalyst, and as a result, in the production of the 4-methyl-1-pentene ‧ α -olefin copolymer (A), the polymerization can be dissolved by Any of a liquid phase polymerization method such as polymerization or suspension polymerization or a gas phase polymerization method.

In the liquid phase polymerization method, an inactive hydrocarbon solvent can be used as a solvent constituting the liquid phase. Specific examples of such an inert hydrocarbon include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane and cyclohexane. , an alicyclic hydrocarbon such as methylcyclopentane or methylcyclohexane; an aromatic hydrocarbon such as benzene, toluene or xylene; and a halogenated hydrocarbon such as vinyl chloride, chlorobenzene, dichloromethane, chloroform or tetrachloromethane. And these a mixture or the like.

Further, block polymerization of 4-methyl-1-pentene and the above-mentioned "α-olefin derived from the constituent unit (ii)" itself as a solvent can also be carried out.

Further, by the stepwise polymerization of 4-methyl-1-pentene and the copolymerization of 4-methyl-1-pentene with the above-mentioned "α-olefin derived from the constituent unit (ii), A 4-methyl-1-pentene‧ α -olefin copolymer (A) having a controlled composition distribution can be obtained.

When the polymerization is carried out, the component (a) is usually 10 ^-8 to 10 ^-2 mol, preferably 10 ^-7 °, in terms of the metal atom per unit of the cycle, per unit reaction volume. Use 10 ^{- 3} moles. The component (b-1) is usually in the range of 0.01 to 5,000, preferably in the molar ratio [(b-1)/M] of the transition metal atom (M) in the component (b-1) and the component (a). It is used in an amount of 0.05 to 2000. The component (b-2) is usually 1 to 10, preferably 1 to 10, in terms of the molar ratio [(b-2)/M] of the transition metal atom (M) in the component (b-2) and the component (a). It is used in an amount of 1 to 5. The component (b-3) is usually 10 to 5,000, preferably 10 to 5,000, in terms of the molar ratio [(b-3)/M] of the transition metal atom (M) in the component (b-3) and the component (a). It will be used in the amount of 20~2000.

The polymerization temperature is usually in the range of -50 to 200 ° C, preferably in the range of 0 to 100 ° C, more preferably in the range of 20 to 100 ° C.

The polymerization pressure is usually atmospheric pressure ~ 10 MPa gauge pressure, preferably atmospheric pressure ~ 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous, and continuous methods. Further, the polymerization may be carried out in two or more stages in which the reaction conditions are different.

In the polymerization, in order to control the molecular weight or polymerization activity of the resulting polymer, hydrogen may be added in an amount corresponding to 4-methyl-1-pentene and the above-mentioned "derived constituent unit (ii) α- The total amount of olefins is about 0.001 to 100 NL.

<Thermoplastic resin (B)>

The thermoplastic resin (B) constituting the resin composition of the present invention is not particularly limited as long as it is a thermoplastic resin other than the 4-methyl-1-pentene ‧ α -olefin copolymer (A), and is preferably a thermoplastic resin (B). For example, an olefin resin (B1) other than the above copolymer (A), a polyamide resin, a polyester resin, and a vinyl aromatic resin may be mentioned. In the present invention, the thermoplastic resin (B) is used to impart good adhesion, formability, and tackiness to the resin composition of the present invention.

Here, specific examples of the olefin-based resin (B1) include a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and a cyclic olefin. a copolymer of ethylene, a copolymer of styrene, vinyl acetate, (meth)acrylic acid, or (meth)acrylate, and a copolymer of propylene and an α-olefin having 4 to 20 carbon atoms. And a copolymer of propylene and a carbon number of 4 to 20 α-olefin and a cyclic olefin, and various vinyl compounds such as styrene, vinyl acetate, (meth)acrylic acid, or (meth)acrylate are comonomers. A vinyl copolymer or the like. More specifically, low density, medium density, high density polyethylene, high pressure low density polyethylene, homogenous polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1- Pentene, poly-3-methyl-1-butene, cyclic olefin copolymer, chlorinated polyolefin, and olefin-based elastomer.

As an example of the olefin-based elastomer, an elastomer containing an olefin-based block copolymer can also be used. For example, a block copolymer which forms a polyolefin block which is a polymer having a high crystallinity such as polypropylene and a monomer copolymer which exhibits an amorphous property which is a soft portion in a hard portion can be exemplified, and specifically, a block copolymer can be exemplified. An olefin (crystalline)-ethylene-butylene-olefin block copolymer, a polypropylene-polyolefin (amorphous)-polypropylene block copolymer, and the like. As a specific example, it is marketed by JSR Co., Ltd. under the trade name DYNARON (registered trademark), and by Mitsui Chemicals Co., Ltd. under the trade name of TAFMER (registered trademark) and NOTIO (registered trademark), by Dow. Chemicals, Inc. is marketed under the tradename ENGAGE ^(TM) , VERSIFY ^(TM) , and by ExxonMobil Chemical Co., Ltd. under the trade name Vistamaxx ^(TM) .

Further, specific examples of the polyamine-based resin include aliphatic polyamines (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, and nylon 612).

Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyester elastomer.

Specific examples of the vinyl aromatic resin include polystyrene, acrylonitrile-butadiene-styrene (ABS, Acrylonitrile-Butadiene-Styrene) resin, and acrylonitrile-styrene (AS, Acrylonitrile-Styrene) resin, styrene-based elastomer (B2), and the like.

The styrene-based elastomer (B2) may, for example, be a block copolymer (SBS) or a hydrogenated styrene which is a polystyrene block of a hard portion (crystal portion) and a diene monomer block which is a soft portion. - Butadiene-styrene block copolymer (HSBR), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-butylene-styrene block copolymer (SEBS), Styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene-styrene copolymer (SIBS), styrene-isobutylene copolymer (SIB), and the like. The styrene-based elastomer may be used alone or in combination of two or more.

Specific examples of the hydrogenated styrene-butadiene-styrene block copolymer are commercially available from JSR Co., Ltd. under the trade name of DYNARON (registered trademark).

The styrene-ethylene-propylene-styrene block copolymerization system is obtained by hydrogenating a styrene-isoprene-styrene block copolymer (SIS). Specific examples of the SIS include those sold by JSR Co., Ltd. under the trade name: JSRSIS (registered trademark). Kuraray Co., Ltd. is marketed under the trade name: HYBRAR (registered trademark) or by the Shell Co., Ltd. under the trade name: Kraton D (registered trademark).

In addition, as a specific example of the SEPS, a product of the trade name: Septon (registered trademark) by Kuraray Co., Ltd., or a trade name of Kraton (registered trademark) by Shell Co., Ltd., etc., may be mentioned.

In addition, as a specific example of the SEBS, a product of the brand name: Tuftec (registered trademark) by Asahi Kasei Co., Ltd., or a trade name of Kraton (registered trademark) by Shell Co., Ltd., etc., may be mentioned.

In addition, as a specific example of the SIB and the SIBS, a product of the brand name: Shibusuta (registered trademark) is available from Kaneka Co., Ltd., and the like.

Moreover, as a special styrene-type elastomer, the market name of S.O.E. by Asahi Kasei Co., Ltd. is mentioned.

Further, examples of the other thermoplastic resin (B) include thermoplastic polyurethane, vinyl chloride resin, vinylidene chloride resin, acrylic resin, ethylene-vinyl acetate copolymer, and ethylene-methacrylic acid acrylic acid. Ester copolymer; ionic polymer; ethylene-vinyl alcohol copolymer; polyvinyl alcohol; fluoro resin polycarbonate; polyacetal; polyphenylene ether; polyphenylene sulfide polyimine; polyaryl ester; Polyether oxime and the like.

In the present invention, among the thermoplastic resins (B), an olefin resin (B1) and a styrene elastomer (B2) are preferably used. Further, in the case where the adherend is an uneven surface, the styrene elastomer (B2) is particularly preferable because the adhesion of the obtained surface protective film is high. Here, when the styrene-based elastomer (B2) is used as the thermoplastic resin (B), it is more preferable that the thermoplastic resin (B) is composed only of the styrene-based elastomer (B2).

These thermoplastic resins may be used alone or in combination of two or more.

The resin composition of the present invention contains such a thermoplastic resin (B) in addition to the above-mentioned copolymer (A). In the present invention, when the total amount of the copolymer (A) and the thermoplastic resin (B) is 100 parts by weight, the above composition is obtained from the viewpoint of adhesion and adhesion followability to the adherend. The upper limit of the content of the copolymer (A) in the compound is 50 parts by weight, preferably 45 parts by weight, particularly preferably 40 parts by weight, and the lower limit is 2 parts by weight, preferably 5 parts by weight, particularly preferably It is 10 parts by weight.

In other words, the lower limit of the content of the thermoplastic resin (B) is 50 parts by weight, more preferably 55 parts by weight, still more preferably 60 parts by weight, and the upper limit is 98 parts by weight, more preferably 95 parts by weight, particularly preferably 90 parts by weight.

<Other ingredients>

The resin composition of the present invention may be composed only of the above-mentioned copolymer (A) and the above thermoplastic resin (B), but may contain, in addition to the above-mentioned copolymer (A) and the above thermoplastic resin (B), Further, an appropriate additive such as an adhesion-imparting agent is contained as another component.

Here, the resin composition of the present invention is mainly used as an adhesive, and in order to adjust the adhesion to the adherend, an adhesion-imparting agent may be further contained as an additive as needed.

Here, as an example of the adhesive agent which can be used in the present invention, a resinous substance which is generally produced and sold as an adhesion-imparting agent, and specifically, a color-filled resin such as a color-filled resin; - phenolic resin such as formaldehyde resin and xylene-formaldehyde resin; terpene resin such as indophenol resin, terpene resin (α, β-pinene resin), aromatic modified terpene resin, hydrogenated terpene resin; Petroleum hydrocarbon resins such as terpene resin, aromatic hydrocarbon resin, aliphatic hydrocarbon resin, aliphatic cyclic hydrocarbon resin, hydrogenated hydrocarbon resin, and hydrocarbon-based adhesive resin; rosin pentaerythritol, rosin pentaerythritol ester, rosin glycerin, rosin glycerin Ester, hydrogenated rosin, hydrogenated rosin, hydrogenated rosin ester, special rosin, special rosin ester and rosin A rosin derivative such as an adhesion-imparting agent.

Among these components, a hydrogenated hydrocarbon resin, a hydrogenated aliphatic cyclic hydrocarbon resin, a hydrogenated aliphatic/alicyclic petroleum resin having a softening point of 70 ° C or higher, preferably 70 to 130 ° C, may be exemplified. Hydrogenated resin such as hydrogenated terpene resin, hydrogenated synthetic polydecene resin; rosin pentaerythritol, rosin pentaerythritol ester, rosin glycerin, rosin glyceride, hydrogenated rosin, hydrogenated rosin, hydrogenated rosin ester, special rosin, special rosin ester and rosin-based adhesion Rosin derivatives such as agents.

The adhesion of the adhesive of the present invention to the adherend can be adjusted by adding an adhesion-imparting agent.

In the case where the resin composition of the present invention contains the above-mentioned adhesion-imparting agent, the amount of the adhesion-imparting agent used is 100 parts by weight in total of the copolymer (A) and the thermoplastic resin (B). 5 to 100 parts by weight.

Further, the resin composition of the present invention may contain a weathering stabilizer, a heat stabilizer, an antistatic agent, an anti-slip agent, and an anti-blocking agent as additives other than the above-mentioned adhesion-imparting agent, depending on the purpose, without departing from the object of the present invention. Agent, anti-fogging agent, slip agent, pigment, dye, plasticizer, anti-aging agent, hydrochloric acid absorbent, antioxidant, crystal nucleating agent, anti-fungal agent, antibacterial agent, flame retardant, filler (inorganic filler) , organic fillers, softeners and other additives.

As the above softener, a previously known softener can be used. Specific examples thereof include processing oils, lubricating oils, paraffin waxes, liquid paraffin waxes, polyethylene waxes, polypropylene waxes, petroleum pitches, and petroleum materials such as petroleum jelly; coal tars such as coal tar and coal tar pitch. Fat oils such as castor oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, 12- Fatty acids such as stearic acid, montanic acid, oleic acid and sinapic acid or Its metal salt; synthetic resin such as petroleum resin, smoked alfalfa-茚 resin and miscellaneous polypropylene; ester plasticizer such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate Other microcrystalline waxes, and liquid polybutadiene or its modified or hydride; liquid polysulfide rubber.

Examples of the filler include a powder filler such as mica, carbon black, cerium oxide, calcium carbonate, talc, graphite, stainless steel, and aluminum; and a fibrous filler such as glass fiber or metal fiber. Further, a hydrophilic layered clay mineral and/or a hydrophilic inorganic compound having a specific shape (excluding a layer) may be mentioned.

Examples of the hydrophilic layered clay mineral include a sheet silicate mineral having a layer in which a plurality of layers are expanded in a planar manner, and examples thereof include bentonite. The bentonite is a mineral of the smectite group, and examples thereof include Montmorillonite, magnesian montmorillonite, iron montmorillonite, and iron magnesian montmorillonite. , beide stone, aluminian beidellite, smectite, aluminian nontronite, saponite, aluminian saponite, lithium bentonite, zinc bentonite, strontium Magnesia, bentonite, etc.

Further, examples of the hydrophilic layered clay mineral include vermiculite, halloysite, swellable mica, and graphite.

These hydrophilic layered clay minerals may be used alone or in combination of two or more. As such a hydrophilic layered clay mineral, a general commercial product can be used. For example, more specifically, as a natural product, for example, Kunipia series (montmorillonite, manufactured by KUNIMINE INDUSTRIES), Bengel series (bentonite, Ho) (manufactured by Jun), Somasif ME series (swellable mica, manufactured by CO-OP. CHEMICAL Co., Ltd.), and the like, for example, Sumecton (saponite, manufactured by KUNIMINE INDUSTRIES), and Lucentite SWN series (lithium bentonite, Co., Ltd., manufactured by CO-OP.CHEMICAL, and laponite (lithium bentonite, manufactured by Rockwood Holdings). In general, The maximum length of the finished product is smaller than that of the natural product, so that smaller oil droplets can be obtained, and from this point of view, it is preferably a synthetic product.

Examples of the flame retardant include inorganic compounds such as a lanthanum-based flame retardant, aluminum hydroxide, magnesium hydroxide, zinc borate, a lanthanum-based flame retardant, and a zirconium-based flame retardant, and ammonium polyphosphate and ethylene. Phosphate esters such as bis(2-cyanoethyl)phosphonium chloride, tris(tribromophenyl)phosphate, tris(tribromophenyl)phosphate, tris(3-hydroxypropyl)phosphine oxide, and other phosphorus compounds Chloride-based flame retardants such as chlorinated paraffin, chlorinated polyolefin, perchlorocyclopentadecane, hexabromobenzene, and ethylidene dibromide a bromine-based flame retardant such as alkanedicarboxylimine, exoethyl bis-tetrabromophthalimide, tetrabromobisphenol A derivative, tetrabromobisphenol S, tetrabromodipentaerythritol, and the like .

The total amount of the additives other than the adhesion-imparting agent such as the softener, the filler, and the flame retardant is set to 100 parts by weight in total of the copolymer (A) and the thermoplastic resin (B). 50 parts by weight.

<Method for Producing Resin Composition of the Present Invention>

The resin composition of the present invention may be blended with the above-mentioned copolymer (A), the above thermoplastic resin (B), and optionally the above-mentioned "other components" in the above-mentioned range, and various known additives are used. Method for manufacturing, for example, a multi-stage polymerization method, using a Plastomill, a Henschel mixer, a V-type mixer, a belt mixer, a rolling mixer, a kneader, etc., or using a single-axis extruder after mixing A method of granulation or pulverization after melt-kneading, such as a twin-screw extruder, a kneader, or a Banbury mixer.

<Grafting modification>

In the present invention, the 4-methyl-1-pentene‧ α -olefin copolymer (A) and the thermoplastic resin (B) may be used in the production of the resin composition of the present invention without modification. Part or all of the above 4-methyl-1-pentene‧ α -olefin copolymer (A) may be graft-modified in a range not degrading the object of the present invention, or a part or all of the thermoplastic resin (B) may be partially Graft modification. Examples of the polar compound to be used for the graft modification and the graft modification include conventionally known compounds and methods. For example, the compounds and methods described in JP-A-2008-127440 can be used.

The graft amount of the graft modified body is usually from 0.1 to 40% by weight, preferably from 0.2 to 30% by weight, more preferably from 0.2 to 20% by weight.

When the 4-methyl-1-pentene‧ α -olefin copolymer (A) or the thermoplastic resin (B) is graft-modified, the compatibility of the components in the composition or the formation of a laminated film is obtained. The aspect in which interlayer peeling is less likely to occur between the films is preferable.

[Laminar, especially surface protection film]

In the present invention, a laminate comprising the above resin composition, that is, a laminate comprising at least one adhesive layer (L1) containing the above resin composition is also provided.

In the laminate of the present invention, when the resin composition is used in the adhesive layer, the adhesive layer follows the uneven shape when attached to various adherends having irregularities, whereby the adhesive area is increased and sufficient Adhesion, and the adhesion can be stabilized due to the increased adhesion area.

Here, the laminate of the present invention includes a substrate layer (L2) and a laminate including at least one adhesive layer (L1) of the resin composition of the present invention, and specifically includes The pressure-sensitive adhesive layer (L1) of the resin composition of the present invention is laminated on a single-sided or double-sided film of a single-layer or multi-layer base material layer (L2). In other words, as a basic aspect of the laminated body of the present invention, a two-layer film in which a base material layer (L2)/adhesive layer (L1) is sequentially laminated or an adhesive layer (L1)/base is used. Material layer (L2) / adhesive layer (L1) A three-layer film laminated.

Here, the material of the base material layer (L2) constituting the laminate of the present invention is not particularly limited, and is preferably a thermoplastic resin such as a polyolefin resin. Specific examples thereof include a polypropylene resin (acrylic resin) a polymer, a random or block copolymer of propylene and a small amount of α-olefin, a polyethylene resin (low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene), known The ethylene-based polymer (ethylene ‧ α -olefin copolymer, ethylene-ethyl acrylate copolymer; ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer), A propylene-based copolymer (propylene ‧ α -olefin copolymer), poly-4-methyl-1-pentene, and combinations thereof are known.

Further, in the laminate of the present invention, for example, a surface layer (L3) may be further provided on the surface of the base material layer (L2) opposite to the side of the adhesive layer (L1). In other words, the laminate of the present invention may have a structure including at least three layers in which the surface layer (L3)/base material layer (L2)/adhesive layer (L1) are sequentially laminated. Here, the surface layer (L3) is sometimes provided in order to easily roll up the laminated body when the laminated body is made into a roll. In this case, as the material of the base material layer (L2) and the surface layer (L3), resins of the same type may be used, or resins of different types may be used.

The surface of the substrate layer (L2) can be treated by a surface treatment such as corona discharge treatment, plasma treatment, flame treatment, electron beam irradiation treatment, and ultraviolet irradiation treatment, and the substrate layer (L2) can be colorless and transparent. The layer may also be a layer that has been colored or printed.

As the base material layer (L2), it is also possible to use an extension in a uniaxial or biaxial direction.

As a method for producing the laminated body of the present invention, for example, a known method for forming a multilayer film can be mentioned, and as a preferred method, a T-shaped film can be used for forming. A method of coextruding an adhesive layer (L1) comprising the resin composition of the present invention with a substrate layer (L2) or extrusion coating on a preformed substrate layer (L2) by a method or an inflation film forming method A method of coating the adhesive layer (L1) containing the resin composition of the present invention. Further, a method in which the resin composition of the present invention is dissolved in a solvent and applied to the base material layer (L2) to form an adhesive layer (L1) on the base material layer (L2) may be mentioned. Among these, it is preferable to form a film by a co-extrusion molding method.

The multilayer film of the present invention may also extend in a uniaxial direction or a biaxial direction. As a preferred method of uniaxial stretching, a roll stretching method which is generally used can be exemplified. As a method of biaxial stretching, a sequential stretching method of performing biaxial stretching after uniaxial stretching or a simultaneous biaxial stretching method such as tubular extension method can be exemplified.

The laminate of the present invention can be obtained in the form of a multilayer film by using the above-described production method. As a preferred use of the multilayer film, a surface protection film can be cited. The thickness of the surface protective film (multilayer film) using the resin composition of the present invention is not particularly limited, but is preferably about 5 to 5,000 μm, more preferably about 10 to 1,000 μm. The thickness of the surface layer (adhesive layer) is not particularly limited and may be selected depending on the type of the adherend or the desired physical properties (for example, adhesive strength), and is usually 1 to 500 μm, preferably 3 to 300 μm. Further, the laminate may have at least two layers of the adhesive layer and the base layer. For example, an intermediate layer (L4) may be provided between the adhesive layer (L1) and the base layer (L2). Here, as a material used for the intermediate layer (L4), a conventionally known one can be used.

In the case where a multilayer film using the resin composition of the present invention is used as a surface protective film, in order to prevent adhesion (adhesion) of the multilayer films to each other, a release paper or a release film may be interposed between the multilayer films, or on the substrate layer. The exposed surface of (L2) was coated with a release agent.

Further, in the present invention, the base material layer (L2) may contain an additive such as a release agent in order to impart a function as a slidability to the surface as needed.

<Method for Producing Surface Protective Film>

The method of laminating the base material layer (L2) and the adhesive layer (L1) and optionally the surface layer (L3) is not particularly limited, and examples thereof include a known lamination method by extrusion lamination, extrusion coating, or the like. a method of laminating a substrate layer (L2) and an adhesive layer (L1) on a surface layer (L3) film obtained by T-die molding or inflation molding, or a substrate layer (L2) and an adhesive layer (L1) A method of laminating each film by dry lamination after independently forming a film, etc., in terms of productivity, a surface layer (L3), a substrate layer (L2), and an adhesive layer (preferably) Each component of L1) is supplied to a multi-layer extruder to form a co-extrusion molding. This case is also suitable for the production of a surface protective film comprising a laminate having the above-mentioned intermediate layer (L4) in addition to the substrate layer (L2), the adhesive layer (L1), and optionally the surface layer (L3). The situation. Based on such a case, in the preferred aspect of the invention, the laminate constituting the surface protective film is, for example, a multilayer film obtained by a T-die film forming method.

The polyolefin-based multilayer film excellent in mold release property is particularly preferably used as a surface by using the substrate layer (L2), the adhesive layer (L1) and the surface layer (L3) which are optionally provided in the above preferred embodiment. Protective film, release film.

<Use>

Examples of the use of the resin composition of the present invention and a laminate comprising the resin composition include an adhesive sheet, a surface protective film, and the like. When the resin composition of the present invention is used as an adhesive layer of a multilayer film, the multilayer film can be preferably used as a metal plate for protecting an aluminum plate, a steel plate, a stainless steel plate, and the like, or a coated plate or glass. A processing member such as a plate or a synthetic resin sheet, and a surface protective film for an electric appliance or an automobile part or an electronic component using the member. Therefore, the resin composition of the present invention can be preferably used for For example, an adhesive such as an adhesive film or a protective film adhesive layer, a semiconductor protective film, a lens protective film, a back grinding tape for a semiconductor wafer, a cut protective tape, a protective film for a printed circuit board, or an electronic film or tape, A film for window glass protection, a film for baking and coating, and the like. In particular, since the resin composition of the present invention has concavo-convex followability, it is preferably used for a sheet or a reflective sheet for protecting a surface having a large uneven structure, a sheet having a wrinkled surface, and the like. In the case of the protective tape for a printed circuit board, a protective film for a plating mask used for the plating treatment of a printed circuit board is exemplified.

The surface protection film of the present invention can be used by being attached to an adherend which is an object to be protected. The composition is adjusted depending on the physical properties of the attached surface of the adherend, for example, the surface roughness (surface roughness). In general, a strongly adhesive type material is used when the surface of the adherend of the adherend is thick.

It is preferable to use a styrene-based elastomer (B2) as the thermoplastic resin (B) for the adhered surface having a large surface unevenness. In this case, the surface unevenness height of the adhered surface is preferably in the range of 0.1 to 300 μm, more preferably in the range of 0.1 to 100 μm, further preferably in the range of 1 to 50 μm, and particularly preferably in the range of 1 to 30 μm. The scope.

In other words, it is also possible to provide a method of protecting an adherend as an object to be protected by using the protective film of the present invention, which is to be protected by an adherend as an object to be protected. It is carried out by attaching the surface protective film of the present invention. In particular, when the styrene-based elastomer (B2) is used as the thermoplastic resin (B), a preferred example of the adherend as the object to be protected is a surface unevenness height of 0.1 to 300 μm, more preferably The surface of 0.1 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 1 to 30 μm, as a more specific example, may be a tantalum sheet.

[Examples]

The invention is illustrated by the following examples, but the invention is not subject to such implementation Any definition of the example.

[Measurement conditions, etc.]

The measurement conditions and the like of the physical properties in the examples are as follows.

[composition]

The content of 4-methyl-1-pentene and α-olefin in the polymer was measured by ¹³ C-NMR using the following apparatus under the following conditions. An ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used as a mixed solvent of o-dichlorobenzene/nonylbenzene (80/20% by volume) as a solvent, and the sample concentration was 55 mg/0.6 mL. The measurement temperature was 120 ° C, and the observation nuclei were ¹³ C (125MHz), the sequence is single pulse proton decoupling, the pulse width is 4.7μs (45° pulse), the repetition time is 5.5 seconds, the cumulative number is more than 10,000 times, and 27.50ppm is set as the reference value of chemical shift. The measurement was carried out.

[density]

The density of the polymer was calculated from the weight of each sample measured in water and air according to ASTM D 1505 (aqueous substitution method) using an electronic hydrometer MD-300S of ALFA MIRAGE.

[melting point (Tm)]

The melting point (Tm) of the polymer was measured by a differential scanning calorimeter (DSC) using a DSC220C apparatus manufactured by Seiko Instruments. 7 to 12 mg of the sample obtained by the polymerization was sealed in an aluminum pan and heated from room temperature to 200 ° C at 10 ° C / min. In order to completely melt the sample, it was kept at 200 ° C for 5 minutes, and then cooled to -50 ° C at 10 ° C / min. After standing at -50 ° C for 5 minutes, the sample was again heated to 200 ° C at 10 ° C / min. The peak temperature in this (second time) heating was used as the melting point (Tm).

[limit viscosity]

The ultimate viscosity [η] (dL/g) was measured using a decalin solvent at 135 °C.

That is, about 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity η _sp was measured in an oil bath at 135 °C. After adding 5 ml of decalin solvent to the decalin solution and diluting, the specific viscosity η _{sp was} measured in the same manner. Further, this dilution operation was repeated twice, and the η _sp /C value when the concentration (C) was extrapolated to 0 as shown in the following formula was defined as the ultimate viscosity [η] (unit: dL/g).

[η]=lim(η _sp /C)(C→0)

[Molecular weight (Mw, Mn), molecular weight distribution (Mw/Mn)]

The molecular weight of the copolymer (A) is a liquid chromatograph: ALC/GPC 150-C plus (differential refractometer detector integrated type) manufactured by Waters, and GMH6-HT manufactured by Tosoh Co., Ltd. as a column system. ×2 and GMH6-HTL×2 were connected in series, and o-dichlorobenzene was used as a mobile phase medium, and the measurement was carried out at 140 ° C at a flow rate of 1.0 ml/min.

The obtained chromatogram was analyzed by a known method using a calibration curve of a standard polystyrene sample, thereby calculating Mw/Mn value and Mz/Mw value. The measurement time for each sample was 60 minutes.

[Manufacturing method of various pressed sheets for measurement]

The adhesives of the examples and the comparative examples (i.e., the adhesive resin for the adhesive layer (L1) were used under a pressure of 10 MPa using a hydraulic hot press manufactured by Shinto Metal Industry Co., Ltd. set at 190 °C. Material) sheet forming. a sheet having a thickness of 1 to 3 mm (slice shape; When taking four 80×80×0.5~3mm) on a plate of 240×240×2mm thickness, keep the residual heat for about 5~7 minutes, pressurize at 10MPa for 1-2 minutes, then use another one set at 20°C. A hydraulic hot press manufactured by Shinto Metal Industries Co., Ltd. was compressed at 10 MPa and cooled for about 5 minutes to prepare a sample for measurement. A brass plate having a thickness of 5 mm was used as the hot plate. The samples prepared by the above methods were used for various physical property evaluation samples.

[Dang's hardness measurement]

In the measurement of Xiao's hardness (according to JIS K6253), a pressed sheet having a thickness of 3 mm was used as a measurement sample, and the probe of the Xiao's A hardness tester or the Xiao's D hardness tester was just started after contact with the self-probe. The scale after 15 seconds of contact.

Then, the change ΔHS of the value of the Shore hardness defined by the following formula was obtained.

△HS=(Which hardness value after the probe has just started contact - Xiao hardness value after 15 seconds from the start of contact of the probe)

Here, the measurement of the Shore hardness is carried out in principle using a Shore A hardness tester, but a measurement sample which is difficult to measure the Shore A hardness is used instead of the Shore D hardness tester.

Here, when the same type of hardness is used, it can be said that the larger the ΔHS, the higher the tracking followability.

[Layered body formation]

Three kinds of three-layer T-die forming machines with a die width of 300 mm and a 30 mm Φ single-axis extruder were used, and the resin supply hoppers connected to the surface layer (L3), the base material layer (L2), and the adhesive layer (L1) were respectively put into the hopper. The resin pellets are melted by a cylinder in a uniaxial extruder, and then extruded by a T-die to obtain a laminate which is an adhesive sheet. at this time, Polypropylene F107 manufactured by Prime Polymer Co., Ltd. was used for the surface layer (L3) and the base material layer (L2), and the adhesive resin composition shown in each of the examples and the comparative examples was used for the adhesive layer (L1).

Here, the thickness of the surface layer (L3), the thickness of the base material layer (L2), the thickness of the adhesive layer (L1), and the total thickness of each of the examples and the comparative examples are shown in Tables 2 to 5, respectively.

[Adhesion evaluation (acrylic board)]

The adhesion of the laminate obtained in each of the examples and the comparative examples was measured in accordance with JIS Z0237-2000. Here, a sheet of polyethylene terephthalate having a thickness of 100 μm was attached to the surface of the laminated body which is a sample of the adhesive sheet, and the adhesive film was formed. On the other hand, a black acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name Acrylite REX, shape 50 × 100 mm gusset) having a width of 50 mm × a length of 100 mm × a thickness of 2 mm was used as a test plate. After the test plate and the adhesive film were allowed to stand in an environment of a temperature of 23 ° C and a relative humidity of 50% for 1 hour, the adhesive film was placed on the test plate, and then a pressure of about 2 kg was applied to the rubber roller to pass it back and forth. And attach the adhesive film to the test plate. After attaching, it was allowed to stand for 1 day in a fixed environment with a temperature of 23 ° C and a relative humidity of 50%, and then measured at a temperature of 23 ° C and a relative humidity of 50% to measure the blackness of the test plate at a speed of 300 mm/min in the direction of 180°. The adhesion of the acrylic plate when peeled off was set at 23 ° C.

The adhesion of each of the examples and the comparative examples is shown in the column of "adhesive strength (acrylic plate) @23 °C" in Tables 2 to 5.

[Adhesion rate]

According to the method and conditions described in the above "Adhesion evaluation (acrylic board)" The test plate to which the adhesive film (that is, the adhesive film obtained from the laminate obtained in each of the examples and the comparative examples) was attached was allowed to stand in a fixed environment at a temperature of 23 ° C and a relative humidity of 50% for 1 day. The test plate was placed in an oven at 60 ° C for 1 day, and after adhesion at a temperature of 23 ° C and a relative humidity of 50%, the adhesion after peeling from the black acrylic plate at a speed of 300 mm/min in the direction of 180° was measured. force. The adhesion at this time was set to the adhesion at 60 °C. The adhesive strength at 60 ° C of each of the examples and the comparative examples is shown in the column of "adhesive strength (acrylic plate) @60 ° C" in Tables 2 to 5.

For each of the examples and comparative examples, the adhesion at 23 ° C and the "adhesive strength (acrylic plate) @60 ° C" column shown in the column of "Adhesive strength (acrylic plate) @23 ° C" in Tables 2 to 5 are shown. The adhesion at 60 ° C is shown to calculate the adhesion rate. Here, the "adhesion rate" is specifically calculated as {(adhesion at 60 ° C) - (adhesion at 23 ° C)} / (adhesion at 23 ° C) × 100.

The adhesion rate of each of the examples and the comparative examples is shown in the "adhesion rate" column of Tables 2 to 5.

[Adhesion evaluation (SUS embossing plate)]

According to WO2011/002083, the adhesion of the laminate obtained in each of the examples and the comparative examples to the SUS embossed plate was measured in the following manner. Here, the laminate obtained in each of the examples and the comparative examples was used as a protective film.

A protective film is attached to a stainless steel plate (SUS304, polished No. 180) having a width of 50 mm, and placed in a fixed environment at a temperature of 23 ° C and a relative humidity of 50% for one day, and then at a temperature of 23 ° C and a relative humidity of 50%, along the 180. The direction of the peel was peeled at a speed of 300 mm/min, and the adhesion was measured. That is, the above-mentioned stainless steel plate was used instead of the above-mentioned black acrylic plate, and the "adhesive film" was replaced with the "protective film", and in addition to the above, "adhesion evaluation" (C) The protective film was attached and measured in the same manner as the olefinic plate.

The adhesive force of each of the examples and the comparative examples is shown in the "adhesive strength (SUS embossing plate)" column of Tables 2 to 5.

[Adhesive stability (SUS embossing plate)]

The adhesion stability of the laminate obtained in each of the examples and the comparative examples to the SUS embossed plate was evaluated in the following manner. Here, the laminate obtained in each of the examples and the comparative examples was used as a protective film.

A protective film was attached to a stainless steel plate (SUS304, polished No. 180), and the attached surface was stored for one day in a fixed environment at a temperature of 23 ° C and a relative humidity of 50%. The number of peeling sheets of the protective film after storage was confirmed and evaluated in the following manner.

×: all peeled off or not adhered to the substrate

△: Part of the film peeling

○: All remain stuck

The evaluations of the respective examples and comparative examples are shown in the column of "adhesion stability (SUS embossing plate)" in Tables 2 to 5.

[Adhesion evaluation (seesaw)]

The adhesion of the laminate obtained in each of the examples and the comparative examples to the raft was measured in the following manner.

A tantalum sheet containing an acrylic resin having a thickness of 110 μm, a pitch of 50 μm, and a height of 35 μm was used as a backing plate, and a laminate obtained in each of Examples and Comparative Examples was used as a protective film. Here, the width of the protective film was set to 50 mm. The protective film was press-bonded to the slab at 20 mm/min using a 2 kg rubber roller, and left at a temperature of 23 ° C and a relative humidity of 50% for 30 minutes, and then peeled at a speed of 300 mm/min in a 180° direction to measure adhesion. force.

The adhesive strengths of the respective examples and comparative examples are shown in the "adhesive strength (seesaw)" column of Tables 2 to 5.

[Adhesive stability (seesaw)]

The adhesion stability of the laminate obtained in each of the examples and the comparative examples to the raft was measured in the following manner.

The laminate obtained in each of the examples and the comparative examples was used as a protective film. Further, the same stainless steel sheet as the user of the above-mentioned "adhesion evaluation (slab)" is used in place of the above-mentioned stainless steel sheet, and a protective film is attached thereto, in addition to the above-mentioned "adhesion stability (SUS embossing sheet) )" Evaluation in the same way.

The evaluations of the respective examples and comparative examples are shown in the "adhesion stability (seesaw)" column of Tables 2 to 5.

[Synthesis Example 1]

750 ml of 4-methyl-1-pentene was charged at 23 ° C in a SUS autoclave having a stirring capacity of 1.5 liters which was sufficiently purged with nitrogen. To the autoclave, 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL) was placed, and the mixer was operated.

Next, the autoclave was heated to an internal temperature of 60 ° C, and pressurized with propylene so that the total pressure became 0.13 MPa (gauge pressure). Then, the previously prepared methylaluminoxane was 1 mmol in terms of Al using nitrogen gas, and contained diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7- A solution of 0.34 ml of a di-t-butyl-indenyl)zirconium dichloride 0.01 mmol toluene solution was introduced into the autoclave to start polymerization. In the polymerization reaction, the internal temperature of the autoclave becomes 60. Temperature adjustment in °C mode. After 60 minutes from the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen gas to stop the polymerization, and the autoclave was released to atmospheric pressure. The mixture was stirred while injecting acetone into the reaction solution.

The obtained powdery polymer containing a solvent was dried at 100 ° C for 12 hours under reduced pressure. The polymer obtained was 36.9 g, the content of 4-methyl-1-pentene in the polymer was 72.5 mol%, and the propylene content was 27.5 mol%.

[Synthesis Example 2]

It was charged with 300 ml of n-hexane (drying on activated alumina in a dry nitrogen atmosphere) at a temperature of 23 ° C in a SUS autoclave with a capacity of 1.5 liters, which was sufficiently purged with nitrogen, 4-methyl-1. -pentene 450 ml. To the autoclave, 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL) was placed, and the mixer was operated.

Next, the autoclave was heated to an internal temperature of 60 ° C, and pressurized with propylene so that the total pressure became 0.19 MPa (gauge pressure). Then, the previously prepared methylaluminoxane was 1 mmol in terms of Al using nitrogen gas, and contained diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7- A solution of 0.34 ml of a di-t-butyl-indenyl)zirconium dichloride 0.01 mmol toluene solution was introduced into the autoclave to start polymerization. The temperature adjustment was carried out in the polymerization reaction so that the internal temperature of the autoclave became 60 °C. After 60 minutes from the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen gas to stop the polymerization, and the autoclave was released to atmospheric pressure. The mixture was stirred while injecting acetone into the reaction solution.

The obtained powdery polymer containing a solvent was dried at 100 ° C for 12 hours under reduced pressure. The polymer obtained was 44.0 g, the content of 4-methyl-1-pentene in the polymer was 84.1 mol%, and the propylene content was 15.9 mol%.

[Synthesis Example 3]

To a SUS autoclave equipped with a stirring blade having a capacity of 1.5 liters sufficiently purged with nitrogen, 50 ml of 4-methyl-1-pentene was charged at 23 °C. To the autoclave, 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL) was placed, and the mixer was operated. Next, the autoclave was heated to an internal temperature of 30 ° C, and pressurized with propylene so that the total pressure became 0.74 MPa, and 12 N ml of hydrogen was added. Then, the previously prepared methylaluminoxane was 1 mmol in terms of Al using nitrogen gas, and contained diphenylmethylene (1-methyl-3-t-butyl-cyclopentadienyl) (2,7- A solution of 0.34 ml of a toluene solution of di-t-butyl-indenyl)zirconium dichloride (0.005 mmol) was pressed into an autoclave to start polymerization. Thereafter, the temperature was adjusted 60 minutes after the internal temperature of the autoclave became 60 °C. After 60 minutes from the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen gas to stop the polymerization, and the autoclave was released to atmospheric pressure. The mixture was stirred while injecting acetone into the reaction solution. The obtained rubbery polymer containing a solvent was dried at 130 ° C for 12 hours under reduced pressure. The polymer obtained was 78.1 g, the content of 4-methyl-1-pentene in the polymer was 8.9 mol%, and the propylene content was 91.1 mol%.

[Synthesis Example 4]

750 ml of 4-methyl-1-pentene was charged at 23 ° C in a SUS autoclave having a stirring capacity of 1.5 liters which was sufficiently purged with nitrogen. To the autoclave, 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL) was placed, and the mixer was operated. Next, the autoclave was heated to an internal temperature of 30 ° C, and pressurized with propylene so that the total pressure became 0.74 MPa, and 12 N ml of hydrogen was added. Then, the previously prepared methylaluminoxane was 1 mmol in terms of Al using nitrogen gas, and contained diphenylmethylene (1-methyl-3-t-butyl-cyclopentadienyl) (2,7- A solution of 0.34 ml of a toluene solution of di-t-butyl-indenyl)zirconium dichloride (0.005 mmol) was pressed into an autoclave to start polymerization. In the next 60 minutes, the internal temperature of the autoclave became 60 ° C. Temperature adjustment. After 60 minutes from the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen gas to stop the polymerization, and the autoclave was released to atmospheric pressure. The mixture was stirred while injecting acetone into the reaction solution. The obtained rubbery polymer containing a solvent was dried at 130 ° C for 12 hours under reduced pressure. The obtained polymer was 56.3 g, the content of 4-methyl-1-pentene in the polymer was 24.7 mol%, and the propylene content was 75.3 mol%.

[Synthesis Example 5]

750 ml of 4-methyl-1-pentene was charged at 23 ° C in a SUS autoclave having a stirring capacity of 1.5 liters which was sufficiently purged with nitrogen. Into the autoclave, 0.75 ml of a 1.0 mmol/ml toluene solution of triisobutylaluminum (TIBAL) was placed, and stirring was started.

Next, the autoclave was heated to an internal temperature of 60 ° C, and pressurized with propylene so that the total pressure became 0.17 MPa. Then, the previously prepared methylaluminoxane was 1 mmol in terms of Al using nitrogen gas, and contained diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7- A solution of 0.34 ml of a toluene solution of di-t-butyl-indenyl)zirconium dichloride (0.005 mmol) was pressed into an autoclave to start polymerization. The temperature adjustment was carried out in the polymerization reaction so that the internal temperature of the autoclave became 60 °C. After 60 minutes from the start of the polymerization, 5 ml of methanol was pressed into the autoclave with nitrogen gas to stop the polymerization, and the autoclave was released to atmospheric pressure. The mixture was stirred while injecting acetone into the reaction solution.

The obtained powdery polymer containing a solvent was dried at 130 ° C for 12 hours under reduced pressure. The weight of the obtained copolymer was 32.0 g, the content of 4-methyl-1-pentene in the copolymer was 92.3 mol%, and the propylene content was 7.7 mol%.

The physical properties of the copolymer obtained in the above synthesis examples are shown in Table 1, respectively.

[Example 1]

20 parts by weight of 4-methyl-1-pentene ‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene) manufactured by JSR Co., Ltd. Copolymer (HSBR)) 80 parts by weight, and 0.2 parts by weight of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat-resistant stabilizer . The obtained mixture was used as an adhesive resin composition, and was molded by three three-layer film forming machines to obtain a laminate (surface protective film) in the form of a multilayer film, and the physical properties of the laminate were measured. Here, the specific molding conditions to be used in obtaining the laminated body are as described in the above-mentioned "Laminated body forming". Various physical properties are shown in Table 2.

[Embodiment 2]

30 parts by weight of 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene) manufactured by JSR Co., Ltd. Copolymer (HSBR)) 70 parts by weight, and n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat resistant stabilizer 0.2 weight Share. The obtained mixture was used as an adhesive resin composition, and then molded by three three-layer film forming machines to obtain a laminate (surface protective film), and the physical properties of the laminate were measured. Here, the specific molding conditions to be used in obtaining the laminated body are as described in the above-mentioned "Laminated body forming". Various physical properties are shown in Table 2.

[Example 3]

In the adhesive layer, 30 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. 70 parts by weight of butadiene-styrene copolymer (HSBR), and changed to 50 parts by weight of 4-methyl-1-pentene ‧ α -olefin copolymer obtained in Synthesis Example 1 and JSR Co., Ltd. An adhesive resin composition sample was prepared in the same manner as in Example 2 except that 50 parts by weight of DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) was produced. Preparation and molding, and measuring the physical properties of the obtained laminate. Various physical properties are shown in Table 2.

[Comparative Example 1]

In the adhesive layer, 20 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. - Butadiene-styrene copolymer (HSBR)) 80 parts by weight, and DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Co., Ltd. 100 weight In the same manner as in Example 1, the same procedure as in Example 1 was carried out, and preparation and molding of a sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 3.

[Comparative Example 2]

In the adhesive layer, 30 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. - Butadiene-styrene copolymer (HSBR)) 70 parts by weight, and using DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Co., Ltd. 100 weight In the same manner as in Example 2, the preparation and molding of the sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 3.

[Comparative Example 3]

In the adhesive layer, 30 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. 70 parts by weight of butadiene-styrene copolymer (HSBR), and 100 parts by weight of 4-methyl-1-pentene ‧ α -olefin copolymer obtained in Synthesis Example 1 was used, and In the same manner as in Example 2, preparation and molding of a sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 3.

[Comparative Example 4]

In the adhesive layer, 30 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. 70 parts by weight of a butadiene-styrene copolymer (HSBR), and 100 parts by weight of a 4-methyl-1-pentene ‧ α -olefin copolymer obtained in Synthesis Example 2 was used. In the same manner as in Example 2, preparation and molding of a sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 3.

[Example 4]

In the adhesive layer, 20 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. 80 parts by weight of butadiene-styrene copolymer (HSBR), and 5 parts by weight of 4-methyl-1-pentene ‧ α -olefin copolymer obtained in Synthesis Example 2, and manufactured by JSR Co., Ltd. An adhesive resin composition sample was prepared in the same manner as in Example 1 except that 95 parts by weight of DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) was used. Preparation and molding, and measuring the physical properties of the obtained laminate. Various physical properties are shown in Table 2.

[Example 5]

The obtained in Synthesis Example 1 of 4-methyl-1-pentene ‧ α - olefin copolymer 20 parts by weight of the laminate was changed to 2 obtained in Synthesis Example of 4-methyl-1-pentene ‧ α - olefin copolymer assembly The preparation and molding of the sample of the adhesive resin composition were carried out in the same manner as in Example 1 except that 20 parts by weight, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 2.

[Embodiment 6]

In the adhesive layer, 30 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. 70 parts by weight of butadiene-styrene copolymer (HSBR), and 30 parts by weight of 4-methyl-1-pentene ‧ α -olefin copolymer obtained in Synthesis Example 1 was produced by Kaneka Co., Ltd. Preparation and formation of a sample of the adhesive resin composition were carried out in the same manner as in Example 2 except that 70 parts by weight of SIBSTAR (registered trademark) 062M (styrene-isobutylene-styrene copolymer (SIBS)) was used. The physical properties of the obtained laminate were measured. Various physical properties are shown in Table 2.

[Embodiment 7]

80 parts by weight of DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Co., Ltd. was changed to EVOLUE (registered trademark) SP0540 (ethylene) manufactured by Prime Polymer Co., Ltd. In the same manner as in Example 1, except that 80 parts by weight of the octene copolymer (LLDPE) was used, the preparation and molding of the sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 4.

[Embodiment 8]

80 parts by weight of DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Co., Ltd. was changed to TAFMER (registered trademark) PN-2060 manufactured by Mitsui Chemicals Co., Ltd. In the same manner as in Example 1, except that 80 parts by weight of the propylene-based elastomer (TPO) was used, the preparation and molding of the sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Shown in Table 4.

[Embodiment 9]

80 parts by weight of DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Co., Ltd. was changed to Prime Polypro (registered trademark) MF257 (produced by Prime Polymer Co., Ltd.) The same procedure as in Example 1 was carried out, except that the same procedure as in Example 1 was carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 4.

[Embodiment 10]

Synthesis Example 2 to obtain the 4-methyl-1-pentene ‧ α - olefin copolymer 20 parts by weight in place of assembly 1 obtained in Synthesis Example of 4-methyl-1-pentene ‧ α - olefin copolymer assembly 20 The same procedure as in Example 8 was carried out, and the preparation and molding of the sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 4.

[Comparative Example 5]

In the adhesive layer, 20 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. - Butadiene-styrene copolymer (HSBR)) 80 parts by weight, and using DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Co., Ltd. 80 weight In the same manner as in Example 1, except that 20 parts by weight of TAFMER (registered trademark) PN-2060 of Mitsui Chemicals Co., Ltd., the preparation and molding of the sample of the adhesive resin composition were carried out, and the obtained sample was obtained. The physical properties of the laminate. Various physical properties are shown in Table 5.

[Comparative Example 6]

In the adhesive layer, 20 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. - 80 parts by weight of butadiene-styrene copolymer (HSBR), and EVOLUE (registered trademark) SP0540 80 parts by weight of Prime Polymer Co., Ltd. and TAFMER (registered trademark) PN manufactured by Mitsui Chemicals, Inc. In the same manner as in Example 1, except that 2060 parts by weight of 2060 parts by weight, the preparation and molding of the sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 5.

[Comparative Example 7]

In the adhesive layer, 20 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. - The same operation as in Example 1 except that 80 parts by weight of butadiene-styrene copolymer (HSBR) was used, and TAFMER (registered trademark) PN-2060 100 parts by weight manufactured by Mitsui Chemicals, Inc. was used. The preparation and molding of the sample of the adhesive resin composition were carried out, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 5.

[Comparative Example 8]

In the adhesive layer, 20 parts by weight of the 4-methyl-1-pentene‧ α -olefin copolymer obtained in Synthesis Example 1 and DYNARON (registered trademark) 1320P (hydrogenated styrene) manufactured by JSR Co., Ltd. were used instead. 80 parts by weight of a butadiene-styrene copolymer (HSBR), and TAFMER (registered trademark) PN-2060 80 parts by weight of Mitsui Chemicals Co., Ltd. and DYNARON (registered trademark) 1320P manufactured by JSR Co., Ltd. The same procedure as in Example 1 was carried out, except that 20 parts by weight of (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) was used, and preparation and molding of a sample of the adhesive resin composition were carried out, and the measurement was obtained. The physical properties of the laminate. Various physical properties are shown in Table 5.

Claims (6)

A surface protective film comprising a laminate comprising at least one adhesive layer comprising a resin composition and a substrate layer; the resin composition comprising: satisfying the following requirements (a), (b) , (c) and (d) 4-methyl-1-pentene ‧ α - olefin copolymer (A) 2 to 50 parts by weight, and the copolymerization of the 4-methyl-1-pentene ‧ α - olefin 98 to 50 parts by weight of the thermoplastic resin (B) other than the combined (A) (wherein the total of the above 4-methyl-1-pentene ‧ α - olefin copolymer (A) and the above thermoplastic resin (B) is 100% by weight (a) comprising a constituent unit derived from 4-methyl-1-pentene (i) 65 to 90 mol% and derived from an α-olefin (excluding 4-methyl-1-pentene) The constituent unit (ii) is 35 to 10 mol%; (b) the ultimate viscosity [η] measured at 135 ° C in decalin is in the range of 0.1 to 5.0 dL/g; (c) by gel permeation. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by chromatography (GPC) (molecular weight distribution, Mw/Mn) is in the range of 1.0 to 3.5; (d) the density is 870 to 830 kg/m. The scope of ³ . The surface protection film of claim 1, wherein in the above-mentioned requirement (a), the ratio of the constituent unit (i) is 80 to 90 mol%, and the ratio of the constituent unit (ii) is 20 10 moles %. The surface protective film according to claim 1 or 2, wherein the thermoplastic resin (B) is a styrene-based elastomer (B2). The surface protective film according to any one of claims 1 to 3, wherein the laminated system is a multilayer film obtained by a T-die film forming method. A method for protecting a surface, which uses a surface protection film of the third application of the patent application to protect a surface having a surface unevenness of 0.1 to 300 μm. A method for protecting a ruthenium sheet, which uses the surface protection film of the third application of the patent scope to protect the ruthenium sheet.