KR20160027176A - Surface protective film - Google Patents

Abstract

An object of the present invention is to provide a surface protective film which is capable of preventing natural peeling from an adherend and adhering adhesion in a pressure-sensitive adhesive layer to be suppressed when adhered to various adherends having flat or concave and convex portions. The surface protective film of the present invention comprises 2 to 50 parts by weight of 4-methyl-1-pentene -olefin copolymer (A) satisfying the following requirements (a), (b), (c) , And 50 to 98 parts by weight of a thermoplastic resin (B), and a laminate having a base layer:
(a) from 65 to 90 mol% of the constituent unit derived from 4-methyl-1-pentene and from 35 to 10 mol% of the constituent unit derived from the -olefin (ii); (b) the intrinsic viscosity [?] measured in decalin at 135 占 폚 in the range of 0.1 to 5.0 dL / g; (c) the molecular weight distribution (Mw / Mn) is in the range of 1.0 to 3.5; (d) the density is in the range of 870 to 830 kg / m ³ .

Description

Surface Protective Film {SURFACE PROTECTIVE FILM}

The present invention relates to a surface protective film comprising a laminate having a pressure-sensitive adhesive layer containing a specific resin composition.

A surface protective film in which a pressure-sensitive adhesive layer and a base layer are laminated is used to protect metal plates such as aluminum plates, steel plates, and stainless steel plates and their coated plates, glass plates or synthetic resin plates and products and parts including these members. The surface protective film is peeled at the time of forming the material or at a predetermined time after the forming process.

This surface protective film can be easily adhered to an adherend and easily adhered. It is required that the surface protective film is not easily peeled off when carrying an adherend, and is easily peelable when peeling off at the time of processing or processing. Therefore, the protective film is preferably provided with mechanical properties such as elongation and the like, depending on the appropriate tackiness to the surface to be protected of the adherend, the suitability of the film itself not to scratch the surface to be protected, Various properties such as suitability and heat resistance are required. Further, depending on the application, it is required to have good appearance, transparency and color tone, and it is required that there is no film defect such as gel, fish eye, and the like. Also, since this type of surface film is consumed in a large amount and is quickly discarded, it is required that it can be produced at low cost.

Conventionally, as this kind of adhesive film, there has been known a film obtained by applying an acrylic or rubber-based pressure-sensitive adhesive on one side of a base film containing a polymer such as low-density polyethylene or polypropylene as a main component or a pressure- And those formed by molding.

For example, Patent Document 1 discloses a pressure-sensitive adhesive and a pressure-sensitive adhesive sheet containing propylene, an? -Olefin having 4 to 12 carbon atoms and a propylene-based polymer containing ethylene as a copolymer component and having low staining property to an adherend .

In addition, there are many members requiring properties such as a polarizing plate, a retardation plate, a light guide plate, a reflection plate, and a prism plate for electric and electronic materials and optical products, and a protective film which maintains a proper adhesive force is desired for these members have. Since an adherend having such irregularities on the surface has a small contact area with the adhesive layer, a high adhesive force is required for the pressure-sensitive adhesive layer. However, by using a high adhesive force, there are concerns such as limitation of the molding method such as coating and application, residual adhesive to the adherend, and the like.

From a more specific point of view, there are some electric and electronic materials and optical products whose surfaces are uneven, such as a polarizing plate, a retardation plate, a light guide plate, a reflection plate, a prism sheet or a diffusion film. The surface of the concavity and convexity is protected by a protective film prior to use so as not to damage the concavity and the convexity, and a surface protective film which maintains an appropriate adhesive strength is also desired for these members. In such a surface protective film, there is a problem of so-called adhesion entanglement depending on external factors such as time and temperature after adhering to the surface of an adherend. In particular, in the case of an adherend having a surface irregularity shape, the adherend is caused by an increase in the contact area between the adherend and the pressure-sensitive adhesive layer, and in particular, Since the increase in the contact area is remarkable, adhesive entanglement is particularly likely to occur.

As a result, the peeling operation from the surface of the adherend becomes difficult, or the adhesive residue which partially remains on the adherend occurs.

Patent Documents 2 and 3 disclose a surface protective film comprising a pressure-sensitive adhesive layer comprising a styrene-based elastomer and an adhesion-imparting resin as an isobutylene block copolymer. However, in the method disclosed in this publication, adhesion to an adherend having high unevenness is insufficient, stickiness and blocking are poor, and productivity due to defective extrusion molding is poor.

Patent Documents 4 and 5 disclose a resin composition and a surface protective film which hardly cause adhesion migration by using a styrene-based elastomer as an adhesive layer. However, the resin composition and the surface protective film are not limited to the evaluation of adhesion on a smooth substrate such as a PET substrate or an acrylic substrate And since the adhesive force is low, it is difficult to expand the substrate to a substrate having a concave-convex shape.

Patent Document 6 discloses a surface protecting film in which adhesive adhesion is suppressed by a stiffness-imparting styrene-based elastomer and a specific fatty acid amide composition in a pressure-sensitive adhesive layer. However, since a low molecular weight compound is used, And so on.

International Publication No. WO2008 / 099865 pamphlet Japanese Patent Application Laid-Open No. 2007-126512 Japanese Patent Application Laid-Open No. 255071/1995 Japanese Patent Application Laid-Open No. 2008-274213 Japanese Patent Application Laid-Open No. 11-126169 Japanese Patent Application Laid-Open No. 2013-121989

It is an object of the present invention to provide a surface protective film in which natural peeling from an adherend is prevented when adhering to various adherends having flat or uneven surfaces. Another object to be solved by the present invention is to provide a surface protective film capable of suppressing adhesion of adhesion in an adhesive layer when adhered to various adherends.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a surface protective film having an adhesive layer containing a specific resin composition comprising a 4-methyl-1-pentene copolymer in combination with a thermoplastic resin exhibits good follow- And found that it has sufficient adhesive strength and sufficient adhesive stability. That is, it is preferable to use a material having a sufficient adhesive force and good uneven follow-up property to adhere to various adherends having irregularities, rather than adhering to an adherend having a small contact area using a material having high adhesiveness as in the prior art The contact area can be increased. As a result, they found that they had good adhesion stability, and they completed the present invention.

The present inventors also found that a specific resin composition comprising a 4-methyl-1-pentene copolymer in combination with a thermoplastic resin combines sufficient adhesive strength and adhesion-inhibiting effect when used as a pressure-sensitive adhesive, It was completed.

In the surface protective film of the present invention,

2 to 50 parts by weight of a 4-methyl-1-pentene -olefin copolymer (A) satisfying the following requirements (a), (b), (c)

98 to 50 parts by weight of a thermoplastic resin (B) other than the 4-methyl-1-pentene /? - olefin copolymer (A)

At least one pressure-sensitive adhesive layer containing a resin composition containing the 4-methyl-1-pentene /? - olefin copolymer (A) and the thermoplastic resin (B) in an amount of 100 parts by weight, Layer < / RTI > comprising:

(ii) a constituent unit derived from (a) 65 to 90 mol% of a constituent unit derived from 4-methyl-1-pentene and an α-olefin (excluding 4-methyl- 35 to 10 mol%;

(b) the intrinsic viscosity [?] measured in decalin at 135 占 폚 in the range of 0.1 to 5.0 dL / g;

(c) the ratio (molecular weight distribution: Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5;

(d) the density is in the range of 870 to 830 kg / m ³ .

The surface protective film of the present invention can exhibit sufficient adhesion when adhering to not only a flat adherend but also various adherends having irregularities and a sufficient contact area with the adherend due to excellent irregularity followability And has adhesion stability. Further, the surface protective film of the present invention can exert a sufficient adhesive force when adhered not only to an adherend which is a flat plate, but also to various adherends, and has a superior adhesive entanglement inhibiting effect.

Hereinafter, the surface protective film of the present invention will be described in more detail.

The surface protective film of the present invention comprises a laminate having at least one pressure-sensitive adhesive layer containing the following resin composition and a base layer.

[Resin composition]

The resin composition used in the present invention is a resin composition comprising a 4-methyl-1-pentene /? - olefin copolymer (A) having a specific physical property and a And contains the thermoplastic resin (B) in a specific ratio.

In the present specification, the 4-methyl-1-pentene /? - olefin copolymer (A) is sometimes simply referred to as "copolymer (A) The thermoplastic resin (B) other than the co-polymer (A) may be simply referred to as " thermoplastic resin (B) ".

<4- methyl -One- Pentene -? - olefin copolymer (A)

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

Requirement (a);

The 4-methyl-1-pentene /? - olefin copolymer (A) used in the present invention is obtained by copolymerizing 65 to 90 mol% of the constituent unit derived from 4-methyl- , And 4-methyl-1-pentene), (ii) from 35 to 10 mol%. Here, &quot; mol% &quot; is a value obtained by assuming that the total amount of the constituent units derived from the total constituent monomers is 100 mol%. For example, when the 4-methyl-1-pentene / In the case where only the unit (i) and the constituent unit (ii) are contained, it is a value when the sum of the constituent unit (i) and the constituent unit (ii) is 100 mol%.

That is, the lower limit of the ratio of the constituent unit (i) is 65 mol%, but preferably 80 mol%, more preferably 81 mol%. On the other hand, the upper limit value of the proportion of the constituent unit (i) is 90 mol%, but more preferably 86 mol%. As described above, in the present invention, the proportion of the constituent unit (i) in the 4-methyl-1-pentene /? - olefin copolymer (A) is at least the lower limit value described above, And is suitably flexible by being below the upper limit value. Further, at 80 to 90 mol%, the resulting surface protective film has a high surface hardness while maintaining excellent adhesive strength to the flat or uneven surface, adhesive stability and appropriate flexibility not causing scratches on the adherend, And the handling of the surface protective film before adhesion is facilitated, and more preferably from 81 to 86 mol%.

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

Examples of the? -Olefin derived from the constituent unit (ii) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, Octadecene, 1-octadecene, 1-octadecene, 1-octadecene and 1-eicosene, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4-methyl-1-butene, Branched olefins having 5 to 20 carbon atoms and preferably 5 to 15 carbon atoms such as 4-dimethyl-1-hexene, 4-ethyl-1-hexene and 3-ethyl- have. Of these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and ethylene and propylene are particularly preferable.

The? -Olefins derived from the above-mentioned constituent unit (ii) may be used singly or in combination of two or more.

Here, in an embodiment of the present invention, the 4-methyl-1-pentene /? - olefin copolymer (A) contains only 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 mol%.

However, the amount of the 4-methyl-1-pentene /? - olefin copolymer (A) is such a small amount as not to impair the object of the present invention, specifically 10 mol% or less, preferably 5 mol% Of the polymerizable monomer other than the constituent unit (i) and the constituent unit (ii) other than the 4-methyl-1-pentene and the constituent unit (ii) And may further contain derived constituent units.

Specific preferred examples of these other polymerizable monomers include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; Vinyl esters such as vinyl acetate; Unsaturated organic acids such as maleic anhydride or derivatives thereof; Conjugated dienes such as butadiene, isoprene, pentadiene and 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, Diene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, Propylidene-2-norbornene, 6-chloromethyl-5-isopropen-2-norbornene, 2,3-diisopropylidene- Non-conjugated polyenes such as lidene-5-norbornene, 2-propenyl-2,2-norbornadiene and the like.

In other words, the 4-methyl-1-pentene /? - olefin copolymer (A) used in the present invention includes the following constitutional units:

65 to 90 mol% of a constituent unit derived from 4-methyl-1-pentene (i);

35 to 10 mol% of a constituent unit derived from an? -olefin (excluding 4-methyl-1-pentene) (ii); And

0 to 10 mol% of constituent units derived from 4-methyl-1-pentene and other polymerizable monomers other than the? -Olefin constituting the constituent unit (ii).

Here, when a constituent unit derived from another polymerizable monomer is present, the total content of the constituent unit derived from the constituent unit (ii) and the other polymerizable monomer satisfies the above-mentioned "proportion of the constituent unit (ii)". In this case, the total amount of the constituent unit (i) and the constituent unit (ii) and the constituent unit derived from the other polymerizable monomer is 100 mol%.

The other polymerizable monomers may be two or more.

In the present specification, when the term "constitutional unit derived from X" (wherein X is a compound having a carbon-carbon double bond)), in the (co) polymer obtained by using X as a monomer, Means a structural unit. For example, when the term "structural unit derived from 4-methyl-1-pentene" refers to a structural unit derived from 4-methyl-1-pentene (co) polymer obtained as a monomer Means a structural unit corresponding to 4-methyl-1-pentene.

Requirement (b);

The intrinsic viscosity [?] Of the 4-methyl-1-pentene /? - olefin copolymer (A) used in the present invention measured at 135 ° C in decalin is in the range of 0.1 to 5.0 dL / g. Details of the measurement conditions and the like are as described in the column of Examples described later.

The intrinsic viscosity [?] Is preferably 0.5 to 4.0 dL / g, more preferably 0.5 to 3.5 dL / g.

When hydrogen is used in combination during polymerization as described later, the molecular weight can be controlled and the intrinsic viscosity [?] Can be adjusted.

If the intrinsic viscosity [?] Is excessively less than 0.1 dL / g or more than 5.0 dL / g, the molding processability in forming the pressure-sensitive adhesive layer constituting the surface protective film, .

Requirement (c);

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the 4-methyl-1-pentene /? - olefin copolymer (A) Molecular weight distribution: Mw / Mn) is in the range of 1.0 to 3.5. Details of the measurement conditions and the like are as described in the column of Examples described later.

The Mw / Mn is preferably 1.2 to 3.0, more preferably 1.5 to 2.8. If the Mw / Mn is more than 3.5, the influence of the low-molecular-weight, low-stereoregularity polymer derived from the composition distribution is a concern, and the adhesion surface of the obtained surface protective film, that is, the surface of the pressure- The feel is deteriorated due to stickiness, and the adherend is easily contaminated.

Here, in the present invention, by using a catalyst described later, the copolymer (A) satisfying the requirement (c) can be obtained within the range of the intrinsic viscosity [] of the requirement (b). The values of Mw / Mn and the following Mw are values measured by a method employed in the following embodiments.

The weight average molecular weight (Mw) of the 4-methyl-1-pentene -olefin copolymer (A) measured by gel permeation chromatography (GPC) is preferably 500 to 10,000,000 , More preferably from 1,000 to 5,000,000, and still more preferably from 1,000 to 2,500,000.

Requirement (d);

4-methyl-1-pentene used in the present invention, the density of the α- olefin copolymer (A) (measured at ASTM D 1505) is 870 to 830kg / m ^3, preferably 865 to 830kg / m ^3, more preferably M &lt; ³ &gt;. Details of the measurement conditions and the like are as described in the column of Examples described later.

The density can be appropriately changed according to the comonomer composition ratio of the 4-methyl-1-pentene -olefin copolymer (A), and the copolymer (A) having the density within the above range is excellent in lightweight pressure- Which is advantageous in manufacturing.

The 4-methyl-1-pentene /? - olefin copolymer (A) used in the present invention has a Shore A hardness (in accordance with JIS K6253, 3 mm Measured in the state of the press sheet of the present invention) is in the range of 5 to 90, preferably 10 to 85, more preferably 15 to 80. [ The production method of the press sheet is as shown in the embodiment.

The 4-methyl-1-pentene /? - olefin copolymer (A) used in the present invention is further characterized by having a Shore A hardness (defined as JIS K6253, It is preferable that the change in the value (DELTA HS) of the value measured in the state of (a) is in the range of 5 to 60, preferably 10 to 50, and more preferably 10 to 45. [

? HS = (Shore A hardness value immediately after the start of the pressure contact - Shore A hardness value after 15 seconds from the start of the pressure contact)

The ΔHS can be arbitrarily changed depending on the comonomer species and the comonomer composition of the 4-methyl-1-pentene / -olefin copolymer (A), and when ΔHS is within the above range, the irregularity followability is excellent.

Further, when it is difficult to measure the Shore A hardness, instead of using the Shore D hardness value,

ΔHS '= (Shore D hardness value immediately after the start of pressure contact - Shore D hardness value after 15 seconds from the start of pressure contact)

Can be obtained. In this case, it is preferable that this? HS 'is in the range of 5 to 50, preferably 5 to 25, more preferably 6 to 20. Similarly to the above-mentioned ΔHS, this ΔHS 'can be optionally changed according to the comonomer constituting the 4-methyl-1-pentene / α-olefin copolymer (A) and the comonomer composition. If ΔHS' , And excellent follow-up irregularity.

<4- methyl -One- Pentene Production method of? -Olefin copolymer (A)

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

The process for producing a 4-methyl-1-pentene /? - olefin copolymer (A) used in the present invention is a process for producing a 4-methyl-1-pentene / Is not particularly limited as long as it can obtain the (meth) acrylic acid-1-pentene /? - olefin copolymer (A). However, in a general form of the present invention, the 4-methyl-1-pentene 占--olefin copolymer (A) is a copolymer of 4-methyl-1-pentene and the above- By polymerization in the presence of a suitable polymerization catalyst. As the polymerization catalyst which can be used in the present invention, conventionally known catalysts such as magnesium-supported titanium catalysts, pamphlets of WO 01/53369, WO 01/27124, JP- A metallocene catalyst described in JP-A-193796 or JP-A-02-41303 is suitably used, and more preferably, an olefin polymerization catalyst containing a metallocene compound represented by the following general formula (1) or Lt; / RTI &gt;

[Chemical Formula (1)

(2)

(In the formula (1), (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, R 13 And R ¹⁴ are selected from hydrogen, a hydrocarbon group and a silicon-containing hydrocarbon group, and may be the same or different, adjacent substituents from R ¹ to R ⁴ may be bonded to each other to form a ring, and R ⁵ to R ¹² , A may be a bivalent hydrocarbon group of 2 to 20 carbon atoms which may contain some unsaturated bonds and / or aromatic rings, A represents a ring formed together with Y, May contain two or more ring structures,

M is a metal selected from Group 4 of the Periodic Table,

Y is carbon or silicon,

Q is selected from the same or different combinations from halogen, a hydrocarbon group and an anionic ligand or a neutral ligand which can be coordinated to a lone electron pair,

j is an integer of 1 to 4)

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is selected from hydrogen, a hydrocarbon group and a silicon-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, And may include a cyclic structure. In addition, some or all of the hydrogen in the hydrocarbon group may be substituted with a functional group such as a hydroxyl group, an amino group, a halogen group or a fluorine-containing hydrocarbon group. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, Methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, Methyl-1-tetrahydronaphthyl, phenyl, biphenyl, naphthyl, tolyl, chlorophenyl, chlorobiphenyl, chloronaphthyl and the like.

The silicon-containing hydrocarbon group is preferably an alkylsilyl group or an arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl, and the like. have.

Adjacent substituents R ⁵ to R ¹² on the fluorene ring may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl, and the like.

The substituents on R ⁵ to R ¹² on the fluorene ring are preferably 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 , And it is more preferable that the fluorene ring is an unsubstituted fluorene, 3,6-iodine fluorene, 2,7-iodine fluorene or 2,3,6,7-tetrasubstituted fluorene. Here, the 3 rd, 6 rd, 2 rd and 7 th positions on the fluorene 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 preferred hydrocarbon groups include the same ones as described above.

Y is carbon or silicon. In the case of the formula (1), R ¹³ and R ¹⁴ are bonded to Y and constitute a substituted methylene group or substituted silylene group as a bridging moiety. Specific preferred examples thereof include methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, fluoromethylphenylmethylene, chloromethylphenylmethylene, diphenylmethylene, dichlorophenylmethylene, Methylphenylmethylene, ethyl-p-methylphenylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, di-n-butylphenylmethylene, Methyl-tert-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, fluoromethylphenylsilylene, chloromethylphenylsilylene, diphenylsilylene, dip-methylphenylsilylene, methylp -Methylphenylsilylene, ethyl-p-methylphenylsilylene, methylnaphthylsilylene, dinaphthylsilylene and the like.

In the case of formula (2), Y may be bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms, which may contain some unsaturated bonds and / or aromatic rings, to form a cycloalkylidene group or a cyclomethylene silylene group, . Specific preferred examples include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetra Examples of the silane coupling agent include silane coupling agents such as cyclopentene, cyclohexane, cyclohexylene, cyclohexylene, cyclohexylene, cyclohexylene, cyclohexylene, cyclohexylene, cyclohexylene, cyclohexylene, have.

M in the formulas (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 selected from the same or different combinations from a halogen, a hydrocarbon group having 1 to 20 carbon atoms, and a neutral ligand capable of coordinating with an anion ligand or a lone electron pair. Specific examples of the halogen include fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group include the same ones as described above. Specific examples of the anionic ligand include an alkoxy group such as methoxy, tert-butoxy and phenoxy, a carboxylate group such as acetate and benzoate, and a sulfonate group such as mesylate and tosylate. Specific examples of the neutral ligands which can be coordinated with the lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, and organic phosphorus compounds such as tetrahydrofuran, diethylether, dioxane, - dimethoxyethane, and the like. Of these, Qs may be the same or different, but at least one of them is preferably a halogen or an alkyl group.

In the above formulas (1) and (2), j is preferably 2.

As the metallocene compound constituting the olefin polymerization catalyst which can be used in the present invention, the metallocene compound represented by the above formula (1) or (2) is particularly suitably used, but the present invention is not limited thereto. For example, another suitable example of the metallocene compound usable in the present invention is a metallocene compound represented by the following chemical formula [I].

[Chemical Formula I]

(Formula [I] ^{of, 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 R ² is a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, R ⁴ is a hydrogen atom, and R ¹ to R ⁴ excluding R ⁴ are independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon- Any two of the substituents up to R ¹⁶ may be bonded to form a ring, M is a Group 4 transition metal, Q is a neutral ligand capable of coordinating to a halogen atom, a hydrocarbon group, an anion ligand, , J is an integer of 1 to 4, and when j is an integer of 2 or more, Q may be selected in the same or different combination)

In the formula [I], it is preferable that R ¹ and R ³ are hydrogen atoms; R ² is preferably a hydrocarbon group having 1 to 20 carbon atoms, and it is preferable that the carbon bonded to the cyclopentadienyl ring is 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 hydrogen atoms; It is preferable that R ¹⁰ , R ¹¹ , R ¹⁴ and R ¹⁵ are hydrocarbon groups, 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.

< R ^One  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 linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon groups, cyclic unsaturated hydrocarbons Group or a group obtained by substituting one or two or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group. The number of carbon atoms of the hydrocarbon group is usually 1 to 20, preferably 1 to 15, more preferably 1 to 10.

Examples of the straight chain hydrocarbon group include linear or branched hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, A straight chain alkyl group such as a decyl group; And straight-chain alkenyl groups such as an allyl group.

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

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 norbornyl group, an adamantyl group, and 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, and an anthracenyl group; Cycloalkenyl groups such as cyclohexenyl group; And a 5-bicyclo [2.2.1] hept-2-enyl group.

Examples of the group obtained by substituting one or two or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include one or two or more groups having an alkyl group such as benzyl group, cumyl group, 1,1-diphenylethyl group, And groups obtained by substituting a hydrogen atom with an aryl group.

Examples of the hetero atom-containing hydrocarbon group in R ¹ to R ¹⁶ (except R ⁴ ) include an alkoxy group such as methoxy group and ethoxy group, an aryloxy group such as phenoxy group, an oxygen atom such as furyl group Containing hydrocarbon group; Amino group such as N-methylamino group, N, N-dimethylamino group and N-phenylamino group, nitrogen atom-containing hydrocarbon group such as pyryl group; Thienyl group, and other sulfur atom-containing hydrocarbon groups. The number of carbon atoms of the hetero atom-containing hydrocarbon group is usually 1 to 20, preferably 2 to 18, more preferably 2 to 15. However, the silicon-containing group is excluded from the hetero atom-containing hydrocarbon group.

Examples of the silicon-containing group in R ¹ to R ¹⁶ (excluding R ⁴ ) include, for example, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, And a group represented by the formula -SiR ₃ (wherein R in the formulas is independently an alkyl group having 1 to 15 carbon atoms or a phenyl group).

Of the substituents from R ^1, except for R ⁴ to R ^16, the adjacent two substituents (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⁾ are bonded to each other and may form a ring, R ⁶ And R ⁷ may combine with each other to form a ring. R ¹ and R ⁸ may be bonded to each other to form a ring. R ³ and R ⁵ may be bonded to each other to form a ring. The ring formation may be present in two or more places in the molecule.

In the present specification, examples of the ring (additional ring) formed by bonding two substituents to each other include, for example, alicyclic rings, aromatic rings and heterocyclic rings. Specifically, cyclohexane ring; Benzene ring; Hydrogenated benzene rings; Cyclopentane ring; A heterocycle such as a furan ring and a thiophene ring, and a corresponding hydrogenated heterocycle, preferably a cyclohexane ring; Benzene ring and hydrogenated benzene ring. Such a ring structure may further have a substituent such as an alkyl group on the ring.

It is preferable that R ¹ and R ³ are hydrogen atoms from the viewpoint of stereoregularity.

At least one selected from R ⁵ , R ⁶ and R ⁷ is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, more preferably R ⁵ is a hydrocarbon group, R ⁵ is a straight- having 2 or more groups such as alkyl group, cycloalkyl group or cycloalkenyl group is more preferable, and particularly preferably R ⁵ is an alkyl group having 2 or more. From the viewpoint of synthesis, it is also preferable that R ⁶ and R ⁷ are hydrogen atoms. It is more preferable that R ⁵ and R ⁷ combine with each other to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring.

R ⁸ is preferably a hydrocarbon group, particularly preferably an alkyl group.

From the viewpoint of stereoregularity, R ² is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, further preferably an aryl group, more preferably a linear hydrocarbon group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group Is particularly preferable, and it is particularly preferable that the carbon having a free valence (carbon bonded to the cyclopentadienyl ring) is a tertiary carbon substituent.

Specific examples of R ² include methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, tert-amyl, 1-methylcyclohexyl and 1-adamantyl. Preferably a tertiary carbon having a free valence such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group and a 1-adamantyl group, particularly preferably a tert- - adamantyl group.

In the formula [I], the fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative, but from the viewpoints of stereoregularity and molecular weight, R ⁹ , R ¹² , R ¹³ and R ¹⁶ are preferably Is 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, Lt; / RTI &gt;

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 substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2, 3,4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorenyl group, 1,1,3,3,6,6,8,8-octamethyl- , 3,6,7,8,10-hexahydro-1H-dicyclopenta [b, h] fluorenyl group, 1 ', 1', 3 ', 6', 8 ''H,8'H-dicyclopenta [b, h] fluorenyl group, particularly preferably 1,1,4,4,7,7,10,10-octamethyl- 4,7,8,9,10,12-octahydro-1H-dibenzo [b, h] fluorenyl group.

&Lt; M, Q, j >

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

Examples of the hydrocarbon group which may be Q include groups similar to the hydrocarbon groups in R ¹ to R ¹⁶ (except R ⁴ ), and preferably alkyl groups such as linear alkyl groups and branched alkyl groups.

Examples of the anion ligand in Q include alkoxy groups such as methoxy and tert-butoxy; An aryloxy group such as phenoxy; Carboxylate groups such as acetate and benzoate; Sulfonate groups such as mesylate and tosylate; And amide groups such as dimethyl amide, diisopropyl amide, methyl anilide and diphenyl amide.

Examples of the neutral ligand capable of coordinating with the lone pair of electrons in Q include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine; And ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

At least one of Q is preferably a halogen atom or an alkyl group.

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

In addition, the positional number used for naming the compound [I] is represented by [1- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [ (5-tert-butyl-1-methyl-3-isopropyl-1,2,3,4-tetrahydropentalene)] zirconium dichloride and [8- (2'-tert-butyl) benzo [b, h] fluorene-12'-yl) -8-methyl-3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene)] zirconium dichloride as an example, ], And the formula [I-2].

As specific examples of the metallocene compound in the present invention, compounds exemplified in WO 01/27124, WO 2006/025540 or WO 01/050817 may suitably be mentioned, The scope of the present invention is not limited thereto.

When a metallocene compound is used in the production of the 4-methyl-1-pentene /? - olefin copolymer (A)

(a) a metallocene compound (for example, a metallocene compound represented by the above formula (1), (2) or [I]),

(b) (b-1) an organoaluminum oxy-compound,

(b-2) a compound which reacts with the metallocene compound (A) to form an ion pair, and

(b-3) Organoaluminum compound

At least one kind of compound selected from

If necessary,

(c)

. As a manufacturing method, for example, the method described in WO 01/27124 can be adopted.

It is also possible to react with an organoaluminum oxy compound (b-1) (hereinafter also referred to as "component (b-1)") and a metallocene compound (a) (Hereinafter also referred to as "component (b-3)") and the particulate carrier (c) (hereinafter also referred to as "component Examples of these compounds or carriers include conventionally known ones in the field of olefin polymerization, for example, those described in WO 01/27124.

Here, in a preferred form of the present invention, the 4-methyl-1-pentene 占--olefin copolymer (A) is a copolymer of 4-methyl-1-pentene and the? -Olefin Can be obtained by polymerization in the presence of the polymerization catalyst. In the production of the 4-methyl-1-pentene /? - olefin copolymer (A), polymerization can be carried out by liquid phase polymerization methods such as dissolution polymerization, Or by any of the following methods.

In the liquid phase polymerization method, an inert hydrocarbon solvent can be used as a solvent constituting the liquid phase. Specific examples of such inert hydrocarbons include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene and xylene; And halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane and tetrachloromethane, and mixtures thereof.

Also, bulk polymerization may be carried out using 4-methyl-1-pentene and the above-mentioned? -Olefin which induces the constituent unit (ii) itself as a solvent.

Further, homopolymerization of 4-methyl-1-pentene and copolymerization of 4-methyl-1-pentene with the &quot; -olefin that induces the constituent unit (ii) &quot; -Methyl-1-pentene /? - olefin copolymer (A).

When performing the polymerization, the component (a) is, per liter of the reaction volume, Group 4 of the periodic table in terms of metal atom of usually 10 to ^-8 to ^10-2 mol, preferably ^10-7 to ^10-3 is used in an amount that mol . The molar ratio [(b-1) / M] of the component (b-1) to the transition metal atom (M) in the component (a) is usually 0.01 to 5000, 2000. &Lt; / RTI &gt; The molar ratio [(b-2) / M] of the component (b-2) and the transition metal atom (M) in the component (a) is usually 1 to 10, preferably 1 to 5 As shown in FIG. The molar ratio [(b-2) / M] of the component (b-3) to the transition metal atom (M) in the component (a) is usually 10 to 5000, preferably 20 to 2000 And the like.

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

The polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by batch, semi-continuous or continuous. It is also possible to carry out polymerization by dividing into two or more stages having different reaction conditions.

Hydrogen may be added for the purpose of controlling the molecular weight or the polymerization activity of the resulting polymer at the time of polymerization, and the amount thereof is preferably 0.001 to 1 kg of the total amount of 4-methyl-1-pentene and the above-mentioned & To about 100 NL is suitable.

&Lt; 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 /? - olefin copolymer (A) For example, an olefin resin (B1) other than the copolymer (A), a polyamide resin, a polyester resin and a vinyl aromatic resin. In the present invention, the thermoplastic resin (B) is used for imparting good tackiness, moldability, tackiness, etc. to the resin composition of the present invention.

Specific examples of the olefin resin (B1) include a copolymer of ethylene and an? -Olefin having 3 to 20 carbon atoms, a copolymer of ethylene and an? -Olefin having 3 to 20 carbon atoms with a cyclic olefin, styrene, vinyl acetate (Meth) acrylic acid and (meth) acrylic acid ester, copolymers of propylene and? -Olefins having 4 to 20 carbon atoms, copolymers of propylene and an? -Olefin having 4 to 20 carbon atoms, A copolymer of an olefin and a cyclic olefin, and an ethylene-based copolymer containing various vinyl compounds as comonomers such as styrene, vinyl acetate, (meth) acrylic acid and (meth) acrylic acid ester. More specifically, there can be mentioned low density, medium density, high density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl- -Butene, cyclic olefin copolymer, chlorinated polyolefin, and olefin elastomer.

As an example of the olefinic elastomer, an elastomer containing an olefinic block copolymer may also be used. For example, a block copolymer of a polyolefin block, which forms a polymer with high crystallinity such as polypropylene, which is hardly added, and a monomer copolymer that exhibits amorphism, which is softened. Specific examples thereof include olefins ) · Ethylene · butylene · olefin block copolymer, polypropylene · polyolefin (amorphous) · polypropylene block copolymer, and the like. Specific examples include DYNARON (registered trademark) manufactured by JSR Corporation under the trade name of DYNARON (registered trademark), TAMMER (registered trademark), NOTIO (registered trademark) manufactured by Mitsui Chemicals, Inc., ENGAGE ^TM , VERSIFY ^TM, ExxonMobil Chemical whether or sikki manufactured include those commercially available as the trade name Vistamaxx ^TM.

Specific examples of the polyamide resin include aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, and nylon 612).

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

Specific examples of the vinyl aromatic resin include polystyrene, ABS resin, AS resin, and styrene elastomer (B2).

Examples of the styrene-based elastomer (B2) include block copolymers (SBS) of a polystyrene block to be a hard part (crystal part) and a dienic monomer block to be softened, a hydrogenated styrene-butadiene styrene block copolymer (HSBR) Styrene-ethylene-butene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), styrene-isobutylene-styrene copolymer SIBS), styrene / isobutylene copolymer (SIB), and the like. The styrene elastomer may be used singly or in combination of two or more.

Specific examples of the hydrogenated styrene / butadiene / styrene block copolymer include those commercially available under the trade name of DYNARON (registered trademark) manufactured by JSR Corporation.

The styrene-ethylene-propylene-styrene block copolymer is obtained by hydrogenating a styrene-isoprene-styrene block copolymer (SIS). As a specific example of the SIS, commercially available as JSR SIS (registered trademark) manufactured by JSR Kabushiki Kaisha under the trade name of Kuraray D (trade name) manufactured by Kabushiki Kaisha Co., Ltd. under the trade name of Heibra (registered trademark) or Shell K.K. And the like.

Specific examples of SEPS include commercially available products such as SEPTON (registered trademark) and KURATE (registered trademark) available from Shell Chemical Industries, Ltd., and the like.

Specific examples of the SEBS include those commercially available under the trade name of Tough Tech (registered trademark) available from Asahi Kasei Kabushiki Kaisha or as Kraton (registered trademark) available from Shell Chemical Co., Ltd.

Specific examples of SIB and SIBS include those commercially available under the trade name of Shibusa (registered trademark) of Kanebo Co., Ltd., and the like.

Further, as a special styrene elastomer, trade name: S.O.E, manufactured by Asahi Kasei Kabushiki Kaisha, and the like can be mentioned.

As the other thermoplastic resin (B), thermoplastic polyurethane; Vinyl chloride resin; Vinylidene chloride resin; Acrylic resin; Ethylene-vinyl acetate copolymer; Ethylene / methacrylic acid acrylate copolymer; Ionomers; Ethylene / vinyl alcohol copolymer; Polyvinyl alcohol; Fluorine resin polycarbonate; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide polyimide; Polyarylates; Polysulfone; Polyethersulfone, and the like.

In the present invention, among these thermoplastic resins (B), the olefin resin (B1) and the styrene elastomer (B2) are suitably used. When the adherend is an uneven surface, the styrene-based elastomer (B2) is particularly preferable because the adhesive strength of the obtained surface protective film is high. When the styrene elastomer (B2) is used as the thermoplastic resin (B), for example, it is more preferable that the thermoplastic resin (B) contains only the styrene elastomer (B2).

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

The resin composition according to the present invention contains such a thermoplastic resin (B) in addition to the copolymer (A). Here, in the present invention, when the total amount of the copolymer (A) and the thermoplastic resin (B) is 100 parts by weight, the upper limit of the content of the copolymer (A) in the composition 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 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, particularly preferably 60 parts by weight, the upper limit is 98 parts by weight, more preferably 95 parts by weight, Preferably 90 parts by weight.

&Lt; Other components >

The resin composition according to the present invention may contain only the copolymer (A) and the thermoplastic resin (B), but in addition to the copolymer (A) and the thermoplastic resin (B) And may further contain a suitable additive such as a tackifier.

Here, the resin composition of the present invention can be mainly used as a pressure-sensitive adhesive, but may further include a tackifier as an additive, if necessary, in order to adjust the adhesive force to the adherend.

Examples of the tackifier that can be used in the present invention include a dendritic substance which is generally manufactured and sold as a tackifier. Specific examples thereof include chroman resins such as chroman-indene resins; Phenol-based resins such as phenol-formaldehyde resin and xylene-formaldehyde resin; Terpene resins such as terpene-phenol resin, terpene resin (?,? -Pinene resin), aromatic-modified terpene resin and hydrogenated terpene resin; Petroleum hydrocarbon resins such as synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, hydrogenated hydrocarbon resins, and hydrocarbon-based tackifying resins; Rosin derivatives such as pentaerythritol ester of rosin, glycerin ester of rosin, hydrogenated rosin, hydrogenated rosin ester, special rosin ester, rosin-based tackifier and the like.

Among these components, a hydrogenated hydrocarbon resin, a hydrogenated aliphatic cyclic hydrocarbon resin, a hydrogenated aliphatic or alicyclic petroleum resin, a hydrogenated terpene resin, a hydrogenated terpene resin, and a hydrogenated hydrocarbon resin having a softening point of 70 ° C or higher, Hydrogenated resins such as synthetic polyterpene resin; Rosin derivatives such as pentaerythritol ester of rosin, glycerin ester of rosin, hydrogenated rosin, hydrogenated rosin ester, special rosin ester, rosin-based tackifier and the like.

By adding the tackifier, it becomes possible to adjust the adhesive force of the tackifier of the present invention to an adherend.

Here, in the case where the resin composition of the present invention contains the tackifier, the amount of the tackifier is preferably from 5 to 100 parts by weight, based on 100 parts by weight of the total of the copolymer (A) and the thermoplastic resin (B) 100 parts by weight.

The resin composition of the present invention may further contain, as additives other than the above-mentioned tackifier, additives such as weather resistance stabilizers, heat stabilizers, antistatic agents, slip inhibitors, anti-blocking agents, antifogging agents, lubricants, Additives such as pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbents, antioxidants, crystal nucleating agents, antiseptics, antimicrobial agents, flame retardants, fillers (inorganic fillers, organic fillers) and softening agents may be included depending on the purpose.

As the softening agent, conventionally known softening agents may be used. Specific examples thereof include petroleum-based materials such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt and petrolatum; Coal tar such as coal tar and coal tar pitch; Castor oils such as castor oil, linseed oil, rape seed oil, soybean oil and palm oil; Waxes such as tall oil, beeswax, carnauba wax and lanolin; Fatty acids or metal salts thereof such as ricinoleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, montanic acid, oleic acid and erucic acid; Synthetic resins such as petroleum resin, coumarone-indene resin and atactic polypropylene; Ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; Other microcrystalline waxes and liquid polybutadiene or modified products thereof or hydrogenated products thereof; Liquid thiokol, and the like.

Examples of the filler include powder fillers such as mica, carbon black, silica, calcium carbonate, talc, graphite, stainless steel and aluminum; And fibrous fillers such as glass fibers and metal fibers. Also included are hydrophilic layered clay minerals and / or hydrophilic inorganic compounds in certain shapes (other than layered).

Examples of the hydrophilic layered clay minerals include, for example, filo-silicate minerals in which a plurality of layers spread in two dimensions are laminated, for example, smectite. Smectites are montmorillonite minerals and include, for example, montmorillonite (montmorillonite), magnesian montmorillonite, ironmonolylonite, ironstone grenaceum montmorillonite, bederite, aluminian beellite, Alumina nontronite, sapphire (saponite), alminic anthracite, hectorite, saponite, stevensite, bentonite, and the like.

Examples of the hydrophilic layered clay mineral include vermiculite, halloysite, swelling mica, and graphite.

These hydrophilic layered clay minerals may be used singly or in combination of two or more. Such hydrophilic layered clay minerals can be used in general marketed products. For example, more specifically, as natural products, there may be mentioned, for example, Ginifia series (montmorillonite, manufactured by Kunimine), Bengel series (bentonite, (Sumonite, manufactured by Kunimi Kogyo Co., Ltd.), Lucentite SWN series (manufactured by Hectolite Co., Ltd.), and the like, (Manufactured by Chemical Co., Ltd.) and laponite (hectorite, manufactured by Lokwood Holdings). Generally, synthetic products are preferable from the viewpoint of obtaining small oil droplets since their maximum length is smaller than that of natural products.

Examples of the flame retardant include inorganic compounds such as antimony flame retardants, aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine flame retardant, and zirconium flame retardant, ammonium polyphosphate, ethylene bistris (2-cyanoethyl) phosphonium chloride, tris Phosphoric acid esters such as tris (tribromophenyl) phosphate, tris (tribromophenyl) phosphate and tris (3-hydroxypropyl) phosphine oxide and other phosphorus compounds, chlorinated paraffin, chlorinated polyolefin, perchlorocyclopentadecane and the like Chlorine-based flame retardant, bromine such as hexabromobenzene, ethylenebisdibromonorobornadicarboximide, ethylenebistetrabromophthalimide, tetrabromobisphenol A derivative, tetrabromobisphenol S, tetrabromodipentaerythritol and the like Based flame retardants and mixtures thereof.

The total amount of the additives other than the tackifier such as softening agent, filler and flame retardant is 0.001 to 50 parts by weight based on 100 parts by weight of the total of the copolymer (A) and the thermoplastic resin (B).

&Lt; Process for producing resin composition according to the present invention &

The resin composition according to the present invention is obtained by compounding the above-mentioned various additives such as the copolymer (A), the thermoplastic resin (B) and, if necessary, the "other components" , A known method such as a multi-stage polymerization method, a method of mixing or mixing with a Plastomill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, a kneader rudder, Kneading with a kneader, a Banbury mixer or the like, followed by assembling or grinding.

< Graft  Denaturation>

In the present invention, the 4-methyl-1-pentene -olefin copolymer (A) and the thermoplastic resin (B) may be used without modification as they are in the production of the resin composition of the present invention. A part or all of the 4-methyl-1-pentene -olefin copolymer (A) may be graft-modified or a part or all of the thermoplastic resin (B) may be graft-modified do. Examples of the polar compound and graft modification used for graft modification include conventionally known compounds and methods. For example, the compounds and methods disclosed in Japanese Patent Application Laid-Open No. 2008-127440 can be employed.

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

When the 4-methyl-1-pentene /? - olefin copolymer (A) or the thermoplastic resin (B) is graft modified, compatibility of each component in the composition or delamination between films It is in superiority in difficulty.

[ The laminate , Especially surface protective film]

The present invention also provides a laminate comprising the resin composition, that is, a laminate comprising at least one pressure-sensitive adhesive layer (L1) comprising the resin composition.

In the laminate of the present invention, when the resin composition is applied to various adherends having irregularities by using the resin composition in the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer follows the convexo-concave shape, thereby increasing the adhesive area, And the adhesive force due to the increase in the adhesive area can be stably maintained.

Here, as the laminate of the present invention, a laminate comprising a base layer (L2) and at least one pressure-sensitive adhesive layer (L1) comprising the above-mentioned resin composition of the present invention, specifically, the above- Layered film in which the pressure-sensitive adhesive layer (L1) comprising the composition is laminated on one side or both sides of the base layer (L2) which is a single layer or a multilayer structure. In other words, as a basic form of the laminate according to the present invention, a two-layer film comprising a base layer (L2) / a pressure-sensitive adhesive layer (L1) laminated in this order or a two-layer film comprising a pressure-sensitive adhesive layer (L1) / a base layer (L2) And a layer L1 laminated in this order.

Here, the material of the base layer (L2) constituting the laminate of the present invention is not particularly limited, but is preferably a thermoplastic resin such as a polyolefin resin. Specific examples thereof include a polypropylene resin (a homopolymer of propylene, (Random or block copolymers of propylene and a small amount of? -Olefin), polyethylene resins (low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene), known ethylene polymers (ethylene- (Ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer), known propylene copolymers (propylene- , Poly-4-methyl-1-pentene, and combinations thereof.

In the laminate of the present invention, for example, the surface layer L3 may be further provided on the surface of the base layer L2 opposite to the pressure-sensitive adhesive layer (L1) side. That is, the laminate of the present invention may have a structure including at least three layers laminated in the order of the surface layer (L3) / the base layer (L2) / the pressure-sensitive adhesive layer (L1). Here, the surface layer L3 may be provided in order to facilitate the unstacking of the laminate when, for example, the laminate is a roll. In this case, as the material of the base layer (L2) and the surface layer (L3), resins of the same kind may be used, or resins of different kinds may be used.

The surface of the base layer L2 may be treated by a surface treatment method such as a corona discharge treatment, a plasma treatment, a frame treatment, an electron beam irradiation treatment and an ultraviolet irradiation treatment. The base layer L2 may be a colorless transparent layer, Or printed layer.

As the base layer (L2), those stretched in the uniaxial or biaxial direction may be used.

As a method for producing the laminate of the present invention, for example, a known method of forming a multilayer film can be cited. As a preferable method, a pressure-sensitive adhesive layer containing the resin composition of the present invention (L1) and the base layer (L2), or a method obtained by extrusion-coating a pressure-sensitive adhesive layer (L1) containing the resin composition of the present invention on a preformed base layer (L2) . Further, a method of dissolving the resin composition of the present invention in a solvent and coating the composition on the base layer (L2), and forming a pressure-sensitive adhesive layer (L1) on the base layer (L2) Of these, film formation by a co-extrusion molding method is preferable.

The multilayered film of the present invention may be stretched in the uniaxial or biaxial direction. As a preferred method of uniaxial stretching, a commonly used roll stretching method can be exemplified. As a biaxial stretching method, a simultaneous biaxial stretching method such as a longitudinal stretching method in which biaxial stretching is performed after uniaxial stretching and a tubular stretching method can be exemplified.

By using the above-described production method, the laminate of the present invention can be obtained as a multilayer film, and a suitable application of the multilayer film is a surface protective film. 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 5000 μm, and more preferably about 10 to 1000 μm. The thickness of the surface layer (pressure-sensitive adhesive layer) is not particularly limited and may be selected depending on the kind of the adherend and the required physical properties (for example, the adhesive strength), but is usually 1 to 500 μm, preferably 3 to 300 μm. The laminate may have at least two layers of a pressure-sensitive adhesive layer and a base layer. For example, an intermediate layer L4 may be provided between the pressure-sensitive adhesive layer (L1) and the base layer (L2). As the material used for the intermediate layer L4, conventionally known materials can be used.

In the case of using a multilayer film using the resin composition of the present invention as a surface protective film, in order to prevent blocking (sticking) between the multilayer films, a peeling or peeling film may be sandwiched between the multilayer films, The release agent may be applied to the surface.

In the present invention, an additive such as a releasing agent may be contained in the base layer (L2) in order to impart a surface-like function to the surface, if necessary.

&Lt; Method for producing surface protective film &

A method of laminating the base layer (L2), the pressure-sensitive adhesive layer (L1) and the surface layer (L3) to be provided as required is not particularly limited, but a surface layer (L3) film obtained in advance by T- A method in which the base layer L2 and the pressure-sensitive adhesive layer L1 are laminated by a known lamination method such as extrusion lamination and extrusion coating or a method in which the base layer L2 and the pressure-sensitive adhesive layer L1 are independently formed into films, From the viewpoint of productivity, a method of providing each of the components of the surface layer L3, the base layer L2 and the pressure-sensitive adhesive layer L1 to a multilayer extruder to form a film Extrusion molding is preferred. This is also suitable when a surface protective film comprising a laminate having the intermediate layer (L4) is produced in addition to the base layer (L2), the pressure-sensitive adhesive layer (L1) and the surface layer (L3) Taking these into consideration, as a suitable form in the present invention, the laminate constituting the surface protective film is a multilayer film obtained by, for example, a T-die film forming method.

By using the base layer (L2), the pressure-sensitive adhesive layer (L1) and the surface layer (L3) as required, the polyolefin multi-layer film having excellent releasability can be suitably used as a surface protective film or release film have.

<Applications>

Examples of applications of the laminate comprising the resin composition and the resin composition of the present invention include a pressure-sensitive adhesive sheet and a surface protective film. When the resin composition of the present invention is used as a pressure-sensitive adhesive layer of a multilayered film, the multilayered film may be a metal plate such as an aluminum plate, a steel plate, or a stainless steel plate and a coated plate thereof, a processing member such as a glass plate or a synthetic resin plate, It can be suitably used as a surface protective film for protecting household appliances, automobile parts, and electronic parts using a member. Therefore, the resin composition of the present invention can be suitably used in various applications such as, for example, a pressure sensitive adhesive such as an adhesive film or a protective film adhesive layer, a process protective film for semiconductor, a lens protective film, a back grind tape for semiconductor wafer, Such as films or tapes in the field of electronics, window glass protective films, baking coating films, and the like. In particular, since the resin composition of the present invention has irregularity, it is suitably used for a prism sheet or a reflective sheet having many concavo-convex structures on its surface, a sheet for protecting a wrinkled surface, and the like. Here, an example of application to a protective tape for a printed board is a protective film for a plating mask used for plating a flexible printed substrate.

The surface protective film of the present invention can be attached to an adherend which is an object of protection. The component is adjusted according to the physical properties of the adherend surface of the adherend, such as the unevenness (surface roughness) of the surface. Generally, when the surface roughness of the adherend surface of the adherend is rough, it is made of a material of a strong adhesion type.

It is preferable to use the styrene-based elastomer (B2) as the thermoplastic resin (B) for the adherend surface having large unevenness on the surface. In this case, the height of the surface irregularities of the adhered surface is preferably in the range of 0.1 to 300 탆, more preferably 0.1 to 100 탆, still more preferably 1 to 50 탆, particularly preferably 1 to 30 탆.

In other words, the present invention also provides a method for protecting an adherend, which is an object to be protected, using the protective film of the present invention. In this method, the surface to be protected By attaching the surface protective film of the present invention. Particularly when a styrene-based elastomer (B2) is used as the thermoplastic resin (B), a suitable example of an adherend to be protected is a surface unevenness height of 0.1 to 300 탆, more preferably 0.1 to 100 탆, And particularly preferably 1 to 30 占 퐉. As a more specific example, a prism sheet can be exemplified.

Example

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited at all by these Examples.

[Measurement conditions, etc.]

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

〔Furtherance〕

The content of 4-methyl-1-pentene and alpha -olefin in the polymer was measured by ¹³ C-NMR according to the following apparatus and conditions. A sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120 占 폚, and an observation nucleus were measured using an ECP500 type nuclear magnetic resonance apparatus manufactured by Nihon Denshi Co., Ltd., and a mixed solvent of orthodichlorobenzene / ¹³ C (125 MHz), the sequence was single pulse proton decoupling, the pulse width was 4.7 占 퐏 ec (45 占 pulse), the repetition time was 5.5 seconds, the cumulative number of times was 10,000 or more, and 27.50 ppm was measured as a reference value of chemical shift.

〔density〕

The density of the polymer was calculated from the weight of each sample measured in water and air using an ALPHA MIRAGE electronic density meter MD-300S according to ASTM D 1505 (Submerged Replacement Method).

[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 from the polymerization was sealed in an aluminum pan and heated from room temperature to 200 占 폚 at 10 占 폚 / min. The sample was kept at 200 캜 for 5 minutes to completely melt, and subsequently cooled to -50 캜 at 10 캜 / minute. After standing at -50 占 폚 for 5 minutes, the sample was heated again to 200 占 폚 at 10 占 폚 / min. The peak temperature in this second (second) heating was adopted as the melting point (Tm).

[Intrinsic viscosity]

The intrinsic viscosity [?] (DL / g) was measured at 135 占 폚 using a decalin solvent.

That is, about 20 mg of a sample was dissolved in 15 ml of decalin and the specific viscosity (? _Sp ) was measured in an oil bath at 135 占 폚. 5 ml of decalin solvent was added to the decalin solution to dilute it, and then the specific viscosity (? _Sp ) was measured in the same manner. This dilution operation was also repeated twice, and the value of? _Sp / C when the concentration (C) was extrapolated to 0 as shown in the following formula was defined as an intrinsic viscosity [?] (Unit: dL / g).

[?] = lim (? _sp / C) (C? 0)

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

The molecular weight of the copolymer (A) was determined by using a liquid chromatograph: A watercolor ALC / GPC 150-C plus type integrated with a refractometer of Waters manufactured by Waters, two columns of GMH6-HT manufactured by Tosoh Corp., × 2 were connected in series, and o-dichlorobenzene was used as a mobile phase medium at a flow rate of 1.0 ml / min and at 140 ° C.

The obtained chromatogram was analyzed by a known method using a calibration curve using a standard polystyrene sample to calculate Mw / Mn value and Mz / Mw value. The measurement time per sample was 60 minutes.

[Production method of press sheet for various measurement]

Each of the pressure-sensitive adhesives of the examples and comparative examples (namely, the pressure-sensitive adhesive resin composition used for the pressure-sensitive adhesive layer (L1)) was formed into a sheet at a pressure of 10 MPa by using a hydraulic hot press machine manufactured by Shinto Kinko Co., Ltd., In the case of a sheet having a thickness of 1 to 3 mm (spacer shape: 80 × 80 × 0.5 to 3 mm on a plate having a size of 240 × 240 × 2 mm, taking four), the heat is left for about 5 to 7 minutes, Thereafter, the sample was compressed at 10 MPa using a separate hydraulic thermo-press machine manufactured by Shinto Kinko Kogyo Co., Ltd. set at 20 占 폚 and cooled for 5 minutes to prepare a sample for measurement. A brass plate of 5 mm thickness was used as a heat plate. Samples prepared by the above method were supplied to various physical property evaluation samples.

[Shore hardness measurement]

In the measurement of the Shore hardness (in accordance with JIS K6253), a press sheet having a thickness of 3 mm was used as a sample for measurement, and scales were read immediately after the start of the pressure-contact with the Shore A durometer or the Shore D durometer and after 15 seconds from the start of the pressure-contact.

Further, a change (? HS) of Shore hardness value defined by the following formula was obtained.

ΔHS = (Shore hardness value immediately after the start of the pressure-contact start-Shore hardness value after 15 seconds from the start of the pressure-contact)

Here, the Shore hardness was measured by using a Shore A hardness meter in principle, but a Shore D hardness meter was used instead of the measurement sample for which it was difficult to measure the Shore A hardness.

Here, when the same kind of hardness meter is used, the greater the? HS, the higher the irregularity followability.

[Laminate Formation]

A resin pellet was fed from a resin feed hopper which is connected to the surface layer L3, the base layer L2, and the pressure-sensitive adhesive layer (L1) using a three-layer three-layer T-die molding machine having a die width of 300 mm and having a 30 mm? Single- After the resin pellets were melted through a cylinder in the single screw extruder, extrusion molding was carried out from the T-die to obtain a laminate to be a pressure-sensitive adhesive sheet. At this time, polypropylene F107 manufactured by Prime Polymer Co., Ltd. was used for the surface layer L3 and the base layer L2, and the pressure-sensitive adhesive resin composition shown in each of Examples and Comparative Examples was used for the pressure-sensitive adhesive layer (L1).

The thicknesses of the surface layer (L3), the base layer (L2), the thickness of the pressure-sensitive adhesive layer (L1), and the total thickness of the examples and comparative examples are shown in Tables 2 to 5, respectively.

[Adhesive strength evaluation (acrylic plate)]

The adhesive strength of the laminate obtained in each Example and Comparative Example was measured in accordance with JIS Z0237-2000. Here, a sheet of polyethylene terephthalate of 100 mu m was attached to the surface of each laminate as the adhesive sheet sample, which was not an object of measurement of the adhesive force, to form an adhesive film. On the other hand, a black acrylic plate (trade name: Acrylite REX, shape 50 × 100 mm square plate) of 50 mm width × 100 mm length × 2 mm thickness was used as a test plate. The test plate and the pressure-sensitive adhesive film were allowed to stand for 1 hour in an environment of a temperature of 23 DEG C and a relative humidity of 50%, and then the pressure-sensitive adhesive film was placed on the test plate. Thereafter, Respectively. After adhering, the sample was allowed to stand for 1 day under a constant temperature of 23 ° C. and a relative humidity of 50%. Thereafter, the sample was transferred from a black acrylic plate at a temperature of 23 ° C. and a relative humidity of 50% in a direction of 180 ° at a speed of 300 mm / The adhesive strength at the time of peeling was measured and defined as the adhesive strength at 23 ° C.

The adhesive strengths in the respective Examples and Comparative Examples are shown in the column of "Adhesive Strength (Acrylic Sheet) @ 23 ° C" in Tables 2 to 5.

[Tensile strength ratio]

A test plate with an adhesive film (that is, an adhesive film obtained from the laminate obtained in each of the examples and the comparative examples) was attached to the test plate at a temperature of 23 ° C and a relative humidity of 50% in accordance with the method and conditions described in the above "Adhesion Force Evaluation (Acrylic Sheet) Instead of being allowed to stand for one day under a constant environment of a temperature of 23 ° C and a relative humidity of 50% in a 180 ° direction at a speed of 300 mm / min. The adhesive strength after peel adhesion was measured. The adhesion at this time was defined as the adhesion at 60 ° C. The adhesive strength at 60 ° C in each of the Examples and Comparative Examples is shown in the column of "Adhesive Strength (Acrylic Sheet) @ 60 ° C" in Tables 2 to 5.

The results are shown in Tables 2 to 5 for the adhesive strength at 23 占 폚 and the "Adhesive Strength (acrylic plate) @ 60 占 폚" in the column of "Adhesive Strength (Acrylic Sheet) @ 23 占 폚" Based on the adhesive strength at 60 占 폚, the adhesive tensile strength was calculated. Here, the &quot; adhesion augmentation rate &quot;

{(Adhesive strength at 60 DEG C) - (Adhesive strength at 23 DEG C}} / (Adhesive strength at 23 DEG C) x 100

.

The adhesion anchorage ratios in each of the examples and comparative examples are shown in the column of &quot; adhesion augmentation rate &quot; in Tables 2 to 5.

[Evaluation of Adhesion (SUS Plate)]

The adhesive strength of the laminate obtained in each of the examples and the comparative examples to the SUS steel plate was measured as follows according to WO2011 / 002083. Here, the laminate obtained in each of the Examples and Comparative Examples was used as a protective film.

A protective film was attached to a 50 mm wide stainless steel plate (SUS304, finish 180) and allowed to stand for one day under a constant temperature of 23 DEG C and a relative humidity of 50% for one day. Then, in an environment of a temperature of 23 DEG C and a relative humidity of 50% Deg.], And the adhesive strength was measured by peeling at a speed of 300 mm / min. That is, in the same manner as in the above "adhesion evaluation (acrylic plate)" except that the stainless steel plate is used instead of the black acrylic plate and the "adhesive film" is replaced with a "protective film" .

Adhesive strengths in the respective Examples and Comparative Examples are shown in the column of "Adhesive Strength (SUS Plate)" in Tables 2 to 5.

[Adhesion Stability (Stainless Steel Plate)]

The adhesion stability of the laminate obtained in each of the Examples and Comparative Examples to the SUS steel plate was evaluated as follows. Here, the laminate obtained in each of the Examples and Comparative Examples was used as a protective film.

A protective film was attached to a stainless steel plate (SUS304, finishing No. 180) and stored for 1 day under a constant environment of a temperature of 23 DEG C and a relative humidity of 50%. The number of peeling of the protective film after storage was checked and evaluated as follows.

X: all peeled off or not adhered to the substrate

DELTA: Partial film peeled off

○: All of them remain attached.

The evaluation on each of the examples and comparative examples is shown in the column of &quot; Adhesion Stability (SUS Coated Steel) &quot; in Tables 2 to 5.

[Evaluation of adhesion (prism plate)]

The adhesion of the laminate obtained in each of the Examples and Comparative Examples to the prism plate was measured as follows.

A prism sheet including an acrylic resin having a thickness of 110 mu m, a prism pitch of 50 mu m, and a height of 35 mu m was used as a prism plate, and the laminate obtained in each of the Examples and Comparative Examples was used as a protective film. Here, the width of the protective film was 50 mm. The protective film was pressed on the prism plate at a rate of 20 mm / min using a 2-kg rubber roller and left for 30 minutes under a constant temperature of 23 ° C and a relative humidity of 50% for 30 minutes. And the adhesive strength was measured.

Adhesive strengths in the respective Examples and Comparative Examples are shown in the column of "Adhesion Strength (Prism Plate)" in Tables 2 to 5.

[Adhesion Stability (Prism Plate)]

The adhesion stability of the laminate obtained in each of the Examples and Comparative Examples to the prism plate was measured as follows.

The laminate obtained in each of the Examples and Comparative Examples was used as a protective film. The stainless steel plate was evaluated in the same manner as the above "Adhesion Stability (SUS Plate)", except that the protective film was attached to the same prism sheet as used in the "Adhesion Force Evaluation (Prism Plate)".

The evaluation on each of the examples and the comparative examples is shown in the column of &quot; adhesion stability (prism plate) &quot; in Tables 2 to 5.

[Synthesis Example 1]

750 ml of 4-methyl-1-pentene at 23 占 폚 was charged into an autoclave made of SUS equipped with a stirrer with a capacity of 1.5 liters sufficiently purged with nitrogen. To the autoclave, 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutyl aluminum (TIBAL) was charged and the agitator was turned.

Then, the autoclave was heated to a temperature of 60 deg. C, which was followed by pressurization with propylene so that the total pressure became 0.13 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane previously prepared in terms of Al, 1 mol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di- 0.34 ml of a toluene solution containing 0.01 mmol of zirconium dichloride was injected into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the autoclave internal temperature became 60 占 폚. After 60 minutes from the start of the polymerization, 5 ml of methanol was introduced into the autoclave with nitrogen, polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. Acetone was injected into the reaction solution with stirring.

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

[Synthesis Example 2]

450 ml of normal hexane (dry nitrogen atmosphere, dried over active alumina) and 4-methyl-1-pentene were charged at 23 占 폚 in an autoclave made of SUS equipped with a stirrer with a capacity of 1.5 liters sufficiently purged with nitrogen. To the autoclave, 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutyl aluminum (TIBAL) was charged and the agitator was turned.

Subsequently, the autoclave was heated to a temperature of 60 deg. C, which was followed by pressurization with propylene so that the total pressure became 0.19 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane previously prepared in terms of Al, 1 mol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di- 0.34 ml of a toluene solution containing 0.01 mmol of zirconium dichloride was injected into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the autoclave internal temperature became 60 占 폚. After 60 minutes from the start of the polymerization, 5 ml of methanol was introduced into the autoclave with nitrogen, polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. Acetone was injected into the reaction solution with stirring.

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

[Synthesis Example 3]

50 ml of 4-methyl-1-pentene at 23 占 폚 was charged into an autoclave made of SUS equipped with a stirrer with a capacity of 1.5 liters sufficiently purged with nitrogen. To the autoclave 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutyl aluminum (TIBAl) was charged and the agitator was turned. Subsequently, the autoclave was heated up to 30 deg. C at which it was sparged, and pressurized with propylene so that the total pressure became 0.74 MPaG, and 12Nml of hydrogen was added. Subsequently, 1 mmol of methyl aluminoxane in terms of Al, which had been prepared in advance, and 4 g of diphenylmethylene (1-methyl-3-t-butyl-cyclopentadienyl) (2,7-di- Nyl) zirconium dichloride in an amount of 0.005 mmol was injected into the autoclave with nitrogen to initiate polymerization. Thereafter, the temperature of the autoclave was adjusted to 60 DEG C for 60 minutes. After 60 minutes from the start of the polymerization, 5 ml of methanol was introduced into the autoclave with nitrogen, polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. Acetone was injected into the reaction solution with stirring. The rubbery polymer containing the obtained solvent was dried at 130 캜 under reduced pressure for 12 hours. The obtained polymer was 78.1 g, the content of 4-methyl-1-pentene in the polymer was 8.9 mol%, and the content of propylene was 91.1 mol%.

[Synthesis Example 4]

750 ml of 4-methyl-1-pentene at 23 占 폚 was charged into an autoclave made of SUS equipped with a stirrer with a capacity of 1.5 liters sufficiently purged with nitrogen. To the autoclave 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutyl aluminum (TIBAl) was charged and the agitator was turned. Subsequently, the autoclave was heated up to 30 deg. C at which it was sparged, and pressurized with propylene so that the total pressure became 0.74 MPaG, and 12Nml of hydrogen was added. Subsequently, 1 mmol of methyl aluminoxane in terms of Al, which had been prepared in advance, and 4 g of diphenylmethylene (1-methyl-3-t-butyl-cyclopentadienyl) (2,7-di- Nyl) zirconium dichloride in an amount of 0.005 mmol was injected into the autoclave with nitrogen to initiate polymerization. Thereafter, the temperature of the autoclave was adjusted to 60 DEG C for 60 minutes. After 60 minutes from the start of the polymerization, 5 ml of methanol was introduced into the autoclave with nitrogen, polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. Acetone was injected into the reaction solution with stirring. The rubbery polymer containing the obtained solvent was dried at 130 캜 under reduced pressure for 12 hours. The obtained polymer was 56.3 g, the content of 4-methyl-1-pentene in the polymer was 24.7 mol%, and the content of propylene was 75.3 mol%.

[Synthesis Example 5]

750 ml of 4-methyl-1-pentene at 23 占 폚 was charged into an autoclave made of SUS equipped with a stirrer with a capacity of 1.5 liters sufficiently purged with nitrogen. To the autoclave, 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutyl aluminum (TIBAL) was charged and stirring was started.

Subsequently, the autoclave was heated to a temperature of 60 deg. C at which it was cooled, and was pressurized with propylene so that the total pressure became 0.17 MPa (gauge pressure). Subsequently, 1 mmol of methylaluminoxane in terms of Al, which had been prepared in advance, and 1 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di- ) Zirconium dichloride in toluene was introduced into an autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the autoclave internal temperature became 60 占 폚. After 60 minutes from the start of the polymerization, 5 ml of methanol was introduced into the autoclave with nitrogen, polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. Acetone was injected into the reaction solution with stirring.

The powder-like polymer containing the obtained solvent was dried at 130 캜 under reduced pressure for 12 hours. 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 content of propylene 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 the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 20 parts by weight of Dynaron (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer (HSBR)) 80 manufactured by JSR Kabushiki Kaisha And 0.2 part by weight of n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propinate as a heat stabilizer. The obtained mixture was molded as a pressure-sensitive adhesive resin composition with a three-kind three-layer film molding machine 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 employed in obtaining the laminate are as described in the section &quot; laminate molding &quot;. Table 2 shows various physical properties.

[Example 2]

30 parts by weight of the 4-methyl-1-pentene 占-olefin copolymer obtained in Synthesis Example 1 and 30 parts by weight of Dynaron 占 1320P (hydrogenated styrene-butadiene styrene copolymer (HSBR)) 70 manufactured by JSR Kabushiki Kaisha And 0.2 part by weight of n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propinate as a heat stabilizer. The obtained mixture was used as a pressure-sensitive adhesive resin composition, and then molded with a three-kind three-layer film molding machine to obtain a laminate (surface protective film), and the physical properties of the laminate were measured. Here, the specific molding conditions employed in obtaining the laminate are as described in the section &quot; laminate molding &quot;. Table 2 shows various physical properties.

[Example 3]

30 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 30 parts by weight of Dynaron (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer Except that 70 parts by weight of 4-methyl-1-pentene 占-olefin copolymer obtained in Synthesis Example 1 and 50 parts by weight of Dynaron 占 1320P (produced by JSR Kabushiki Kaisha, -Butadiene-styrene copolymer (HSBR)) was changed to 50 parts by weight, a sample of a pressure-sensitive adhesive resin composition sample was produced and molded, and physical properties of the resultant laminate were measured. Table 2 shows various physical properties.

[Comparative Example 1]

20 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 20 parts by weight of DYNARON (registered trademark) 1320P (produced by JSR Kabushiki Kaisha) (hydrogenated styrene · butadiene · styrene copolymer Except that 100 weight parts of Dynaron (registered trademark) 1320P (hydrogenated styrene · butadiene · styrene copolymer (HSBR)) manufactured by JSR Corporation was used instead of 80 weight parts of ethylene / To prepare a pressure-sensitive adhesive resin composition sample and molding, and the physical properties of the resulting laminate were measured. Table 3 shows various physical properties.

[Comparative Example 2]

30 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 30 parts by weight of Dynaron (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer Except that 100 weight parts of Dynaron (registered trademark) 1320P (hydrogenated styrene · butadiene · styrene copolymer (HSBR)) manufactured by JSR Kabushiki Kaisha was used instead of 70 weight parts of To prepare a pressure-sensitive adhesive resin composition sample and molding, and the physical properties of the resulting laminate were measured. Table 3 shows various physical properties.

[Comparative Example 3]

30 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 30 parts by weight of Dynaron (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer Except that 70 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer (HSBR)) was used in place of 100 parts by weight of the 4-methyl- A sample was produced and molded, and the physical properties of the resulting laminate were measured. Table 3 shows various physical properties.

[Comparative Example 4]

30 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 30 parts by weight of Dynaron (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer Except that 70 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 2 was used instead of 70 parts by weight of the pressure-sensitive adhesive resin composition A sample was produced and molded, and the physical properties of the resulting laminate were measured. Table 3 shows various physical properties.

[Example 4]

20 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 20 parts by weight of DYNARON (registered trademark) 1320P (produced by JSR Kabushiki Kaisha) (hydrogenated styrene · butadiene · styrene copolymer 5 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 2 and 15 parts by weight of Dynaron (registered trademark) 1320P (produced by JSR Kabushiki Kaisha) Butadiene-styrene copolymer (HSBR)) was used in place of the ethylene / α-olefin copolymer (A) to prepare a pressure-sensitive adhesive resin composition sample and molding, and the properties of the resulting laminate were measured. Table 2 shows various physical properties.

[Example 5]

Except that 20 parts by weight of the 4-methyl-1-pentene 占-olefin copolymer obtained in Synthesis Example 1 was changed to 20 parts by weight of the 4-methyl-1-pentene 占-olefin copolymer obtained in Synthesis Example 2 The same operation as in Example 1 was carried out to prepare and form a pressure-sensitive adhesive resin composition sample, and the physical properties of the resulting laminate were measured. Table 2 shows various physical properties.

[Example 6]

30 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 30 parts by weight of Dynaron (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer 30 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 30 parts by weight of Shibusa (registered trademark) 062M (styrene / Was used in place of 70 parts by weight of an isobutylene-styrene copolymer (SIBS), to obtain a pressure-sensitive adhesive resin composition sample and molding, and the properties of the resulting laminate were measured. Table 2 shows various physical properties.

[Example 7]

80 parts by weight of DYNARON (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer (HSBR)) manufactured by JSR Corporation were mixed with 80 parts by weight of EVOLU (registered trademark) SP0540 (ethylene-octene copolymer LLDPE)) was changed to 80 parts by weight, a sample of a pressure-sensitive adhesive resin composition sample was produced and molded, and the physical properties of the resulting laminate were measured. Table 4 shows various physical properties.

[Example 8]

Except that 80 parts by weight of DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene styrene copolymer (HSBR)) manufactured by JSR Corporation was used as a thermoplastic elastomer (trade name: TFMER (registered trademark) PN-2060 manufactured by Mitsui Chemicals, (TPO)) was changed to 80 parts by weight, a sample of a pressure-sensitive adhesive resin composition sample was produced and molded, and the physical properties of the resulting laminate were measured. Table 4 shows various physical properties.

[Example 9]

80 parts by weight of DYNARON (registered trademark) 1320P (hydrogenated styrene-butadiene styrene copolymer (HSBR)) manufactured by JSR Corporation were mixed with 80 parts by weight of Prime Polypropylene (registered trademark) MF257 (PP) manufactured by Prime Polymer Co., The procedure of Example 1 was otherwise repeated to produce and form a pressure-sensitive adhesive resin composition sample, and the properties of the resulting laminate were measured. Table 4 shows various physical properties.

[Example 10]

Except that 20 parts by weight of the 4-methyl-1-pentene 占-olefin copolymer obtained in Synthesis Example 2 was used instead of 20 parts by weight of the 4-methyl-1-pentene 占-olefin copolymer obtained in Synthesis Example 1, The same operation as in Example 8 was carried out to produce and form a pressure-sensitive adhesive resin composition sample, and the properties of the resulting laminate were measured. Table 4 shows various physical properties.

[Comparative Example 5]

20 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 20 parts by weight of DYNARON (registered trademark) 1320P (produced by JSR Kabushiki Kaisha) (hydrogenated styrene · butadiene · styrene copolymer (HSBR)), 80 parts by weight of Dynaron (registered trademark) 1320P (a hydrogenated styrene-butadiene styrene copolymer (HSBR)) manufactured by JSR Corporation, and 80 parts by weight of a tapermer available from Mitsui Chemicals, (Registered trademark) PN-2060 (20 parts by weight) were used in place of the acrylic pressure-sensitive adhesive, to prepare a pressure-sensitive adhesive resin composition sample and molding, and the physical properties of the resulting laminate were measured. Table 5 shows various physical properties.

[Comparative Example 6]

20 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 20 parts by weight of DYNARON (registered trademark) 1320P (produced by JSR Kabushiki Kaisha) (hydrogenated styrene · butadiene · styrene copolymer Except that 80 parts by weight of Epoly (registered trademark) SP0540 manufactured by Prime Polymer Co., Ltd. and 20 parts by weight of TFMER (registered trademark) PN-2060 manufactured by Mitsui Chemicals, Inc. were used instead of 80 parts by weight of HSBR Was subjected to the same operation as in Example 1 to produce and form a pressure-sensitive adhesive resin composition sample, and the properties of the resulting laminate were measured. Table 5 shows various physical properties.

[Comparative Example 7]

20 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 20 parts by weight of DYNARON (registered trademark) 1320P (produced by JSR Kabushiki Kaisha) (hydrogenated styrene · butadiene · styrene copolymer Except that 80 parts by weight of TMPER (registered trademark) PN-2060 (manufactured by Mitsui Chemicals, Inc.) was used in place of 80 parts by weight of HSBR (manufactured by Mitsui Chemicals, Inc.) to prepare a pressure-sensitive adhesive resin composition sample And molding, and the physical properties of the resultant laminate were measured. Table 5 shows various physical properties.

[Comparative Example 8]

20 parts by weight of the 4-methyl-1-pentene /? - olefin copolymer obtained in Synthesis Example 1 and 20 parts by weight of DYNARON (registered trademark) 1320P (produced by JSR Kabushiki Kaisha) (hydrogenated styrene · butadiene · styrene copolymer Except that 80 parts by weight of Tafmer (registered trademark) PN-2060 manufactured by Mitsui Chemicals, Inc. and 80 parts by weight of Dynaron (registered trademark) 1320P (produced by JSR Kabushiki Kaisha) (hydrogenated styrene / butadiene Styrene copolymer (HSBR)) was used in place of 20 parts by weight of the polypropylene resin (A) to prepare a pressure-sensitive adhesive resin composition sample and molding, and the physical properties of the resultant laminate were measured. Table 5 shows various physical properties.

Claims (6)

2 to 50 parts by weight of a 4-methyl-1-pentene -olefin copolymer (A) satisfying the following requirements (a), (b), (c)
98 to 50 parts by weight of a thermoplastic resin (B) other than the 4-methyl-1-pentene /? - olefin copolymer (A)
At least one pressure-sensitive adhesive layer comprising a resin composition containing
The substrate layer
Wherein the surface protective film comprises a laminated body having a laminated structure.
(Wherein the sum of the 4-methyl-1-pentene /? - olefin copolymer (A) and the thermoplastic resin (B) is 100 parts by weight)
(ii) a constituent unit derived from (a) 65 to 90 mol% of a constituent unit derived from 4-methyl-1-pentene and an α-olefin (excluding 4-methyl- 35 to 10 mol%;
(b) the intrinsic viscosity [?] measured in decalin at 135 占 폚 in the range of 0.1 to 5.0 dL / g;
(c) the ratio (molecular weight distribution: Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5;
(d) the density is in the range of 870 to 830 kg / m ³ . The method according to claim 1,
Wherein the ratio of the constituent unit (i) is 80 to 90 mol% and the proportion of the constituent unit (ii) is 20 to 10 mol% in the above requirement (a). 3. The method according to claim 1 or 2,
Wherein the thermoplastic resin (B) is a styrene-based elastomer (B2). 4. The method according to any one of claims 1 to 3,
Wherein the above-mentioned laminate is a multilayer film obtained by a T-die film forming method. A method for protecting a surface having a surface irregularity height of 0.1 to 300 占 퐉 by using the surface protective film according to claim 3. A method for protecting a prism sheet using the surface protective film according to claim 3.