WO2015012274A1 - Surface protective film - Google Patents

Abstract

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

Description

Surface protection film

This invention relates to the surface protection film which consists of a laminated body which has an adhesive layer containing a specific resin composition.

Surface protection film in which an adhesive layer and a base material layer are laminated to protect metal plates such as aluminum plates, steel plates, stainless steel plates, and their coated plates, glass, or synthetic resin plates and products and parts made of these members Is used. This surface protection film is peeled off at a predetermined time after molding or after molding.

This surface protective film can be easily adhered by adhering to the adherend, and is not easily peeled off during transportation of the adherend, and can be easily peeled off when peeled off during processing or after processing. Is required. Therefore, the protective film has an appropriate adhesion to the protected surface of the adherend, an appropriate flexibility so that the film itself does not damage the protected surface, and an elongation characteristic depending on the processing and molding of the adherend. Various characteristics such as appropriate mechanical characteristics and heat resistance are required. Further, depending on the application, it is necessary to have a good appearance, transparency and color tone, and it is required that there are no film defects such as gel and fish eye. Furthermore, since this type of surface film is consumed in large quantities and promptly discarded, it is required that the surface film can be manufactured at low cost.

Conventionally, as this type of adhesive film, a base film mainly composed of a polymer such as low density polyethylene or polypropylene is coated with an acrylic or rubber adhesive on one side, and polyolefin and styrene elastomers. Examples of the pressure-sensitive adhesive pellets include those formed by extrusion molding with a base material layer.

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

In addition, for electrical and electronic materials and optical products, there are many members that require characteristics such as polarizing plates, retardation plates, light guide plates, reflectors, and prism plates. There is a need for a protective film that retains force. Since such an adherend having an uneven surface has a small contact area with the adhesive layer, the adhesive layer is required to have high adhesive strength. However, there are concerns about the limitation of molding methods such as coating, adhesive residue on the adherend, and the like due to the high adhesive strength.

Looking at this from a more specific aspect, for electrical and electronic materials and optical products, the surface is uneven, such as for example polarizing plates, retardation plates, light guide plates, reflectors, prism sheets and diffusion films. There is something. Prior to use, the uneven surface is protected with a protective film so as not to damage the unevenness, and a surface protective film that maintains an appropriate adhesive force for these members is also desired. . In such a surface protective film, there is a problem of so-called adhesion progress due to external factors such as time and temperature after being attached to the adherend surface. Adhesion progress is caused by an increase in the contact area between the adherend and the pressure-sensitive adhesive layer, particularly when the surface has an uneven shape. Among them, adherends with relatively small unevenness, such as diffusion films and reflective films. In this case, since the increase in the contact area is remarkable, adhesion progress is particularly likely to occur.
As a result, the peeling operation from the adherend surface is difficult, or an adhesive residue in which the adhesive portion partially remains on the adherend may occur.

Patent Documents 2 and 3 disclose a surface protective film comprising an adhesive layer containing a styrene elastomer which is an isobutylene block copolymer and a tackifying resin. However, in the method of the publication, when bonded to a highly uneven adherend, the adhesive strength is insufficient, stickiness and blocking are poor, and productivity due to defective extrusion is difficult.

Further, Patent Documents 4 and 5 disclose a resin composition and a surface protective film that use a styrene-based elastomer for the adhesive layer and are less prone to adhesion progress. However, in a smooth substrate such as a PET substrate or an acrylic substrate, Since the adhesive strength is limited and the adhesive strength is low, it has been difficult to develop the substrate on a concavo-convex shape.

In addition, Patent Document 6 discloses a surface protective film in which adhesion progress is suppressed by a composition of a strongly-adhesive styrene elastomer and a specific fatty acid amide in the adhesive layer, but because a low molecular weight compound is used. There are concerns about contamination of the adherend.

International Publication No. WO2008 / 099865 Pamphlet JP 2007-126512 A JP 2012-255071 A JP 2008-274213 A JP 2011-126169 A JP 2013-121989

The problem to be solved by the present invention is to provide a surface protective film in which natural peeling from an adherend is prevented when it is attached to various adherends having a flat surface or irregularities. Another object of the present invention is to provide a surface protective film capable of suppressing the progress of adhesion in the adhesive layer when it is attached to various adherends.

As a result of intensive studies to solve the above problems, the present inventors have obtained a surface having an adhesive layer containing a specific resin composition obtained by blending a thermoplastic resin with a 4-methyl-1-pentene copolymer. It has been found that the protective film exhibits good unevenness followability and has both sufficient adhesive strength and sufficient adhesive stability. That is, various adherends with unevenness using materials having both sufficient adhesive force and good unevenness followability rather than pasting to an adherend with a small contact area using a material having high adhesiveness as in the past It is possible to increase the contact area when affixed to. As a result, it has been found that it has good adhesive stability, and the present invention has been completed.

In addition, the present inventors have found that a specific resin composition obtained by blending a thermoplastic resin with a 4-methyl-1-pentene copolymer has a sufficient adhesive strength and an effect of suppressing the adhesion progress when used as an adhesive. And the present invention has been completed.

The surface protective film of the present invention is
2 to 50 parts by weight of 4-methyl-1-pentene / α-olefin copolymer (A) satisfying the following requirements (a), (b), (c) and (d):
A resin composition containing 98 to 50 parts by weight of a thermoplastic resin (B) other than the 4-methyl-1-pentene / α-olefin copolymer (A) (provided that the 4-methyl-1-pentene A total of 100 parts by weight of the α-olefin copolymer (A) and the thermoplastic resin (B)) and a base material layer. :
(A) 65 to 90 mol% of the structural unit (i) derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin (excluding 4-methyl-1-pentene) (ii ) In an amount of 35 to 10 mol%.

(B) the intrinsic viscosity [η] measured at 135 ° C. in decalin is 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) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. It is in;
(D) The density is in the range of 870 to 830 kg / m ³ .

The surface protective film of the present invention can exhibit a sufficient adhesive force when applied to not only a flat adherend but also various adherends having unevenness, and has excellent uneven followability. Adhesive stability is sufficient by increasing the contact area to the adherend. In addition, the surface protective film of the present invention can exhibit a sufficient adhesive force when adhered to not only a flat adherend but also various adherends, and has an excellent adhesive progress suppressing 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 material layer.

[Resin composition]
The resin composition used in the present invention comprises a 4-methyl-1-pentene / α-olefin copolymer (A) having specific physical properties and the 4-methyl-1-pentene / α-olefin copolymer ( A thermoplastic resin (B) other than A) is contained in a specific ratio.

In this specification, the 4-methyl-1-pentene / α-olefin copolymer (A) may be simply referred to as “copolymer (A)”, and 4-methyl-1-pentene / The thermoplastic resin (B) other than the α-olefin copolymer (A) may be simply referred to as “thermoplastic resin (B)”.

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

Requirement (a);
The 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention comprises 65 to 90 mol% of the structural unit (i) derived from 4-methyl-1-pentene, and an α-olefin. The structural unit (ii) derived from (excluding 4-methyl-1-pentene) comprises 35 to 10 mol%. Here, “mol%” is a value when the total of structural units derived from all the constituent monomers is 100 mol%. For example, 4-methyl-1-pentene / α-olefin copolymer (A) However, when it consists only of structural unit (i) and structural unit (ii), it is a value when the sum total of structural unit (i) and structural unit (ii) is 100 mol%.

That is, the lower limit of the proportion of the structural unit (i) is 65 mol%, preferably 80 mol%, and more preferably 81 mol%. On the other hand, the upper limit of the proportion of the structural unit (i) is 90 mol%, and more preferably 86 mol%. Thus, in the present invention, the proportion of the structural unit (i) in the 4-methyl-1-pentene / α-olefin copolymer (A) is not less than the lower limit value, so that the unevenness of the surface protective film to be obtained is Excellent trackability and moderate flexibility by being below the upper limit. Further, in the case of 80 to 90 mol%, the surface protective film obtained has a surface which is excellent in adhesive strength and adhesion stability to a flat plate or uneven surface, and maintains an appropriate flexibility that does not damage the adherend. Increased hardness facilitates film formability and handling of the surface protective film before adhesion, and is preferably 81 to 86 mol%.

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

Examples of the α-olefin that leads to the structural unit (ii) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and 1-tetradecene. 1-hexadecene, 1-octadecene, 1-eicosene, etc., a linear α-olefin having 2 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, 3- Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, Examples thereof include branched α-olefins having 5 to 20 carbon atoms, preferably 5 to 15 carbon atoms, such as 4-ethyl-1-hexene and 3-ethyl-1-hexene. Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and ethylene and propylene are particularly preferable.

Such an α-olefin that leads to the structural unit (ii) may be one kind alone, or may be a combination of two or more kinds.

Here, in one embodiment of the present invention, the 4-methyl-1-pentene / α-olefin copolymer (A) comprises only the structural unit (i) and the structural unit (ii). In this case, the sum total of structural unit (i) and structural unit (ii) is 100 mol%.

However, the 4-methyl-1-pentene / α-olefin copolymer (A) is a small amount that does not impair the object of the present invention, specifically 10 mol% or less, preferably 5 mol% or less, more preferably Is 3 mol% or less, in addition to the structural unit (i) and the structural unit (ii), other polymerizability that is neither 4-methyl-1-pentene nor an α-olefin leading to the structural unit (ii) A structural unit derived from a monomer may further be included.

Preferred specific examples of such 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 compounds such as maleic anhydride. Acids or derivatives thereof; conjugated dienes such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1 , 5-heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene- 2-norbornene, 5-isopropyl Den-2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2, Non-conjugated polyenes such as 2-norbornadiene are exemplified.

In other words, the 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention comprises the following structural units:
Structural unit (i) derived from 4-methyl-1-pentene, 65 to 90 mol%;
a structural unit (ii) derived from an α-olefin (excluding 4-methyl-1-pentene) (35) to 10 mol%; and 4-methyl-1-pentene and the structural unit (ii) 0 to 10 mol% of structural units derived from other polymerizable monomers excluding α-olefin.

Here, when there is a structural unit derived from another polymerizable monomer, the total content of the structural unit (ii) and the structural unit derived from the other polymerizable monomer is the above-mentioned “ratio of the structural unit (ii)”. Fulfill. In this case, the total of the structural unit (i), the structural unit (ii), and the structural unit derived from the other polymerizable monomer is 100 mol%.

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

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

Requirement (b);
The intrinsic viscosity [η] of the 4-methyl-1-pentene / α-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. is there. The details of the measurement conditions and the like are as described in the column of Examples described later.

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

As described later, when hydrogen is used in combination during polymerization, the molecular weight can be controlled and the intrinsic viscosity [η] can be adjusted.

When the intrinsic viscosity [η] is less than 0.1 dL / g or more than 5.0 dL / g, a pressure-sensitive adhesive layer constituting the surface protection film is formed particularly when processed into a surface protection film. In some cases, the molding processability may be impaired.

Requirement (c);
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention are measured by gel permeation chromatography (GPC). (Molecular weight distribution; Mw / Mn) is in the range of 1.0 to 3.5. The 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, there is a concern about the influence of the low molecular weight, low stereoregular polymer derived from the composition distribution, and the pressure-sensitive adhesive surface of the resulting surface protective film, that is, the surface protective film is Since the surface of the pressure-sensitive adhesive layer to be formed is sticky, the tactile sensation is deteriorated and the adherend is easily contaminated.

Here, in the present invention, by using the catalyst described later, the copolymer (A) satisfying the requirement (c) can be obtained within the range of the intrinsic viscosity [η] indicated by the requirement (b). it can. In addition, the value of said Mw / Mn and the following Mw is a value at the time of measuring by the method employ | adopted in the Example mentioned later.

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

Requirement (d);
The density (measured by ASTM D 1505) of the 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention is 870 to 830 kg / m ³ , preferably 865 to 830 kg / m ³ , More preferably, it is 855 to 830 kg / m ³ . The details of the measurement conditions and the like are as described in the column of Examples described later.

The density can be appropriately changed depending on the comonomer composition ratio of the 4-methyl-1-pentene / α-olefin copolymer (A), and the copolymer (A) having a density within the above range is a lightweight pressure-sensitive adhesive. And it is advantageous in manufacturing an adhesive sheet.

The 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention further has a Shore A hardness (according to JIS K6253) 15 seconds after the start of contact with the pusher needle. (Measured in the state of a press sheet having a thickness of 3 mm according to the standard) is desirably in the range of 5 to 90, preferably 10 to 85, and more preferably 15 to 80. The method of creating the press sheet is as shown in the examples.

The 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention further has a Shore A hardness (conforming to JIS K6253, It is desirable that the change ΔHS of the value (measured in the state of a 3 mm-thick press sheet) is in the range of 5 to 60, preferably 10 to 50, more preferably 10 to 45.

ΔHS = (Shore A hardness value immediately after start of pressing needle contact−Shore A hardness value 15 seconds after start of pressing needle contact)
ΔHS can be arbitrarily changed depending on the comonomer type and comonomer composition constituting the 4-methyl-1-pentene / α-olefin copolymer (A), and if ΔHS is within the above range, the unevenness followability is excellent. .

If it is difficult to measure Shore A hardness, use the Shore D hardness value instead.
ΔHS ′ = (Shore D hardness value immediately after the start of pressing needle contact−Shore D hardness value 15 seconds after the start of pressing needle contact)
Can be requested. In this case, it is desirable that this ΔHS ′ is in the range of 5 to 50, preferably 5 to 25, more preferably 6 to 20. This ΔHS ′ can be arbitrarily changed depending on the comonomer type and comonomer composition constituting the 4-methyl-1-pentene / α-olefin copolymer (A), as in the case of ΔHS, and ΔHS ′ is within the above range. If there is, it is excellent in uneven followability.

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

The method for producing the 4-methyl-1-pentene / α-olefin copolymer (A) used in the present invention comprises 4-methyl which satisfies the requirements (a), (b), (c) and (d) described above. The 1-pentene / α-olefin copolymer (A) is not particularly limited as long as it can be obtained. However, in the general embodiment of the present invention, the 4-methyl-1-pentene / α-olefin copolymer (A) comprises 4-methyl-1-pentene and the above-mentioned “α-derived unit (ii)”. It can be obtained by polymerizing "olefin" in the presence of a suitable polymerization catalyst. Here, as a polymerization catalyst that can be used in the present invention, a conventionally known catalyst, for example, a magnesium-supported titanium catalyst, WO 01/53369 pamphlet, WO 01/27124 pamphlet, and Japanese Patent Laid-Open No. 3-193796. The metallocene catalyst described in JP-A No. 02-41303 or the like is preferably used, and more preferably an olefin polymerization catalyst containing a metallocene compound represented by the following general formula (1) or (2) Used for.

(The above 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, and adjacent substituents from R ¹ to R ⁴ are bonded to each other to form a ring. The adjacent substituents from R ⁵ to R ¹² may be bonded to each other to form a ring, and A may contain a partially unsaturated bond and / or an aromatic ring. A divalent hydrocarbon group of ˜20, and A may contain two or more ring structures including a ring formed with Y;
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, hydrocarbon groups, and anionic ligands or neutral ligands capable of coordinating with lone pairs;
j is an integer of 1 to 4. )
The general formula (1) or ^{(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 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. Yes, it may contain one or more ring structures. Moreover, a part or all of hydrogen of 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, 1,1-diethylpropyl, 1-ethyl-1 -Methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl -1-cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, biphenyl, Naphthyl, tolyl, chlorophenyl, chlorobipheny , Chloronaphthyl, and the like.

The silicon-containing hydrocarbon group is preferably an alkylsilyl group or 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. Is mentioned.

Adjacent substituents from 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 R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ , and R ⁸ = R ^9. The fluorene ring is preferably unsubstituted fluorene, 3,6-disubstituted fluorene, 2,7-disubstituted fluorene or 2,3,6,7-tetrasubstituted fluorene. Wherein the 3-position on the fluorene ring, 6-position, 2-position, 7-position corresponds to the ^{R 7, R 10, R 6} , R 11 , respectively.

R ¹³ and R ^{14 in} the general 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 as those described above.

Y is carbon or silicon. In the case of the general formula (1), R ¹³ and R ¹⁴ are bonded to Y to form a substituted methylene group or a substituted silylene group as a bridging part. Preferred examples include methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, fluoromethylphenylmethylene, chloromethylphenylmethylene, diphenylmethylene, dichlorophenylmethylene, difluorophenylmethylene. Methylnaphthylmethylene, dibiphenylmethylene, di-p-methylphenylmethylene, methyl-p-methylphenylmethylene, ethyl-p-methylphenylmethylene, dinaphthylmethylene or dimethylsilylene, diisopropylsilylene, methyl-tert-butylsilylene, dicyclohexyl Silylene, methylcyclohexylsilylene, methylphenylsilylene, fluoromethyl Enirushiriren, chloromethyl silylene, diphenyl silylene, mention may be made of di-p- methylphenyl silylene, methyl -p- methylphenyl silylene, ethyl -p- methylphenyl silylene, methyl naphthyl silylene, a dinaphthyl silylene like.

In the case of the general formula (2), Y is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring, and a cycloalkylidene group or It constitutes a cyclomethylenesilylene group and the like. Preferred examples include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanidene. Examples include lidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene, and the like.

In the general formulas (1) and (2), M 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 halogen, a hydrocarbon group having 1 to 20 carbon atoms, and an anionic ligand or a neutral ligand capable of coordinating with 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 as those described above. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, and tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.

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

As the metallocene compound constituting the olefin polymerization catalyst that can be used in the present invention, the metallocene compound represented by the above general formula (1) or (2) is particularly preferably exemplified, but is not limited thereto. For example, other suitable examples of metallocene compounds that can be used in the present invention include metallocene compounds represented by the following general formula [I].

(In the formula [I], R ¹ , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each Independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, R ² is a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, R ⁴ is a hydrogen atom, Of the substituents R ¹ to R ¹⁶ excluding R ⁴ , any two substituents may be bonded to each other to form a ring, M is a Group 4 transition metal, and Q is a halogen atom. , A hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, j is an integer of 1 to 4, and when j is an integer of 2 or more, Q is the same or (You may choose a different combination.)
In the general formula [I], it is preferable that R ¹ and R ³ is a hydrogen atom; preferably R ² is a hydrocarbon group having 1 to 20 carbon atoms, carbon bonded to the cyclopentadienyl ring 3 It is preferably a substituent which is a secondary 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 each a hydrogen atom. Preferably; 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. It is preferable to form.

<R ¹⁶ from R ^1>
In the general formula [I], examples of the hydrocarbon group that can be R ¹ to R ¹⁶ (excluding R ⁴ ) include, for example, a linear hydrocarbon group, a branched hydrocarbon group, and a cyclic saturated hydrocarbon group. , A cyclic unsaturated hydrocarbon group, or a group obtained by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group. The carbon number of the hydrocarbon group is usually 1-20, preferably 1-15, more preferably 1-10.

Examples of the linear hydrocarbon group include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, and n-nonyl. And straight-chain alkyl groups such as n-decanyl group; straight-chain alkenyl groups such as allyl group.

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

Examples of the cyclic saturated hydrocarbon group include cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and methylcyclohexyl group; and polycyclic groups such as norbornyl group, adamantyl group, and methyladamantyl group. It is done.

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; a cycloalkenyl group such as a cyclohexenyl group; and 5-bicyclo [2.2. 1] Polycyclic unsaturated alicyclic groups such as a hepta-2-enyl group.

Examples of the group formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include a benzyl group, a cumyl group, a 1,1-diphenylethyl group, a triphenylmethyl group, and the like. And a group formed by substituting one or two or more hydrogen atoms of the alkyl group with an aryl group.

Examples of the hetero atom-containing hydrocarbon group in R ¹ to R ¹⁶ (excluding R ⁴ ) include, for example, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an oxygen atom such as a furyl group -Containing hydrocarbon group; nitrogen atom-containing hydrocarbon group such as amino group such as N-methylamino group, N, N-dimethylamino group, N-phenylamino group, pyryl group; hydrocarbon group containing sulfur atom such as thienyl group Is mentioned. The carbon number of the heteroatom-containing hydrocarbon group is usually 1-20, preferably 2-18, more preferably 2-15. However, the silicon-containing group is excluded from the heteroatom-containing hydrocarbon group.

Examples of the silicon-containing group in R ¹ to R ¹⁶ (excluding R ⁴ ) include, for example, a formula —SiR ₃ such as trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, triphenylsilyl group, etc. (Wherein the plurality of R's are each independently an alkyl group having 1 to 15 carbon atoms or a phenyl group).

Of the substituents from R ¹ to R ¹⁶ excluding R ⁴ , two adjacent substituents (eg, 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 together to form a ring. even if well attached R ⁶ and R ⁷ together may form a ring, may form a ring R ¹ and R ⁸ together, R ³ and R ⁵ are mutually It may combine to form a ring. Two or more ring formations may exist in the molecule.

In this specification, examples of the ring (additional ring) formed by bonding two substituents to each other include an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specific examples include a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; a hetero ring such as a furan ring and a thiophene ring and a corresponding hydrogenated hetero ring, preferably a cyclohexane ring; a benzene ring and a hydrogen Benzene ring. Such a ring structure may further have a substituent such as an alkyl group on the ring.

R ¹ and R ³ are preferably 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, ⁵ is more preferably an alkyl group having 2 or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, and R ⁵ is an alkyl group having 2 or more carbon atoms. Especially preferred. From the viewpoint of synthesis, R ⁶ and R ⁷ are preferably hydrogen atoms. R ⁵ and R ⁷ are more preferably bonded to each other to form a ring, and the ring is particularly preferably a 6-membered ring such as a cyclohexane ring.

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

R ² is preferably a hydrocarbon group from the viewpoint of stereoregularity, more preferably a hydrocarbon group having 1 to 20 carbon atoms, still more preferably not an aryl group, and a linear hydrocarbon Group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group is particularly preferable, and a substituent having a free valence (carbon bonded to a cyclopentadienyl ring) being a tertiary carbon is particularly preferable. preferable.

Specific examples of R ² include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group, and more preferable. Is a substituent in which the carbon having a free valence is a tertiary carbon, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, or a 1-adamantyl group, particularly preferably a tert-butyl group, 1- An adamantyl group;

In general formula [I], the fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative, but R ⁹ , R ¹² , R ¹³ and R ¹⁶ are preferably from the viewpoint of stereoregularity and molecular weight. Is a hydrogen atom.

R ^10, R ^11, R ¹⁴ and R ¹⁵ is 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, more preferably It is a hydrocarbon group having 1 to 20 carbon atoms.

R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of such a substituted fluorenyl group include 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-2,3, 6,7,8,10-hexahydro-1H-dicyclopenta [b, h] fluorenyl group, 1 ', 1', 3 ', 6', 8 ', 8'-hexamethyl-1'H, 8'H-dicyclopenta [B, h] fluorenyl group is exemplified, and 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro- is particularly preferred. 1H-dibenzo [b, h] fluorenyl group.

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

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

Examples of the hydrocarbon group that can be Q include the same groups as the hydrocarbon groups in R ¹ to R ¹⁶ (excluding R ⁴ ), preferably alkyls such as linear alkyl groups and branched alkyl groups. It is a group.

Examples of the anion ligand in Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; dimethylamide and diisopropylamide Amide groups such as methylanilide and diphenylamide.

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

It is preferable that at least one Q is a halogen atom or an alkyl group.

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

The position number used for naming the compound [I] is [1- (1 ′, 1 ′, 4 ′, 4 ′, 7 ′, 7 ′, 10 ′, 10′-octamethyloctahydrodibenzo [ b, h] fluoren-12'-yl) (5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)] zirconium dichloride, and [8- (1 ', 1', 4 ', 4', 7 ', 7', 10 ', 10'-octamethyloctahydrodibenzo [b, h] fluoren-12'-yl) (2-tert-butyl-8-methyl -3,3b, 4,5,6,7,7a, 8-octahydrocyclopenta [a] indene)] zirconium dichloride as an example, one of the enantiomers is represented by the formula [I-1], the formula [ I-2].

Specific examples of the metallocene compound in the present invention include compounds exemplified in International Publication No. 01/27124, International Publication No. 2006/025540, or International Publication No. 2014/050817. This does not limit the scope of the present invention.

When a metallocene compound is used in the production of the 4-methyl-1-pentene / α-olefin copolymer (A), the catalyst component is:
(A) a metallocene compound (for example, a metallocene compound represented by the above general formula (1), (2) or [I]);
(B) (b-1) an organoaluminum oxy compound,
(B-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) at least one compound selected from organoaluminum compounds;
If necessary,
(C) It is comprised from a particulate carrier. As a production method, for example, the method described in International Publication No. 01/27124 pamphlet can be employed.

Further, it reacts with the organoaluminum oxy compound (b-1) (hereinafter also referred to as “component (b-1)”) and the metallocene compound (a) (hereinafter also referred to as “component (a)”) to form an ion pair. Specific examples of compound to be formed (hereinafter also referred to as “component (b-2)”), organoaluminum compound (b-3) (hereinafter also referred to as “component (b-3)”), and particulate carrier (c) Examples include those compounds or carriers conventionally known in the field of olefin polymerization, such as the specific examples described in WO 01/27124.

Here, in a preferred embodiment of the present invention, the 4-methyl-1-pentene / α-olefin copolymer (A) contains 4-methyl-1-pentene and the above-described “α-derivative unit (ii)”. In the production of 4-methyl-1-pentene / α-olefin copolymer (A), polymerization may be solution polymerization, suspension polymerization, etc. The liquid phase polymerization method or the gas phase polymerization method can be used.

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, kerosene; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, etc. And alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, trichloromethane, and tetrachloromethane, and mixtures thereof.

In addition, bulk polymerization using 4-methyl-1-pentene and the above-mentioned “α-olefin leading to the structural unit (ii)” itself as a solvent can also be carried out.

In addition, the composition distribution can be controlled by performing the homopolymerization of 4-methyl-1-pentene and the copolymerization of 4-methyl-1-pentene and the above “α-olefin leading to structural unit (ii)” stepwise. It is also possible to obtain the 4-methyl-1-pentene / α-olefin copolymer (A).

In carrying out the polymerization, the component (a) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol in terms of Group 4 metal atom in the periodic table per liter of reaction volume. Used in various amounts. The component (b-1) has a molar ratio [(b-1) / M] of the component (b-1) and the transition metal atom (M) in the component (a) of usually 0.01 to 5000, Preferably, it is used in an amount of 0.05 to 2000. The component (b-2) has a molar ratio [(b-2) / M] of the component (b-2) to the transition metal atom (M) in the component (a) of usually 1 to 10, preferably 1. It is used in such an amount that it becomes ˜5. Component (b-3) has a molar ratio [(b-2) / M] of component (b-3) to transition metal atom (M) in component (a) of usually 10 to 5000, preferably 20 It is used in such an amount that it becomes ˜2000.

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

The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

Hydrogen may be added for the purpose of controlling the molecular weight and polymerization activity of the polymer produced during the polymerization, and the amount is based on a total of 1 kg of 4-methyl-1-pentene and the above “α-olefin leading to the structural unit (ii)”. About 0.001 to 100 NL is appropriate.

<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 4-methyl-1-pentene / α-olefin copolymer (A). Examples of the thermoplastic resin (B) include an olefin resin (B1) excluding 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 adhesiveness, moldability, tackiness and the like to the resin composition of the present invention.

Here, specific examples of the olefin resin (B1) include a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and a copolymer of ethylene, an α-olefin having 3 to 20 carbon atoms and a cyclic olefin. , Ethylene copolymers having various vinyl compounds such as styrene, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, etc. as comonomers, copolymers of propylene and α-olefins having 4 to 20 carbon atoms, Ethylene copolymer containing propylene, a copolymer of α-olefin having 4 to 20 carbon atoms and cyclic olefin, and various vinyl compounds such as styrene, vinyl acetate, (meth) acrylic acid and (meth) acrylic acid ester as comonomers. Examples include coalescence. More specifically, low density, medium density, high density polyethylene, high pressure method low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl-1-pentene, poly 3-methyl Examples include -1-butene, cyclic olefin copolymer, chlorinated polyolefin, and olefin elastomer.

As an example of the olefin-based elastomer, an elastomer made of an olefin-based block copolymer can also be used. For example, a block copolymer of a polyolefin block that forms a polymer with high crystallinity such as polypropylene that becomes a hard part and a monomer copolymer that shows amorphousness that becomes a soft part can be mentioned. Specifically, an olefin ( Crystalline) / ethylene / butylene / olefin block copolymer, polypropylene / polyolefin (amorphous) / polypropylene block copolymer, and the like. As specific examples, trade names DYNARON (registered trademark) from JSR Corporation, trade names Toughmer (registered trademark), Notio (registered trademark) from Mitsui Chemicals, Inc., trade names ENGAGE ^™ and VERSIFY from Dow Chemical Corporation. ^TM , commercially available from ExxonMobil Chemical Co., Ltd. under the trade name Vistamaxx ^TM .

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

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

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

As the styrene elastomer (B2), a block copolymer (SBS) of a polystyrene block that becomes a hard part (crystal part) and a diene monomer block that becomes a soft part, a hydrogenated styrene / butadiene / styrene block copolymer (HSBR), styrene / ethylene / propylene / styrene block copolymer (SEPS), styrene / ethylene / butene / styrene block copolymer (SEBS), styrene / isoprene / styrene block copolymer (SIS), styrene / isobutylene -A styrene copolymer (SIBS), a styrene-isobutylene copolymer (SIB), etc. can be illustrated. Styrenic elastomers are used singly or in combination of two or more.

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

The styrene / ethylene / propylene / styrene block copolymer is obtained by hydrogenating a styrene / isoprene / styrene block copolymer (SIS). As specific examples of SIS, JSR Corporation as trade name: JSR SIS (registered trademark), Kuraray Co., Ltd. as trade name: Hibler (registered trademark), or Shell Corporation as trade name: Clayton D (registered trademark) The thing marketed etc. are mentioned.

Also, specific examples of SEPS include those commercially available from Kuraray Co., Ltd. under the trade name: Septon (registered trademark), or from Shell Co., Ltd. under the trade name: Clayton (registered trademark).

Further, specific examples of SEBS include those commercially available from Asahi Kasei Corporation under the trade name: Tuftec (registered trademark), or from Shell Corporation as trade name: Clayton (registered trademark).

Also, specific examples of SIB and SIBS include those commercially available from Kaneka Corporation under the trade name: Shivstar (registered trademark).

Also, as a special styrene elastomer, trade name: Asahi Kasei Co., Ltd. O. E etc. are also mentioned.

Further, as other thermoplastic resins (B), thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; ethylene / vinyl acetate copolymer; ethylene / methacrylic acid acrylate copolymer; ionomer; Examples of the copolymer include polyvinyl alcohol, fluororesin polycarbonate, polyacetal, polyphenylene oxide, polyphenylene sulfide polyimide, polyarylate, polysulfone, and polyethersulfone.

In the present invention, among these thermoplastic resins (B), an olefin resin (B1) and a styrene elastomer (B2) are preferably used. Further, when the adherend is an uneven surface, the styrene elastomer (B2) is particularly preferable because the surface protective film to be obtained has high adhesive strength. Here, when the styrene elastomer (B2) is used as the thermoplastic resin (B), for example, it is more preferable that the thermoplastic resin (B) is made of only the styrene elastomer (B2).

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

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, in the composition, from the viewpoint of adhesive strength and unevenness followability to the adherend. The upper limit of the copolymer (A) content 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. Part.

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

<Other ingredients>
The resin composition according to the present invention may be composed only of the copolymer (A) and the thermoplastic resin (B), but the copolymer (A) and the thermoplastic resin (B). In addition to the above, if necessary, an appropriate additive such as a tackifier may be further contained as another component.

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

Here, examples of tackifiers that can be used in the present invention include resinous substances that are generally produced and sold as tackifiers. Specifically, chroman resins such as chroman and indene resins; Phenolic resins such as phenol / formaldehyde resins and xylene / formaldehyde resins; terpene resins such as terpenes / phenolic resins, terpene resins (α, β-pinene resins), aromatic modified terpene resins, hydrogenated terpene resins; synthetic polyterpene resins; Petroleum hydrocarbon resins such as aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, hydrogenated hydrocarbon resins and hydrocarbon tackifying resins; rosin pentaerythritol ester, rosin Glycerin ester, hydrogenated rosin, hydrogenated rosin ester, special rosin Examples thereof include rosin derivatives such as esters and rosin tackifiers.

Among these components, hydrogenated hydrocarbon resins, hydrogenated aliphatic cyclic hydrocarbon resins, hydrogenated aliphatic / alicyclic petroleum resins having a softening point of 70 ° C. or higher, preferably in the range of 70 to 130 ° C., Hydrogenated resins such as hydrogenated terpene resins and hydrogenated synthetic polyterpene resins; rosin pentaerythritol ester, rosin glycerin ester, hydrogenated rosin, hydrogenated rosin ester, special rosin ester, rosin tackifier, etc. And the like.

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

Here, when the resin composition of the present invention contains the tackifier, the amount of the tackifier used is 100 parts by weight of the total of the copolymer (A) and the thermoplastic resin (B). As 5 to 100 parts by weight.

In addition, the resin composition of the present invention includes, as an additive other than the above-described tackifier, a weather resistance stabilizer, a heat stabilizer, an antistatic agent, an anti-slip agent, and an anti-blocking agent as long as the object of the present invention is not impaired. Agent, antifogging agent, lubricant, pigment, dye, plasticizer, anti-aging agent, hydrochloric acid absorbent, antioxidant, crystal nucleating agent, antifungal agent, antibacterial agent, flame retardant, filler (inorganic filler, organic filler) Agents) and additives such as softeners may be included depending on the purpose.

As the softener, a conventionally known softener can be used. Specific examples thereof include petroleum-based substances such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt and petroleum jelly; coal tars such as coal tar and coal tar pitch; Fat oils such as oil, linseed oil, rapeseed oil, soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax and lanolin; ricinoleic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, montanic acid Fatty acids such as oleic acid and erucic acid or metal salts thereof; synthetic polymers such as petroleum resins, coumarone indene resins and atactic polypropylene; ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate; Lee black wax, and liquid polybutadiene or its modified product or hydrogenated product; and 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; fibrous fillers such as glass fiber and metal fiber. Further, hydrophilic layered clay minerals and / or hydrophilic inorganic compounds having a specific shape (excluding layered) are also included.

As the hydrophilic layered clay mineral, for example, a phyllosilicate mineral in which a plurality of layers extending in two dimensions is laminated, for example, smectite can be mentioned. Smectite is a montmorillonite group mineral, for example, montmorillonite (montmorillonite), magnesia montmorillonite, tetsu montmorillonite, tectum magnesia montmorillonite, beidellite, aluminian beidellite, nontronite, aluminian non Examples include tronite, saponite (saponite), aluminian sapphire, hectorite, soconite, stevensite, and bentonite.

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

These hydrophilic layered clay minerals can be used alone or in combination of two or more. As such hydrophilic layered clay minerals, general commercial products can be used. For example, more specifically, as natural products, for example, Kunipia series (montmorillonite, manufactured by Kunimine Kogyo Co., Ltd.), Bengel series ( Bentonite, manufactured by Hojun Co., Ltd.), Somasif ME Series (swellable mica, manufactured by Corp Chemical Co.), and the like. Examples of synthetic products include Smecton (Saponite, manufactured by Kunimine Industries), Lucentite SWN Series (Hectorite, Corp Chemical) and Laponite (hectorite, manufactured by Rockwood Holdings). In general, since a synthetic product has a smaller maximum length than a natural product, a synthetic product is preferable from the viewpoint of obtaining small oil droplets.

Examples of the flame retardants include antimony flame retardants, aluminum hydroxide, magnesium hydroxide, zinc borate, guanidine flame retardants, inorganic compounds such as zirconium flame retardants, ammonium polyphosphate, ethylene bistris (2-cyanoethyl) Phosphonium chloride, tris (tribromophenyl) phosphate, tris (tribromophenyl) phosphate, phosphate esters such as tris (3-hydroxypropyl) phosphine oxide and other phosphorus compounds, chlorinated paraffin, chlorinated polyolefin, Chlorinated flame retardants such as chlorocyclopentadecane, hexabromobenzene, ethylenebisdibromonorbornanedicarboximide, ethylenebistetrabromophthalimide, tetrabromobisphenol A derivatives, tetrabromobis Phenol S, a bromine-based flame retardants, and mixtures thereof, such as tetrabromobisphenol dipentaerythritol.

The total amount of additives other than tackifiers such as these softeners, fillers, flame retardants, etc. is 100 parts by weight of the total of the copolymer (A) and the thermoplastic resin (B). 0.001 to 50 parts by weight.

<The manufacturing method of the resin composition which concerns on this invention>
The resin composition according to the present invention includes the copolymer (A), the thermoplastic resin (B), and, if necessary, various additives listed in the above-mentioned “other components” section as described above. And blended in various known methods, for example, a multistage polymerization method, a plastmill, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, a kneader ruder or the like, or after mixing, a single screw extruder, twin screw After melt-kneading with an extruder, a kneader, a Banbury mixer, etc., it can be manufactured by adopting a granulation or pulverization method.

<Graft modification>
In the present invention, the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic resin (B) may be used as they are for the production of the resin composition of the present invention without modification. However, a part or all of the 4-methyl-1-pentene / α-olefin copolymer (A) may be graft-modified within a range not impairing the object of the present invention, and the thermoplastic resin (B ) May be partly or entirely graft-modified. Examples of the polar compound used for graft modification and the graft modification method include conventionally known compounds and methods. For example, the compounds and methods described in JP-A-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, and more preferably 0.2 to 20% by weight.

When the 4-methyl-1-pentene / α-olefin copolymer (A) or the thermoplastic resin (B) is graft-modified, the compatibility of each component in the composition or a laminated film is obtained. Furthermore, it is advantageous in that it is difficult to delaminate between films.

[Laminate, especially surface protective film]
In this invention, the laminated body using the said resin composition, ie, the laminated body containing the at least 1 adhesive layer (L1) which consists of the said resin composition is also provided.

In the laminate of the present invention, by using the above resin composition for the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer follows the concavo-convex shape when pasted on various adherends having unevenness, thereby increasing the adhesive area. In addition, sufficient adhesive strength can be exhibited, and the adhesive strength due to an increase in the adhesive area can be stably maintained.

Here, as a laminate of the present invention, a laminate comprising a base material layer (L2) and at least one pressure-sensitive adhesive layer (L1) comprising the above-described resin composition of the present invention, specifically, the above-described laminate. The multilayer film formed by laminating | stacking the adhesive layer (L1) which consists of a resin composition of this invention on the single side | surface or both surfaces of the base material layer (L2) of a single layer or a multilayer structure is mentioned. In other words, as a basic aspect of the laminate according to the present invention, a two-layer film laminated in the order of the base material layer (L2) / adhesive layer (L1), or the adhesive layer (L1) / group A three-layer film formed by laminating in the order of material layer (L2) / adhesive layer (L1) can be mentioned.

Here, the material of the base material layer (L2) constituting the laminate of the present invention is not particularly limited, but is preferably a thermoplastic resin such as a polyolefin resin, and specific examples thereof include a polypropylene resin ( Propylene homopolymer and random or block copolymer of propylene and a small amount of α-olefin), polyethylene resin (low density polyethylene, medium density polyethylene, high density polyethylene and linear low density polyethylene), known ethylene Polymer (ethylene-α-olefin copolymer, ethylene-ethyl acrylate copolymer; ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-n-butyl acrylate copolymer), known Propylene copolymer (propylene-α-olefin copolymer), poly-4- Chill-1-pentene, as well as to illustrate these combinations.

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

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

As the base material layer (L2), one stretched in a uniaxial or biaxial direction can also be used.

Examples of the method for producing the laminate of the present invention include a known multilayer film molding method, and a preferable method is a pressure-sensitive adhesive comprising the resin composition of the present invention using a T-die film molding method or an inflation film molding method. A method of co-extrusion of the agent layer (L1) and the base material layer (L2), or an extrusion coating of the pressure-sensitive adhesive layer (L1) made of the resin composition of the present invention on a preformed base material layer (L2) The method of obtaining can be illustrated. Moreover, the method of dissolving the resin composition of this invention in a solvent, apply | coating on a base material layer (L2), and forming an adhesive layer (L1) on the said base material layer (L2) is also mentioned. Among these, film formation by a coextrusion molding method is preferable.

The multilayer film of the present invention may be stretched uniaxially or biaxially. As a preferred method for uniaxial stretching, a commonly used roll stretching method can be exemplified. Examples of the biaxial stretching method include a sequential stretching method in which biaxial stretching is performed after uniaxial stretching, and a simultaneous biaxial stretching method such as a tubular stretching method.

By using the production method as described above, the laminate of the present invention can be obtained as a multilayer film. A suitable application of this 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, more preferably about 10 to 1000 μm. The thickness of the surface layer (adhesive layer) is not particularly limited and can be selected according to the type of adherend and the required physical properties (for example, adhesive strength), but is usually 1 to 500 μm, preferably 3 to 300 μm. . Moreover, the laminated body should just have two layers, an adhesive layer and a base material layer, for example, provides an intermediate | middle layer (L4) between an adhesive layer (L1) and a base material layer (L2). Also good. Here, conventionally known materials can be used as the material used for the intermediate layer (L4).

When the multilayer film using the resin composition of the present invention is used as a surface protective film, in order to prevent blocking (sticking) between the multilayer films, a release paper or a release film is sandwiched between the multilayer films, or a base material layer (L2 ) May be applied to the exposed surface.

In the present invention, the base material layer (L2) may contain an additive such as a mold release agent in order to impart a function such as slipperiness to the surface as necessary.

<Method for producing surface protective film>
There is no particular limitation on the method of laminating the base material layer (L2), the pressure-sensitive adhesive layer (L1), and the surface layer (L3) provided as necessary, but it is obtained in advance by T-die molding or inflation molding. A method of laminating the base material layer (L2) and the pressure-sensitive adhesive layer (L1) on the surface layer (L3) film obtained by a known laminating method such as extrusion lamination and extrusion coating, and the base material layer (L2) and the adhesive Examples include a method of laminating each film by dry lamination after the agent layer (L1) is made into a film independently, but from the viewpoint of productivity, the surface layer (L3), the base material layer (L2), the adhesive Coextrusion molding in which each component of the agent layer (L1) is subjected to molding in a multilayer extruder is preferred. This produces a surface protective film comprising a laminate having the intermediate layer (L4) in addition to the base layer (L2), the pressure-sensitive adhesive layer (L1) and the surface layer (L3) provided as necessary. The same applies to Considering these things, in the suitable aspect in this invention, the laminated body which comprises a surface protection film is a multilayer film obtained by the T-die film shaping | molding method, for example.

By using the base layer (L2), the pressure-sensitive adhesive layer (L1), and the surface layer (L3) provided as necessary, the polyolefin-based multilayer film having excellent releasability is particularly surface protective. It can be suitably used as a film or a release film.

<Application>
Examples of the use of the resin composition and the laminate comprising the resin composition of the present invention include an adhesive sheet and a surface protective film. When the resin composition of the present invention is used as an adhesive layer of a multilayer film, the multilayer film is composed of a metal plate such as an aluminum plate, a steel plate, and a stainless plate, and a coated plate thereof, or a glass plate or a synthetic resin plate. It can utilize suitably as a surface protection film for protecting the processing members, such as household appliances, automobile parts, and electronic parts using these members. Therefore, the resin composition of the present invention is, for example, an adhesive such as an adhesive film, a protective film adhesive layer, a semiconductor process protective film, a lens protective film, a semiconductor wafer back grind tape, a dicing tape, and a printed circuit board protective tape. Such a film or tape in the electronics field, a window glass protective film, a baking coating film, and the like can be suitably used. In particular, since the resin composition of the present invention has irregularity followability, it is suitably used for prism sheets and reflective sheets having many irregular structures on the surface, sheets for protecting the textured surface, and the like. Here, as an example of application to the protective tape for printed circuit boards, a protective film for a plating mask used in the plating process of a flexible printed circuit board can be given.

The surface protective film of the present invention can be used by being attached to an adherend that is an object to be protected. Components are adjusted according to the physical properties of the adherend surface of the adherend, such as surface irregularities (surface roughness). Generally, when the surface of the adherend is rough, the material is a strong adhesion type.

It is preferable to use a styrene elastomer (B2) as the thermoplastic resin (B) for the adherend surface with large surface irregularities. In that case, the height of the uneven surface of the adherend surface is preferably in the range of 0.1 to 300 μm, more preferably 0.1 to 100 μm, still more preferably 1 to 50 μm, and particularly preferably 1 to 30 μm.

In other words, the present invention also provides a method of protecting an adherend that is an object to be protected using the protective film of the present invention, and such a method is an adherend that is an object to be protected. It is made by sticking the surface protective film of the present invention on the surface to be protected in the body. In particular, when the styrene elastomer (B2) is used as the thermoplastic resin (B), the surface unevenness height is more preferably 0.1 to 300 μm as a suitable example of the adherend that is the object of protection. Is a surface having a thickness of 0.1 to 100 μm, more preferably 1 to 50 μm, particularly preferably 1 to 30 μm, and a more specific example is a prism sheet.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

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

〔composition〕
The 4-methyl-1-pentene and α-olefin contents in the polymer were measured by ¹³ C-NMR with the following apparatus and conditions. Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of orthodichlorobenzene / heavy benzene (80/20% by volume) as a solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45 ° pulse), repetition time is 5.5 seconds, integration number is 10,000 times or more, 27.50 ppm as standard for chemical shift Measured as a value.

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

[Melting point (Tm)]
The melting point (Tm) of the polymer was measured with a differential scanning calorimeter (DSC) using a DSC220C apparatus manufactured by Seiko Instruments Inc. Samples 7-12 mg obtained from the polymerization were sealed in an aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. The sample was held at 200 ° C. for 5 minutes to completely melt and then cooled to −50 ° C. at 10 ° C./min. After 5 minutes at −50 ° C., the sample was reheated to 200 ° C. at 10 ° C./min. This peak temperature in the second heating (second time) was adopted as the melting point (Tm).

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

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

[Η] = lim (η _sp / C) (C → 0)
[Molecular weight (Mw, Mn) / Molecular weight distribution (Mw / Mn)]
The molecular weight of the copolymer (A) was determined by using a liquid chromatograph: Waters ALC / GPC 150-C plus type (incorporated refractometer detector type), and Tosoh Corporation GMH6-HT × 2 and GMH6 as columns. -Two HTLs were connected in series, and o-dichlorobenzene was used as a mobile phase medium, and the measurement was performed at a flow rate of 1.0 ml / min and 140 ° C.

The Mw / Mn value and the Mz / Mw value were calculated by analyzing the obtained chromatogram by a known method using a calibration curve using a standard polystyrene sample. The measurement time per sample was 60 minutes.

[Methods for producing various measurement press sheets]
Each pressure-sensitive adhesive of Examples and Comparative Examples (that is, the pressure-sensitive adhesive resin composition used for the pressure-sensitive adhesive layer (L1)) was subjected to a pressure of 10 MPa using a hydraulic hot press machine manufactured by Shindo Metal Industry Co., Ltd. set to 190 ° C. A sheet was formed. In the case of a sheet with a thickness of 1 to 3 mm (spacer shape; 80 × 80 × 0.5 to 3 mm, 4 pieces on a 240 × 240 × 2 mm thick plate), the residual heat is reduced to about 5 to 7 minutes and 1 to 2 at 10 MPa. After pressurizing for a minute, using another hydraulic hot press machine manufactured by Shinfuji Metal Industry Co., Ltd. set to 20 ° C., the sample was compressed at 10 MPa and cooled for about 5 minutes to prepare a measurement sample. A 5 mm thick brass plate was used as the hot plate. Samples prepared by the above method were used for various physical property evaluation samples.

[Shore hardness measurement]
For the measurement of Shore hardness (conforming to JIS K6253), a press sheet with a thickness of 3 mm is used as a measurement sample, and the scale immediately after the start of contact with the Shore A hardness meter or Shore D hardness meter and after 15 seconds from the start of contact with the needle I read.

Further, the change ΔHS of the Shore hardness value defined by the following equation was obtained.

ΔHS = (Shore hardness value immediately after start of pressing needle contact-Shore hardness value 15 seconds after start of pressing needle contact)
Here, the Shore hardness was measured using a Shore A hardness meter in principle, but for a measurement sample in which the Shore A hardness is difficult to measure, a Shore D hardness meter was used instead.

Here, when the same type of hardness tester is used, it can be said that the greater the ΔHS, the higher the unevenness followability.

[Laminate molding]
Resin supply that connects to the surface layer (L3), base material layer (L2), and adhesive layer (L1) using a three-layer, three-layer T-die molding machine with a die width of 300 mm that also has a 30 mmφ single screw extruder Resin pellets were put in from a hopper, and the resin pellets were melted through a cylinder in a single screw extruder, and then extruded from a T-die to obtain a laminate to be an adhesive sheet. At this time, polypropylene F107 manufactured by Prime Polymer Co., Ltd. was used for the surface layer (L3) and the base material layer (L2), and the adhesive resin composition shown in each example and comparative example was used for the adhesive layer (L1). I used a thing.

Here, the surface layer (L3) thickness, the base material layer (L2) thickness, the pressure-sensitive adhesive layer (L1) thickness, and the total thickness for each example and comparative example are shown in Tables 2 to 5, respectively.

(Adhesive strength evaluation (acrylic plate))
In accordance with JIS Z0237-2000, the adhesive strength of the laminates obtained in each Example and Comparative Example was measured. Here, a sheet of 100 μm polyethylene terephthalate was attached to the surface of each laminate, which is a pressure-sensitive adhesive sheet sample, which is not the target for measuring the pressure-sensitive adhesive force, to obtain a pressure-sensitive adhesive film. On the other hand, a 50 mm wide × 100 mm long × 2 mm thick black acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name Acrylite REX, shape 50 × 100 mm square plate) was used as a test plate. The test plate and the adhesive film were allowed to stand in an environment of a temperature of 23 ° C. and a relative humidity of 50% for 1 hour. After the adhesive film was placed on the test plate, the pressure was applied with a rubber roll of about 2 kg while applying pressure. The sample was passed back and forth and attached to the test plate. After pasting, the test plate was placed in a constant environment at a temperature of 23 ° C. and a relative humidity of 50% for one day, and then at a speed of 300 mm / min in a 180 ° direction at a temperature of 23 ° C. and a relative humidity of 50%. The adhesive strength when peeled from the acrylic plate was measured and determined as the adhesive strength at 23 ° C.

The adhesive strength of each example and comparative example is shown in the column of “Adhesive strength (acrylic plate) @ 23 ° C.” in Tables 2 to 5.

[Adhesion progress rate]
A test plate on which an adhesive film (that is, an adhesive film obtained from the laminate obtained in each of Examples and Comparative Examples) was attached in accordance with the method and conditions described in the above “Adhesive strength evaluation (acrylic plate)” was tested at a temperature of 23. Instead of being placed in a constant environment of 50 ° C. and 50% relative humidity for 1 day, after being placed in an oven at 60 ° C. for 1 day, the temperature is 23 ° C. and the relative humidity is 50%. The adhesive strength after the adhesion progress was measured when it was peeled off from the black acrylic plate at / min. The adhesive strength at this time was determined as the adhesive strength at 60 ° C. The adhesive strength at 60 ° C. for each example and comparative example is shown in the column of “Adhesive strength (acrylic plate) @ 60 ° C.” in Tables 2 to 5.

For each Example and Comparative Example, the adhesive strength at 23 ° C. and the “Adhesive strength (acrylic plate) @ 60 ° C.” column shown in the column “Adhesive strength (acrylic plate) @ 23 ° C.” of Tables 2 to 5 Based on the adhesive strength at 60 ° C. shown, the adhesion progress rate was calculated. Here, the “adhesion progress rate” is specifically,
{(Adhesive strength at 60 ° C.) − (Adhesive strength at 23 ° C.)} / (Adhesive strength at 23 ° C.) × 100
Calculated as

The adhesion progress rate for each example and comparative example is shown in the column of “Adhesion progress rate” in Tables 2-5.

[Adhesive strength evaluation (SUS uneven plate)]
The adhesive strength of the laminates obtained in each Example and Comparative Example to the SUS uneven plate was measured as follows based on WO2011 / 002083. Here, the laminated body obtained by each Example and the comparative example was used as a protective film.

A protective film is pasted on a 50 mm wide stainless steel plate (SUS304, No. 180 finish) and placed in a constant environment at a temperature of 23 ° C. and a relative humidity of 50% for 1 day. The peel adhesive strength was measured at a speed of 300 mm / min. That is, in place of the black acrylic plate, the stainless steel plate was used, and the “adhesive film” was replaced with “protective film”. Pasting and measurement were performed.

The adhesive strength of each example and comparative example is shown in the column of “Adhesive strength (SUS uneven plate)” in Tables 2-5.

[Adhesion stability (SUS uneven plate)]
The adhesion stability of the laminates obtained in each Example and Comparative Example to the SUS uneven plate was evaluated as follows. Here, the laminated body obtained by each Example and the comparative example was used as a protective film.

A protective film was affixed to a stainless steel plate (SUS304, No. 180 finish) and stored for 1 day with the surface affixed in a constant environment at a temperature of 23 ° C. and a relative humidity of 50%. The number of peeled protective films after storage was confirmed and evaluated as follows.

×: All peeled off or did not stick to the substrate Δ: Some films peeled off ○: All remained sticky Evaluation for each example and comparative example was evaluated as “Adhesion stable” in Tables 2 to 5 Property (SUS uneven plate) "column.

(Adhesive strength evaluation (prism plate))
The adhesive strength of the laminates obtained in each Example and Comparative Example to the prism plate was measured as follows.

A prism sheet made of an acrylic resin having a thickness of 110 μm, a prism pitch of 50 μm, and a height of 35 μm 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 this protective film was 50 mm. The protective film is pressure-bonded to this prism plate at 20 mm / min using a 2 kg rubber roller, left in a constant environment at a temperature of 23 ° C. and a relative humidity of 50% for 30 minutes, and then at a speed of 300 mm / min in the 180 ° direction. The peel adhesive strength was measured.

The adhesive strength of each example and comparative example is shown in the column of “Adhesive strength (prism plate)” in Tables 2-5.

(Adhesive stability (prism plate))
The adhesion stability of the laminates obtained in each Example and Comparative Example to the prism plate was measured as follows.

The laminate obtained in each example and comparative example was used as a protective film. Then, instead of the stainless steel plate, the “adhesion stability (SUS uneven plate)” except that a protective film was applied to the same prism sheet used in the “adhesive strength evaluation (prism plate)”. ”Was evaluated in the same manner.

The evaluation of each example and comparative example is shown in the column of “Adhesive stability (prism plate)” in Tables 2 to 5.

[Synthesis Example 1]
750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a 1.5-liter stirring SUS autoclave sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.13 MPa (gauge pressure). Subsequently, methylaluminoxane prepared in advance was converted to 1 mmol in terms of Al, diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride. The toluene solution containing 0.01 mmol of 0.34 ml of the solution was pressed into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

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

[Synthesis Example 2]
A 1.5-liter SUS autoclave with sufficient nitrogen substitution was charged with 300 ml of normal hexane at 23 ° C. (dried in a dry nitrogen atmosphere and activated alumina) and 450 ml of 4-methyl-1-pentene. . The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and the stirrer was rotated.

Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.19 MPa (gauge pressure). Subsequently, methylaluminoxane prepared in advance was converted to 1 mmol in terms of Al, diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium dichloride. The toluene solution containing 0.01 mmol of 0.34 ml of the solution was pressed into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

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

[Synthesis Example 3]
50 ml of 4-methyl-1-pentene was charged at 23 ° C. into a SUS autoclave with a stirring blade having a capacity of 1.5 liters thoroughly purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAl), and the stirrer was rotated. Next, the autoclave was heated to an internal temperature of 30 ° C., pressurized with propylene so that the total pressure became 0.74 MPaG, and 12 Nml of hydrogen was added. Subsequently, methylaluminoxane prepared in advance, 1 mmol in terms of Al, diphenylmethylene (1-methyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) A toluene solution containing 0.35 ml of zirconium dichloride in an amount of 0.005 mmol was pressed into the autoclave with nitrogen to initiate polymerization. Thereafter, the temperature of the autoclave was adjusted to 60 ° C. for 60 minutes. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring. The resulting rubbery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 78.1 g, and the 4-methyl-1-pentene content in the polymer was 8.9 mol%, and the propylene content was 91.1 mol%.

[Synthesis Example 4]
750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a 1.5-liter stirring SUS autoclave sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAl), and the stirrer was rotated. Next, the autoclave was heated to an internal temperature of 30 ° C., pressurized with propylene so that the total pressure became 0.74 MPaG, and 12 Nml of hydrogen was added. Subsequently, methylaluminoxane prepared in advance, 1 mmol in terms of Al, diphenylmethylene (1-methyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) A toluene solution containing 0.35 ml of zirconium dichloride in an amount of 0.005 mmol was pressed into the autoclave with nitrogen to initiate polymerization. Thereafter, the temperature of the autoclave was adjusted to 60 ° C. for 60 minutes. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring. The resulting rubbery polymer containing the solvent was dried at 130 ° C. under reduced pressure for 12 hours. The obtained polymer was 56.3 g, and the 4-methyl-1-pentene content in the polymer was 24.7 mol%, and the propylene content was 75.3 mol%.

[Synthesis Example 5]
750 ml of 4-methyl-1-pentene was charged at 23 ° C. into a 1.5-liter stirring SUS autoclave sufficiently purged with nitrogen. The autoclave was charged with 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL), and stirring was started.

Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure was 0.17 MPa (gauge pressure). Subsequently, methylaluminoxane prepared in advance, 1 mmol in terms of Al, diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-butyl-fluorenyl) zirconium Polymerization was initiated by injecting 0.34 ml of a toluene solution containing 0.005 mmol of dichloride into an autoclave with nitrogen. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C. Sixty minutes after the start of polymerization, 5 ml of methanol was injected into the autoclave with nitrogen to stop the polymerization, and the autoclave was depressurized to atmospheric pressure. Acetone was poured into the reaction solution with stirring.

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

Table 1 shows the physical properties of the copolymers obtained in the above synthesis examples.

[Example 1]
20 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer (HSBR) manufactured by JSR Corporation) ) 80 parts by weight, 0.2 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer was blended. The obtained mixture was molded as a pressure-sensitive adhesive resin composition with a three-type 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 when obtaining the laminate are as described in the above section “Molding the laminate”. Various physical properties are shown in Table 2.

[Example 2]
30 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer (HSBR) manufactured by JSR Corporation) ) 70 parts by weight, 0.2 parts by weight of n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propinate as a heat stabilizer was blended. The resulting mixture was used as a pressure-sensitive adhesive resin composition, and then molded with a three-layer / 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 when obtaining the laminate are as described in the above section “Molding the laminate”. Various physical properties are shown in Table 2.

[Example 3]
In the pressure-sensitive adhesive layer, 30 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation (Compound (HSBR)) Instead of using 70 parts by weight, 50 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (manufactured by JSR Corporation) Hydrogenated styrene / butadiene / styrene copolymer (HSBR)) A pressure-sensitive adhesive resin composition sample was prepared and molded in the same manner as in Example 2 except that the amount was changed to 50 parts by weight. The physical properties of the laminate were measured. Various physical properties are shown in Table 2.

[Comparative Example 1]
In the pressure-sensitive adhesive layer, 20 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation Example 1 Except for using 100 parts by weight of Dynalon (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Corporation instead of using 80 parts by weight of coalesced (HSBR). In the same manner as described above, a pressure-sensitive adhesive resin composition sample was prepared and molded, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 3.

[Comparative Example 2]
In the pressure-sensitive adhesive layer, 30 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation Example 2 except that 70 parts by weight of union (HSBR)) 100 parts by weight of Dynalon (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Corporation was used. In the same manner as described above, a pressure-sensitive adhesive resin composition sample was prepared and molded, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 3.

[Comparative Example 3]
In the pressure-sensitive adhesive layer, 30 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation (HSBR)) Similar to Example 2 except that 100 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 was used instead of 70 parts by weight. The operation was performed to prepare and mold a pressure-sensitive adhesive resin composition sample, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 3.

[Comparative Example 4]
In the pressure-sensitive adhesive layer, 30 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation Combined (HSBR)) Similar to Example 2, except that 100 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 2 was used instead of 70 parts by weight. The operation was performed to prepare and mold a pressure-sensitive adhesive resin composition sample, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 3.

[Example 4]
In the pressure-sensitive adhesive layer, 20 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation (HSBR) Instead of using 80 parts by weight, 5 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 2 and Dynalon (registered trademark) 1320P (water) manufactured by JSR Corporation Preparation and molding of a pressure-sensitive adhesive resin composition sample by performing the same operation as in Example 1 except that 95 parts by weight of styrene / butadiene / styrene copolymer (HSBR)) was used, and the resulting laminate was obtained. The physical properties of the body were measured. Various physical properties are shown in Table 2.

[Example 5]
20 parts by weight of the 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 is added to 20 parts by weight of the 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 2 Except that it was changed to, the same operation as in Example 1 was performed to prepare and mold the pressure-sensitive adhesive resin composition sample, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 2.

[Example 6]
In the pressure-sensitive adhesive layer, 30 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation Copolymer (HSBR)) Instead of using 70 parts by weight, 30 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Shibustar (registered trademark) manufactured by Kaneka Corporation The same procedure as in Example 2 was performed except that 70 parts by weight of 062M (styrene / isobutylene / styrene copolymer (SIBS)) was used, and a pressure-sensitive adhesive resin composition sample was prepared and molded. The physical properties of the laminated body were measured. Various physical properties are shown in Table 2.

[Example 7]
80 parts by weight of Dynalon (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Corporation, and Evolue (registered trademark) SP0540 (ethylene-octene copolymer (LLDPE) manufactured by Prime Polymer Co., Ltd.) )) Except having been changed to 80 parts by weight, the same operation as in Example 1 was performed to prepare and mold a pressure-sensitive adhesive resin composition sample, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 4.

[Example 8]
80 parts by weight of Dynalon (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Corporation, and Tafmer (registered trademark) PN-2060 (propylene elastomer (TPO) manufactured by Mitsui Chemicals, Inc.) Except for changing to 80 parts by weight, the same operation as in Example 1 was performed to prepare and mold a pressure-sensitive adhesive resin composition sample, and the physical properties of the obtained laminate were measured. Shown in

[Example 9]
80 parts by weight of Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer (HSBR)) manufactured by JSR Corporation is added to 80 parts by weight of Prime Polypro (registered trademark) MF257 (PP)) manufactured by Prime Polymer Co., Ltd. Except having changed, operation similar to Example 1 was performed, the adhesive resin composition sample was prepared and shape | molded, and the physical property of the obtained laminated body was measured. Various physical properties are shown in Table 4.

[Example 10]
4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 2 instead of 20 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 20 Except having used the weight part, operation similar to Example 8 was performed, the adhesive resin composition sample was prepared and shape | molded, and the physical property of the obtained laminated body was measured. Various physical properties are shown in Table 4.

[Comparative Example 5]
In the pressure-sensitive adhesive layer, 20 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation Instead of using 80 parts by weight of coalescence (HSBR), 80 parts by weight of Dynalon (registered trademark) 1320P (hydrogenated styrene-butadiene-styrene copolymer (HSBR)) manufactured by JSR Corporation and Mitsui Chemicals Toughmer (registered) The same operation as in Example 1 was performed except that 20 parts by weight of PN-2060 (trademark) was used, and a pressure-sensitive adhesive resin composition sample was prepared and molded, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 5.

[Comparative Example 6]
In the pressure-sensitive adhesive layer, 20 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation (Unified (HSBR)) Instead of using 80 parts by weight, except that 80 parts by weight of Prime Polymer Co., Ltd. Evolue (registered trademark) SP0540 and 20 parts by weight of Mitsui Chemicals Co., Ltd., Tafmer (registered trademark) PN-2060 were used. The same operation as in Example 1 was performed to prepare and mold an adhesive resin composition sample, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 5.

[Comparative Example 7]
In the pressure-sensitive adhesive layer, 20 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation Combined (HSBR)) Instead of using 80 parts by weight, the same procedure as in Example 1 was performed except that 100 parts by weight of Mitsui Chemicals Co., Ltd. Tafmer (registered trademark) PN-2060 was used. A physical sample was prepared and molded, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 5.

[Comparative Example 8]
In the pressure-sensitive adhesive layer, 20 parts by weight of 4-methyl-1-pentene / α-olefin copolymer obtained in Synthesis Example 1 and Dynalon (registered trademark) 1320P (hydrogenated styrene / butadiene / styrene copolymer) manufactured by JSR Corporation Instead of using 80 parts by weight of coalescence (HSBR), 80 parts by weight of Mitsui Chemicals Co., Ltd. Sex Tafmer (registered trademark) PN-2060 and Dynalon (registered trademark) 1320P manufactured by JSR Corporation (both hydrogenated styrene / butadiene / styrene) Polymer (HSBR)) Except for using 20 parts by weight, the same operation as in Example 1 was performed to prepare and mold a pressure-sensitive adhesive resin composition sample, and the physical properties of the obtained laminate were measured. Various physical properties are shown in Table 5.

Claims (6)

1. 2 to 50 parts by weight of 4-methyl-1-pentene / α-olefin copolymer (A) satisfying the following requirements (a), (b), (c) and (d):
   At least one pressure-sensitive adhesive layer comprising a resin composition containing 98 to 50 parts by weight of a thermoplastic resin (B) other than the 4-methyl-1-pentene / α-olefin copolymer (A);
   A base material layer;
   Surface protective film comprising a laminate having the above (wherein the total of the 4-methyl-1-pentene / α-olefin copolymer (A) and the thermoplastic resin (B) is 100 parts by weight):
   (A) 65 to 90 mol% of the structural unit (i) derived from 4-methyl-1-pentene and a structural unit derived from an α-olefin (excluding 4-methyl-1-pentene) (ii ) From 35 to 10 mol%;
   (B) the intrinsic viscosity [η] measured at 135 ° C. in decalin is 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) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.0 to 3.5. It is in;
   (D) The density is in the range of 870 to 830 kg / m ³ .
2. The surface protective film according to claim 1, wherein, in the requirement (a), the proportion of the structural unit (i) is 80 to 90 mol% and the proportion of the structural unit (ii) is 20 to 10 mol%.
3. The surface protective film according to claim 1 or 2, wherein the thermoplastic resin (B) is a styrene elastomer (B2).
4. The surface protective film according to any one of claims 1 to 3, wherein the laminate is a multilayer film obtained by a T-die film molding method.
5. A method for protecting a surface having a surface irregularity height of 0.1 to 300 μm using the surface protective film according to claim 3.
6. A method for protecting a prism sheet using the surface protective film according to claim 3.