JP2008231264A - Self-adhesive film for surface protection - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a self-adhesive film for surface protection including a new self-adhesive layer having excellent balance between blocking resistance and self-adhesiveness. <P>SOLUTION: The adhesive film for surface protection includes the self-adhesive layer comprising an ethylene-based copolymer obtained by copolymerizing ethylene with a 4-10C α-olefin and simultaneously satisfying the following requirements (1)-(4): (1) a melt flow rate in a specific range, (2) density in a specific range, (3) a weight average molecular weight in a specific range and (4) a ratio (H/W) of the height (H) of a peak having the most strong peak intensity over a width (W) at 1/2 height of the peak and the density (D) satisfy a certain relative equation depending on values of the melt flow rate in an elution curve obtained by temperature rising elution fractionation (TREF). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive film for surface protection. More specifically, the present invention relates to a pressure-sensitive adhesive film for surface protection comprising a pressure-sensitive adhesive layer having a good balance between blocking resistance and pressure-sensitive adhesiveness.

  Ethylene copolymers are molded by various molding methods and are used for various purposes. Various ethylene-based copolymers that are characterized by moldability and molded product performance have been developed.

  High-pressure low-density polyethylene is used for applications such as films and hollow containers because of its high melt tension and good moldability. However, the high-pressure low-density polyethylene has a problem that it has inferior mechanical strength such as tensile strength, tear strength or impact strength because it has many long-chain branched structures.

  The ethylene-based copolymer obtained using a Ziegler catalyst is superior in mechanical strength such as tensile strength, tear strength or impact strength strength as compared with high pressure method low density polyethylene. However, since the composition distribution is wide, a molded article such as a film is sticky, resulting in poor blocking resistance. If the density of the ethylene copolymer is increased, the blocking resistance is improved, but in that case, there is a problem that the low-temperature heat sealability and flexibility are deteriorated.

In order to solve such problems, various ethylene copolymers using a metallocene catalyst which is a homogeneous catalyst (single site catalyst) have been disclosed.
Patent Document 1 (Japanese Patent Laid-Open No. 2005-97481) discloses an ethylene copolymer obtained by gas phase polymerization in the presence of a catalyst comprising racemic-ethylenebis (1-indenyl) zirconium diphenoxide. (Japanese Patent Laid-Open No. 9-111208) discloses an ethylene copolymer obtained by using a metallocene compound as a polymerization catalyst (trade name EXACT, manufactured by Exxon Chemical Co., Ltd.) and Patent Document 3 (Japanese Patent Laid-Open No. 11-269324). ) Includes ethylene-bis (
An ethylene copolymer obtained by high-pressure ion polymerization in the presence of a catalyst comprising 4,5,6,7-tetrahydroindenyl) zirconium dichloride and methylalumoxane is disclosed in JP-A-2002-3661. (Patent Publication) discloses an ethylene copolymer obtained using a catalyst comprising bis (n-butylcyclopentadienyl) zirconium dichloride and methylalumoxane. Although these ethylene copolymers have a narrower composition distribution than ethylene copolymers obtained using conventional Ziegler catalysts, the composition distribution is still wide to completely eliminate blocking properties. . For this reason, there was a lot of residue to use as an adhesive film for surface protection using these as an adhesive layer.

As a result of studies conducted in view of such circumstances, the present inventor has found that a specific MFR range and a specific density range are satisfied, a molecular weight distribution satisfies a specific range, and is defined by a temperature rising elution fractionation (TREF). An ethylene-based copolymer in which W and density satisfy a specific relationship, and [η] and MFR satisfy a specific relationship, is particularly excellent in blocking resistance and adhesiveness as a molded body, and has mechanical strength. As a result, the present invention has been completed.
JP 200597481 A JP-A-9-111208 JP-A-11-269324 JP 2002-3661 A

  The present invention provides a pressure-sensitive adhesive film for surface protection comprising a novel pressure-sensitive adhesive layer having a good balance between blocking resistance and pressure-sensitive adhesive properties as compared with a conventionally known surface protective pressure-sensitive adhesive film. It is aimed.

  The present inventors have found that a surface protecting adhesive film having an adhesive layer made of a specific ethylene copolymer has an excellent balance between blocking resistance and adhesiveness. That is, the present invention is as follows.

  A surface comprising an adhesive layer made of an ethylene copolymer that simultaneously satisfies the following requirements (I) to (IV), obtained by copolymerizing ethylene and an α-olefin having 4 to 10 carbon atoms: It is a protective adhesive film.

(I) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.10 to 50 g / 10 min.
(II) The density (D) is in the range of 860 to 930 kg / m ³ .

(III) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is in the range of 1.50 to 3.00.
(IV) In the elution curve obtained by temperature rising elution fractionation (TREF), the ratio (H) of the peak height (H) having the strongest peak intensity to the width (W) at half the height of the peak (H / W) and density (D) satisfy any of the following relational expressions (Eq-1) to (Eq-3) according to the MFR value of requirement (I).

[When 0.10 ≦ MFR ≦ 1.00]
0.0163 × D-14.00 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.21
... (Eq-1)
[If 1.00 <MFR ≦ 10.0]
0.0163 × D-14.02 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.30
... (Eq-2)
[If 10.0 <MFR ≦ 50]
0.0163 × D-14.10 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.40
... (Eq-3)
Moreover, it is preferable that the adhesion layer of this invention satisfy | fills the following requirements (V) further.

(V) The intrinsic viscosity [[η] (dl / g)] measured in decalin at 135 ° C. and the melt flow rate (MFR) satisfy the following relational expression (Eq-4).
−0.21 × Log ₁₀ MFR + 0.16 ≦ Log ₁₀ [η] ≦ −0.21 × Log ₁₀ M
FR + 0.31 (Eq-4)

  The present invention can provide an adhesive film for surface protection including an adhesive layer excellent in the balance between blocking resistance and adhesiveness.

Next, the surface protecting adhesive film of the present invention will be specifically described.
The pressure-sensitive adhesive film for surface protection of the present invention is characterized in that it comprises a pressure-sensitive adhesive layer comprising the following specific ethylene copolymer and at least one kind of base material layer.

[Ethylene copolymer]
The ethylene-based copolymer according to the present invention is a copolymer of ethylene and an α-olefin having 4 to 10 carbon atoms, preferably ethylene and an α-olefin having 6 to 10 carbon atoms. Examples of the α-olefin having 4 to 10 carbon atoms used for copolymerization with ethylene include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. When the α-olefin has 4 or more carbon atoms, the probability that the α-olefin is incorporated into the crystal is low (Polymer, VOL31, 1999, 1999), and thus the mechanical strength is excellent. When the number of carbon atoms of the α-olefin is 10 or less, the flow activation energy is small, and the viscosity change during molding is small.

The type of α-olefin in the ethylene copolymer is usually a ¹³ C-NMR spectrum of a feed in which about 200 mg of the ethylene copolymer is uniformly dissolved in 1 ml of hexachlorobutadiene in a 10 mmφ sample tube. It can be identified by measuring under measurement conditions of 120 ° C., frequency 25.05 MHz, spectrum width 1500 Hz, pulse repetition time 4.2 seconds, and 45 ° pulse width 6 μsec.

Such an ethylene copolymer satisfies the following requirements (I) to (IV).
(I) Melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is 0.1.
0-50 g / 10 min, preferably 0.50-30.0 g / 10 min, more preferably 1.0
The range is 0 to 20.0 g / 10 minutes.

When the melt flow rate (MFR) of the ethylene copolymer is 0.10 g / 10 min or more, the shear viscosity is not too high and the moldability is good. Further, when the melt flow rate (MFR) is 50 g / 10 minutes or less, the resulting ethylene copolymer has good tensile strength.

The melt flow rate (MFR) strongly depends on the molecular weight. The smaller the melt flow rate (MFR), the larger the molecular weight, and the larger the melt flow rate (MFR), the smaller the molecular weight. Further, it is known that the molecular weight of an ethylene copolymer is determined by the composition ratio (hydrogen / ethylene) of hydrogen and ethylene in the polymerization system (for example, Kazuo Saga, KODASHA “CATALITY OLEFIN PO”).
LYMERIZATION ", p. 376 (1990)) For this reason, an ethylene copolymer having a melt flow rate (MFR) that is the upper limit or lower limit of the requirement (I) of the present invention is produced by increasing / decreasing hydrogen / ethylene. Is possible.

In the present invention, the melt flow rate (MFR) is a value measured under conditions of 190 ° C. and 2.16 kg load according to ASTM D1238-89.
(II) Density (D) is 860 to 930 kg / m ³ , preferably 870 to 925 kg /
m ³ , more preferably 875-920 kg / m ³ , particularly preferably 880-920 kg / m
It is in the range of m ³ .

When the density (D) is 860 kg / m ³ or more, the resulting ethylene copolymer has good blocking resistance, and when the density (D) is 930 kg / m ³ or less, the obtained ethylene copolymer Good low-temperature sealability of coalescence.

The density depends on the α-olefin content of the ethylene copolymer. The smaller the α-olefin content, the higher the density, and the higher the α-olefin content, the lower the density. In addition, it is known that the α-olefin content in the ethylene copolymer is determined by the composition ratio (α-olefin / ethylene) of the α-olefin and ethylene in the polymerization system (for example, Walter Kaminsky, Makromol. Chem. 193, 606 (1992)). For this reason, by increasing / decreasing α-olefin / ethylene, the requirement of the present invention (
It is possible to produce an ethylene-based copolymer having a density from the upper limit to the lower limit of II).

Density (D) is a pre-heating temperature of 190 ° C., a pre-heating time of 5 minutes, a heating temperature of 190 ° C., a heating time of 2 minutes, a heating pressure of 100 kg / cm ² , a cooling temperature of 20 ° C. Thickness of 0.5 mm formed by press molding under conditions of cooling time of 5 minutes and cooling pressure of 100 kg / cm ²
It is obtained by measuring with a density gradient tube using a press sheet of mm as a measurement sample.

(III) The ratio (Mw / Mn) between the weight average molecular weight and the number average molecular weight measured by GPC is 1.50 or more and 3.00 or less, preferably 1.50 or more and 2.50 or less, more preferably 1.5.
It is in the range of 0 to 2.20, particularly preferably 1.60 to 2.10.

  When Mw / Mn is 1.50 or more, the moldability of the resulting ethylene copolymer is good. When Mw / Mn is 3.00 or less, the impact strength of the resulting ethylene copolymer is good. is there.

In this invention, ratio (Mw / Mn) of a weight average molecular weight and a number average molecular weight was measured as follows using GPC-150C by Waters. Separation column is TSKgel
GMH6-HT and TSKgel GMH6-HTL, the column size is 7.5 mm in inner diameter and 600 mm in length, the column temperature is 140 ° C., the mobile phase is o-dichlorobenzene (Wako Pure Chemical Industries) and oxidation BHT (Takeda Pharmaceutical) 0.025 wt% was used as an inhibitor, moved at 1.0 ml / min, the sample concentration was 0.1 wt%, the sample injection volume was 500 μL, and a differential refractometer was used as the detector. Was used. The standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw ≦ 1000 and Mw ≧ 4 × 10 ⁶ , and manufactured by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ . The molecular weight calculation is a value calibrated to polyethylene after universal calibration.

(IV) In the elution curve obtained by temperature rising elution fractionation (TREF), the ratio (H) of the peak height (H) having the strongest peak intensity to the width (W) at half the height of the peak (H / W) and density (D) satisfy any of the following relational expressions (Eq-1) to (Eq-3) according to the MFR value of requirement (I).

[When 0.10 ≦ MFR ≦ 1.00]
0.0163 × D-14.00 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.21
... (Eq-1)
[If 1.00 <MFR ≦ 10.0]
0.0163 × D-14.02 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.30
... (Eq-2)
[10.0 <MFR ≦ 50]
0.0163 × D-14.10 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.40
(Eq-3)
Preferably, any one of the following relational expressions (Eq-1 ′) to (Eq-3 ′) is satisfied.
[When 0.10 ≦ MFR ≦ 1.00]
0.0163 × D-13.83 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.21
... (Eq-1 ')
[If 1.00 <MFR ≦ 10.0]
0.0163 × D-13.92 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.30
... (Eq-2 ')
[10.0 <MFR ≦ 50]
0.0163 × D-14.02 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.40
... (Eq-3 ')
In temperature rising elution fractionation (TREF), a component having a higher α-olefin content is eluted at a lower temperature, and a component having a lower α-olefin content is eluted at a higher temperature. H / W is the height (H) of the peak with the strongest peak intensity and the width (W) at half the height of the peak with the strongest peak in the elution curve obtained by temperature rising elution fractionation (TREF). Therefore, when compared with an ethylene copolymer having the same density, the larger the H / W, the more uniformly the α-olefin is introduced into the molecular chain, and the composition distribution becomes narrower. Therefore, Log ₁₀ (H / W) is 0.0163 × D-13.83 or more when 0.10 ≦ MFR ≦ 1.00, and 0.0163 when 1.00 <MFR ≦ 10.0. When D × 13.92 or more and 10.0 ≦ MFR ≦ 50, 0.0163 × D-14.02 or more, the composition distribution of the resulting ethylene copolymer is narrow, and no sticky component is generated. Excellent in blocking resistance.

It is known that H / W strongly depends on the composition distribution of the obtained ethylene-based copolymer, and this composition distribution becomes narrower when the active sites of the catalyst become uniform and becomes wider when the catalyst becomes nonuniform. .
In the present invention, H / W was determined as follows.

First, the elution curve by temperature rise elution fractionation (TREF) was measured as follows using a cross fractionation chromatograph CFCF-150A manufactured by Mitsubishi Oil Chemical Co., Ltd. A measurement sample was used at 140 ° C. using a solvent (o-dichlorobenzene) so that the concentration was 4 mg / ml.
And is injected into the sample loop in the measuring device. The sample solution is injected into a TREF separation column (a stainless steel column attached to the apparatus filled with glass beads as an inert carrier, a volume of 0.88 ml, a pipe capacity of 0.07 ml). Next, the sample solution is cooled from 140 ° C. to 0 ° C. at a rate of 1 ° C./min, and coated on an inert carrier. At this time, a polymer layer is formed on the surface of the inert carrier in the order of the high crystalline component to the low crystalline component. After the TREF separation column was held at 0 ° C. for another 30 minutes, 2 ml of the component dissolved at the temperature of 0 ° C. was transferred from the TREF separation column to the SEC separation column (Showex Electric Corporation Shodex AT) at a flow rate of 1 ml / min. -806MS x 3). While the molecular size fractionation is performed in the SEC separation column, the temperature is raised to the next elution temperature (5 ° C.) in the TREF separation column, and the temperature is maintained for about 30 minutes. The elution temperature is raised stepwise at the following temperature.

[Elution temperature] 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 49, 52, 55, 58, 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 102, 120, 140 ° C
The molecular weight of the components eluted at each temperature was measured, and the molecular weight of polyethylene was determined using a general calibration curve. The SEC temperature is 140 ° C. and the data sampling time is 0.50 seconds. The sample solution that has passed through the SEC separation column is measured for absorbance in proportion to the polymer concentration with an infrared spectrophotometer (wavelength: 3.42 μm, 2924 cm ⁻¹ ), and a chromatogram of each elution temperature section is obtained. Using the built-in data processing software, the base line of the chromatogram of each elution temperature segment obtained by the above measurement is drawn and processed. The area of each chromatogram is integrated and an integrated elution curve is calculated. Also, the differential elution curve is calculated by differentiating the integral elution curve with temperature.

Next, the differential elution curve obtained is plotted with the elution temperature on the horizontal axis of 89.3 m per 100 ° C.
m, the vertical axis is the differential amount (the total integral elution amount is standardized to 1.0, and the amount of change at 1 ° C. is the differential amount), and the peak height of this differential elution curve is 0.16.5 mm. A value obtained by dividing (mm) by a width (mm) of ½ height was defined as H / W.

It is preferable that the ethylene copolymer according to the present invention further satisfies the following requirement (V) in addition to the above requirements (I) to (IV).
(V) The intrinsic viscosity [[η] (dl / g)] measured in 135 ° C. decalin and the melt flow rate (MFR) with a load of 2.16 kg at 190 ° C. are expressed by the following relational expression (Eq-4). Fulfill.

−0.21 × Log ₁₀ MFR + 0.16 ≦ Log ₁₀ [η] ≦ −0.21 × Log ₁₀ MFR + 0.31 (Eq-4)
It is known that the relationship between the intrinsic viscosity ([η]) and the melt flow rate (MFR) is strongly governed by the long chain branching structure in the molecular chain (for example, Kenzo Hirayama, Polymer Chemistry, Vol. 28, No. 310, pp. 156-160 (1971)). When comparing ethylene-based copolymers having the same melt flow rate (MFR), when long chain branching is introduced, the molecular chain spread in the solution is reduced, and the intrinsic viscosity ([η]) is reduced. When Log ₁₀ [η] is (−0.21 × Log ₁₀ MFR + 0.26) or more, long chain branching does not exist in the molecular chain, and thus the tear strength is excellent.

Accordingly, with regard to requirement (V), when the ethylene-based copolymer is developed for use as a molded product, a preferred embodiment is divided into two depending on what characteristics are required. That is, the short chain branch resulting from the α-olefin that is subjected to the copolymerization reaction together with ethylene (for example, when 1-butene is used as the α-olefin, an ethyl group is introduced as a short chain branch). An ethylene copolymer that has a branched structure and contains almost no long-chain branched structure formed via a macromonomer having a vinyl group at the end (hereinafter abbreviated as “short-chain branched ethylene-based copolymer”) Is desirable, an ethylene-based copolymer satisfying the range represented by the following relational expression (Eq-4a) is preferable.

−0.21 × Log ₁₀ MFR + 0.26 ≦ Log ₁₀ [η] ≦ −0.21 × Log ₁₀ MFR + 0.31 (Eq−4a)
On the other hand, an ethylene copolymer containing a small amount of a long-chain branched structure content produced via a macromonomer (hereinafter sometimes abbreviated as “long-chain branched ethylene-based copolymer”) is desired. In such a case, an ethylene copolymer satisfying a range represented by the following relational expression (Eq-4b) is preferable. Such long-chain branched ethylene-based copolymers exhibit higher elasticity against slow deformation in the molten state than short-chain branched ethylene-based copolymers, and in fields where good moldability is required. You can apply it as you like.

−0.21 × Log ₁₀ MFR + 0.16 ≦ Log ₁₀ [η] <− 0.21 × Log ₁₀ MFR + 0.26 (Eq−4b)
In the case of coordination polymerization as in the examples described later, the long-chain branched structure in the ethylene-based copolymer is reinserted with a molecular chain (macromonomer) having a terminal vinyl group generated by a β-hydrogen elimination reaction. It is thought to generate by doing. Therefore, increasing or decreasing the ratio of macromonomer concentration to ethylene concentration ([macromonomer] / [ethylene]) in the solution increases or decreases the amount of long chain branching in the ethylene copolymer. It is possible to produce an ethylene copolymer having an intrinsic viscosity [η] that is the upper limit or the lower limit of the requirement (V) of the invention. Generally, when [macromonomer] / [ethylene] is high, the amount of long chain branching in the ethylene copolymer increases, and when [macromonomer] / [ethylene] is low, the long chain branching in the ethylene copolymer is increased. The amount drops. Specific methods for increasing / decreasing [macromonomer] / [ethylene] in the solution include the following methods.

[1] Polymerization temperature The higher the polymerization temperature, the more likely the β-hydrogen elimination reaction occurs. Therefore, if the polymerization temperature is increased, [macromonomer] / [ethylene] increases and the amount of long chain branching in the ethylene copolymer increases.

[2] Polymer concentration If the polymer concentration in the solution is increased, the macromonomer concentration is also relatively increased. Therefore, [macromonomer] / [ethylene] increases, and the amount of long chain branching in the ethylene copolymer is To increase.

[3] Ethylene conversion rate If the ethylene conversion rate is increased, the ethylene concentration in the solution decreases, so [macromonomer] / [ethylene] increases and the amount of long chain branching in the ethylene copolymer increases. .

[4] Solvent type When the polymerization solvent is a low-boiling solvent, the ethylene concentration in the solution decreases, so [macromonomer] / [ethylene] increases and the amount of long-chain branching in the ethylene copolymer increases. To do.

  In addition to controlling the β-hydrogen elimination reaction, the [macromonomer] / [ethylene]) can be increased or decreased by controlling the chain transfer reaction to Al, etc., and long chain branching in the ethylene copolymer The amount can also be changed.

The intrinsic viscosity [[η] (dl / g)] was measured using a decalin solvent as follows. About 20 mg of an ethylene copolymer is dissolved in 15 ml of decalin, and the specific viscosity η _SP is 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 is measured in the same manner. This dilution operation is further repeated twice, and the value of η _SP / C when the concentration (C) is extrapolated to 0 is determined as the intrinsic viscosity. That is, the intrinsic viscosity [η] is represented by the following formula.

[η] = lim (η _SP / C) (C → 0)
[Polymerization catalyst]
The ethylene copolymer according to the present invention includes, for example, (A) a crosslinked metallocene compound represented by the following general formula [I], and (B) (b-1) an organoaluminum oxy compound,
(B-2) at least one compound selected from (b-3) a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound. In the presence of a catalyst for olefin polymerization comprising: one or more monomers selected from ethylene and α-olefin at a temperature of 120 to 300 ° C. in the presence of a solvent (in the following description, “high temperature solution polymerization”). It may be referred to as “.”). However, the method for producing an ethylene copolymer according to the present invention is not limited to the above production method as long as the ethylene copolymer defined in the claims of the present application is satisfied. For example, a metallocene compound having a structure different from that of the general formula [I] may be used, a promoter different from the component (B) may be used, or two or more known ethylene copolymers may be used. May be prepared by techniques such as reactor blending or physical blending.

(In the above general formula [I], M represents a transition metal, p represents the valence of the transition metal, X may be the same or different, and each represents a hydrogen atom, a halogen atom or a hydrocarbon group, R ¹ and R ² represent a π-electron conjugated ligand coordinated to M, which may be the same or different, and Q represents a divalent bridge that bridges ^two π-electron conjugated ligands R ¹ and R ^2. Represents a group of
In the general formula [I], examples of the transition metal represented by M include Zr, Ti, Hf, V, Nb, Ta, and Cr. Preferred transition metals are Zr, Ti, and Hf, and more preferable. The transition metal is Zr or Hf.

In the general formula [I], π-electron conjugated ligands represented by R ¹ and R ² include η-cyclopentadienyl structure, η-benzene structure, η-cycloheptatrienyl structure, and η-cyclo Examples thereof include a ligand having an octatetraene structure, and a particularly preferable ligand is a ligand having a η-cyclopentadienyl structure. Examples of the ligand having an η-cyclopentadienyl structure include a cyclopentadienyl group, an indenyl group, a hydrogenated indenyl group, and a fluorenyl group. These groups are further substituted with a hydrocarbon group such as a halogen atom, alkyl, aryl, aralkyl, alkoxy or aryloxy, a hydrocarbon group-containing silyl group such as a trialkylsilyl group, a chain or cyclic alkylene group, etc. Also good.

In general formula [I], the group that crosslinks R ¹ and R ² represented by Q is not particularly limited as long as it is a divalent group. For example, a linear or branched alkylene group, unsubstituted or Examples thereof include a substituted cycloalkylene group, an alkylidene group, an unsubstituted or substituted cycloalkylidene group, an unsubstituted or substituted phenylene group, a silylene group, a dialkyl-substituted silylene group, a germyl group, and a dialkyl-substituted germyl group.

  In the examples described later, metallocene complexes represented by di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride are used as metallocene compounds satisfying the above general formula [I]. Although used, the metallocene compound according to the present invention is not limited to this.

Next, a preferable embodiment when the metallocene compound (A) described above is used as a polymerization catalyst component for producing the ethylene copolymer of the present invention will be described.
When the metallocene catalyst containing the metallocene compound (A) is used as an olefin polymerization catalyst for producing an ethylene copolymer, the polymerization catalyst is represented by (A) the above general formula [I] as described above. A metallocene compound, and (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) an organoaluminum compound. Preferably, it is composed of at least one compound. Here, as the catalyst component (B), any one of the following [c1] to [c4] is preferably used from the viewpoint of polymerization activity and properties of the produced olefin polymer.

[C1] (b-1) Organoaluminum oxy compound only,
[C2] (b-1) an organoaluminum oxy compound and (b-3) an organoaluminum compound,
[C3] (b-2) a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound,
[C4] (b-1) A compound that reacts with the organoaluminum oxy compound and (b-2) the metallocene compound (A) to form an ion pair.

However, when a metallocene compound in which Q is a silylene group in the general formula [I] is used as the component (A), the component (B-2) is an ion that reacts with the metallocene compound (A) (b-2). A compound that forms a pair is not used. Therefore, only [c1] and [c2] are adopted also in the above-mentioned preferable component (B), [c1] to [c4].

Hereinafter, each component which can comprise (B) component is demonstrated concretely.
(B-1) Organoaluminum oxy compound As the organoaluminum oxy compound (b-1), a conventionally known aluminoxane can be used as it is. Specifically, the following general formula [II] and / or general formula [III]

(In the formula [II] or [III], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.) In particular, R is a methyl group. A methylaluminoxane having n of 3 or more, preferably 10 or more is used. (The organoaluminumoxy compound in which R is a methyl group in the general formula [II] or [III] may be referred to as “methylaluminoxane” hereinafter.)
Methylaluminoxane is an organoaluminum oxy compound that has been widely used in the polyolefin industry due to its availability and high polymerization activity, but it is difficult to dissolve in saturated hydrocarbons, and it has a huge environmental impact, such as toluene and benzene. Has been used as an aromatic hydrocarbon solution. Under such circumstances, methylaluminoxane analogues that are soluble in saturated hydrocarbons have been developed. Examples of such analogs include modified methylaluminoxanes represented by the following general formula [IV]. In the present invention, such a modified methylaluminoxane is also included as the organoaluminum oxy compound (b-1).

(In the formula [IV], R represents a hydrocarbon group having 2 to 20 carbon atoms, and m and n represent an integer of 2 or more.)
The modified methylaluminoxane represented by the general formula [IV] is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum (for example, disclosed in US4960878, US5041584, etc.), and trimethyl from a manufacturer such as Tosoh Finechem. Those prepared using aluminum and triisobutylaluminum and having R as an isobutyl group are commercially produced under trade names such as MMAO and TMAO (see, for example, “Tosoh Research and Technical Report” Vol. 47, 55 (2003)). ). However, the present applicant has confirmed that even if MMAO or TMAO is polymerized in the form of a saturated hydrocarbon solution outside the technical scope of the high-temperature solution polymerization method of the present invention, the activity exceeding methylaluminoxane cannot be achieved. . According to the high temperature solution polymerization method according to the present invention, high polymerization activity is exhibited even when a saturated hydrocarbon solution of the modified aluminoxane represented by the general formula [IV] is used.

  In the high temperature solution polymerization according to the present invention, a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687 can also be applied as the organoaluminum oxy compound (b-1).

  Furthermore, examples of the organoaluminum oxy compound (b-1) used in the present invention include an organoaluminum oxy compound containing boron represented by the following general formula [V].

(In the formula [V], Rc represents a hydrocarbon group having 1 to 10 carbon atoms. Rd may be the same as or different from each other, and may be a hydrogen atom, a halogen atom or a carbon atom having 1 to 10 carbon atoms. Indicates a hydrogen group.)
Note that a slight amount of organoaluminum compound may be mixed in the above-described (b-1) organoaluminum oxy compound.
(B-2) Compound that reacts with metallocene compound (A) to form an ion pair Compound (b-2) that reacts with metallocene compound (A) to form an ion pair (hereinafter abbreviated as “ionic compound”) Are disclosed in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, Examples include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Kaihei 3-207704, USP5321106, and the like. Furthermore, examples of the ionic compound (b-2) include heteropoly compounds and isopoly compounds.

  In the present invention, the ionic compound (b-2) preferably employed is a compound represented by the following general formula [VI].

In the formula [VI], R ^{e +} includes H ⁺ , carbenium cation, oxonium cation,
Examples thereof include an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, and a ferrocenium cation having a transition metal. Rf to Ri may be the same or different from each other, and are an organic group, preferably an aryl group.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among these, as R ^{e +} , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

Specific examples of the ionic compound (b-2) that is a carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5- Examples thereof include ditrifluoromethylphenyl) borate, tris (4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbeniumtetrakis (pentafluorophenyl) borate.

Examples of the ionic compound (b-2) that is an ammonium salt include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.

Specific examples of the ionic compound (b-2) that is a trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, and trimethylammonium. Tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluoro) Phenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetra Kis (3,5-dimethylphenyl) borate, tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (N-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium Tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis ( , 5-dimethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, such as dioctadecyl methyl ammonium.

Specific examples of the ionic compound (b-2) that is an N, N-dialkylanilinium salt include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl), and the like. ) Borate, N, N-dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pen polyfluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-
Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate .

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pen polyfluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

As the other ionic compound (b-2), an ionic compound disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can be used without limitation.
Said ionic compound (b-2) may be used individually by 1 type, and 2 or more types may be mixed and used for it.
(B-3) Organoaluminum Compound Forming an Olefin Polymerization Catalyst (b-3) The organoaluminum compound is, for example, an organoaluminum compound represented by the following general formula [VII], represented by the following general formula [VIII] A complex alkylated product of a Group 1 metal and aluminum can be used.

R ^a _m Al (OR ^b ) _n H _p X _q ... [VII]
(In the formula [VII], R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <3, and m + n + p + q = 3.)
Specific examples of the organoaluminum compound represented by the general formula [VII] include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum; Tri-branched alkyl aluminum such as triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricyclohexylaluminum, tricyclooctyl Tricycloalkylaluminum such as aluminum; triarylaluminum such as triphenylaluminum and tolylylaluminum Miniumu; diisopropyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are located in the positive number , Z ≦ 2x
It is. Alkenyl aluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; Alkyl aluminum sesquialkoxides such as sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _{0.5 and the} like; diethylaluminum phenoxide, diethyl Alkyl aluminum compounds such as aluminum (2,6-di-t-butyl-4-methylphenoxide) Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides such as dichloride; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride and others Min hydrogenated alkyl aluminum, ethyl aluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, etc. partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide and the like.

M ² AlR ^a ₄ [VIII]
(In the formula [VIII], M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Complex alkylated product of Group 1 metal and aluminum. Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

A compound similar to the compound represented by the general formula [VII] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

From the viewpoint of easy availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
In the polymerization, the method of using each component and the order of addition are arbitrarily selected. For example, a method of adding the catalyst component (A) and the catalyst component (B) to the polymerization vessel in any order can be exemplified. .

In the said method, two or more of each catalyst component may be contacted previously.
When the ethylene-based copolymer of the present invention is produced by copolymerizing ethylene and an α-olefin having 4 to 10 carbon atoms using the olefin polymerization catalyst as described above, the catalyst component (A) is: The amount used is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² mol, per liter of reaction volume.

Component (b-1) has a molar ratio [(b-1) / M] of component (b-1) to all transition metal atoms (M) in component (A) usually from 0.01 to 5, 000, preferably 0.05 to 2,000. Component (b-2) has a molar ratio [(b-2) / M] of the aluminum atoms in component (b-2) to the total transition metals (M) in component (A) usually 10 to 10. 5,000
The amount is preferably 20 to 2,000. Component (b-3)
b-3) is used in such an amount that the molar ratio [(b-3) / M] of the transition metal atom (M) in the component (A) is usually 1 to 10,000, preferably 1 to 5000. It is done.

[Polymerization method]
In the high-temperature solution polymerization according to the present invention, copolymerization of ethylene and an α-olefin having 4 to 10 carbon atoms is performed in the presence of the metallocene catalyst as described above, thereby increasing the comonomer content and the composition distribution. An ethylene copolymer having a narrow molecular weight distribution can be efficiently produced. Here, the charged molar ratio of ethylene to the α-olefin having 4 to 10 carbon atoms is usually ethylene: α-olefin = 10: 90 to 99.9: 0.1, preferably ethylene: α-olefin = 30:70 to 99.9: 0.1, more preferably ethylene: α-olefin = 50: 50 to 99.9: 0.1.

Examples of the α-olefin having 4 to 10 carbon atoms include linear or branched α-olefins such as propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, and 1-hexene. Examples include 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and 1-degree lines. The α-olefin that can be used in the high-temperature solution polymerization of the present invention includes polar group-containing olefins. Examples of polar group-containing olefins include α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid and maleic anhydride, and metal salts such as sodium salts thereof; methyl acrylate, ethyl acrylate, Α, β-unsaturated carboxylic acid esters such as n-propyl acrylate, methyl methacrylate and ethyl methacrylate; vinyl esters such as vinyl acetate and vinyl propionate; unsaturated glycidyl such as glycidyl acrylate and glycidyl methacrylate And the like. Vinylcyclohexane, diene or polyene; aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, methyl vinylbenzoate Styrenes such as vinyl benzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene; and 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, etc. can coexist in the reaction system to proceed with high-temperature solution polymerization Is possible. Among the α-olefins described above, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferably used. In the high temperature solution polymerization method according to the present invention, cyclic olefins having 4 to 10 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, etc. may be used in combination. Good.

  “Solution polymerization” according to the present invention is a general term for methods in which polymerization is performed in a state where the polymer is dissolved in an inert hydrocarbon solvent described later at a temperature equal to or higher than the melting point of the polymer. In the solution polymerization according to the present invention, the polymerization temperature is usually 120 ° C. to 300 ° C., preferably 130 ° C. to 250 ° C., more preferably 130 ° C. to 200 ° C. As described above, in this specification, “high temperature solution polymerization” "

  In the high-temperature solution polymerization according to the present invention, when the polymerization temperature is less than 120 ° C., the polymerization activity is extremely lowered, so that it is not practical in terms of productivity. Further, in the polymerization temperature range of 120 ° C. or higher, as the temperature increases, the solution viscosity at the time of polymerization decreases, the heat of polymerization is easily removed, and the resulting olefin polymer can have a high molecular weight. However, if the polymerization temperature exceeds 300 ° C., the resulting polymer may be deteriorated, which is not preferable. Further, from the viewpoint of the properties of the ethylene-based copolymer that is preferably produced in the high temperature solution polymerization according to the present invention, the polymerization temperature is preferably used in many industrial fields such as a film in the region of 120 to 200 ° C., which will be described later. An ethylene copolymer can be produced efficiently. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 8 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the resulting ethylene copolymer can also be adjusted by changing the hydrogen concentration and polymerization temperature in the polymerization system within the scope of the present invention. Furthermore, it can also adjust with the quantity of the catalyst component (B) to be used. When hydrogen is added, the amount is suitably about 0.001 to 5,000 NL per 1 kg of the produced ethylene copolymer.

The solvent used in the high temperature solution polymerization according to the present invention is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50 ° C. to 200 ° C. under normal pressure. Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane are also included in the category of “inert hydrocarbon solvents” related to the high-temperature solution polymerization of the present invention. There is no limit. As described above, in the high temperature solution polymerization according to the present invention, MMAO that dissolves in aliphatic hydrocarbons and alicyclic hydrocarbons as well as conventionally used aromatic hydrocarbon-soluble organoaluminum oxy compounds. A modified methylaluminoxane can be used. As a result, if aliphatic hydrocarbons or alicyclic hydrocarbons are used as the solvent for the solution polymerization, the possibility of aromatic hydrocarbons mixing in the polymerization system or the ethylene copolymer produced is almost completely eliminated. It became possible to eliminate. That is, the high-temperature solution polymerization method according to the present invention has a feature that the environmental load can be reduced and the influence on human health can be minimized.

  In order to suppress variations in physical property values, the ethylene copolymer particles obtained by the polymerization reaction and other components added as desired may be melted and kneaded or granulated by any method. preferable.

[Base material layer]
Examples of the resin used for the base material layer include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, and a copolymer of ethylene and a long-chain olefin monomer such as 1-butene or 1-pentene. Polyethylene resins such as copolymers; polypropylene resins such as propylene homopolymer, high crystallinity propylene homopolymer, propylene / ethylene random copolymer, propylene / ethylene block copolymer; ethylene / ethyl acrylate copolymer, ethylene / Examples thereof include an n-butyl acrylate copolymer, an ethylene / vinyl acetate copolymer, and an ionomer resin. These polyolefin resin may be used independently and 2 or more types may be used together. Furthermore, a conventionally well-known raw material can also be used.

The base material layer may contain an antioxidant, an antistatic agent, other additives, etc., if necessary, and these may be used alone or in combination of two or more.
[Surface protective adhesive film]
The pressure-sensitive adhesive film for surface protection of the present invention is used, for example, for preventing damage during processing of products such as semiconductor wafers and displays or during storage and transportation.

The adhesive film for surface protection of the present invention may be a film having a base material layer on one surface and the above adhesive layer on the other surface, and if necessary, two or more base material layers are provided. Also good.
The thickness of the laminate of the present invention is usually 5 to 300 μm, preferably 10 to 200 μm, more preferably 10 to 150 μm.

[Method for producing adhesive film for surface protection]
The pressure-sensitive adhesive film for surface protection of the present invention may form a pressure-sensitive adhesive layer on the base material layer, or may simultaneously form the base material layer and the pressure-sensitive adhesive layer. Examples of the method for forming the adhesive layer on the base material layer include a solvent coating method and an emulsion coating method. Examples of a method for simultaneously forming the base material layer and the adhesive layer include a coextrusion molding method.

〔Example〕
The following surface protective adhesive film of the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

<Film forming method>
T-die coextrusion molding was performed under the following molding conditions to produce a three-layer multilayer film comprising a base material A layer, a base material B layer and an adhesive layer having a thickness of 50 μm and a width of 400 mm.
For the adhesive layer, the ethylene polymer described in Example 1, Example 2, or Comparative Example 1 was used alone. The base material A layer and the base material B layer were prepared by mixing Prime Polymer Hi-Zex 2200J and Prime Polymer Mirason 11P in a ratio of 50:50 parts by weight.

<Film forming conditions>
Molding machine: 65mmφ x 3 cast molding machine made by modern machinery Screw: Barrier type screw Dies: 800mm (width), 1.6mm (lip width)
Cooling roll temperature: 40 ° C. (The layer touching the cooling roll is the base layer side)
Layer structure: Base material A layer / Base material B layer / Adhesive layer = 20/20/10 (μm)
Take-up speed: 40 m / min
Regarding the physical properties of the multilayer film molded under the above conditions, the following items were measured.

<Blocking resistance>
The blocking test was measured as an index of blocking resistance.
In accordance with ASTM-D1893, the inner surface of the film was allowed to stand at 10 kg load for 3 days under an environment of 50 ° C., and then the blocking coefficient was measured.

<Adhesiveness>
The adhesive strength test was measured as an adhesive index.
In accordance with JIS Z 0237, 180 ° peeling adhesive strength was measured.

[Production Example 1]
Ethylene and 1-octene copolymer were produced using ethylene and 1-octene as monomers. Details are shown below.
Dehydrated and purified n-hexane is supplied to one feed port of a 136 liter continuous polymerization vessel.
A hexane slurry (5 mmol / liter as an aluminum atom) of TMAO-341 (manufactured by Tosoh Finechem) at a rate of liter / hr was di (p-tolyl) methylene (cyclopentadiene) at a rate of 0.2 liter / hr. (Ethyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride in hexane (0.1 mmol / liter) at a rate of 0.02 liter / hr in triisobutylaluminum in hexane (
2 mmol / liter) was continuously fed at a rate of 2.1 liter / hr (total hexane 10.4 liter / hr). At the same time, ethylene is supplied at a rate of 4.5 kg / hr and hydrogen at a rate of 30 liters / hr to another supply port of the continuous polymerizer, and 1-octene is supplied to another supply port at a rate of 2.5 kg / hr. Continuous feeding at a rate of hr, polymerization temperature 130 ° C., total pressure 3 MP
Continuous solution polymerization was carried out under the conditions of aG, residence time 70 min, and stirring speed 250 rpm.
The hexane solution of ethylene / 1-octene copolymer produced in the polymerization vessel is continuously discharged at a rate of 24 liter / hr through the discharge port provided in the side wall of the polymerization vessel, and the jacket portion is 8 kg / hr. It was led to a connecting pipe heated with cm ² steam. A hexane solution of an ethylene-octene copolymer heated to 170 ° C. in a connecting pipe with a steam jacket is
By adjusting the opening of the liquid level control valve provided at the end of the connection pipe so as to maintain the solution volume in the polymerization tank of about 28 liters, it is continuously passed through the double pipe inner pipe heated by 10 kg / cm ² steam. The solution was sent to the flash tank. Immediately after the liquid level control valve, a supply port for injecting methanol as a catalyst deactivator is attached, and the hexane solution is injected as a 1.0 vol% hexane diluted solution at a rate of 12 liters / hr. To join. In the transfer to the flash tank, the solution temperature and the pressure adjustment valve opening were set so that the pressure in the flash tank was 0.04 MPa-G and the temperature of the vapor part in the flash tank was maintained at 180 ° C. .
As a result, an ethylene / 1-octene copolymer was obtained at a production speed of 4.5 kg / hr. The obtained ethylene / 1-octene copolymer had an MFR (190 ° C., 2.16 kg) of 5.6 g / 10 min and a density of 899 kg / m ³ .

  The ethylene / 1-octene copolymer produced in Production Example 1 was used for the adhesive layer, and a multilayer film was produced by the above molding method. The intrinsic viscosity [η], molecular weight distribution (Mw / Mn) of the ethylene / 1-octene copolymer produced in Production Example 1, H / W, the blocking coefficient of the multilayer film, and the 180 ° peel-off adhesive strength were determined by the above method. The results are shown in Table 1.

[Production Example 2]
One feed port of a continuous polymerization vessel with a capacity of 136 liters was subjected to dehydration and purification of n-hexane at a rate of 10.2 liters / hr in hexane slurry of TMAO-341 (manufactured by Tosoh Finechem) (5 mmol / a as aluminum atoms). Liter) at a rate of 0.2 liter / hr, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride in hexane (0.1 mmol / liter) A hexane solution (2 mmol / liter) of triisobutylaluminum was continuously fed at a rate of 2.1 liter / hr at a rate of 0.02 liter / hr (total hexane of 12.5 liter / hr). At the same time, ethylene is supplied at a rate of 4 kg / hr and hydrogen at a rate of 10 liters / hr to another supply port of the continuous polymerization vessel, and 2 octene is supplied to another supply port.
Continuous supply at a rate of kg / hr was carried out, and continuous solution polymerization was carried out under conditions of a polymerization temperature of 150 ° C., a total pressure of 3 Mpa-G, a residence time of about 75 min, and a stirring speed of 250 rpm.

The hexane solution of ethylene / 1-octene copolymer produced in the polymerization vessel is continuously discharged at a rate of about 22.4 liter / hr through a discharge port provided on the side wall of the polymerization vessel. Was led to a connecting pipe heated with 8 kg / cm ² steam. The hexane solution of the ethylene-octene copolymer heated to 170 ° C. in the connection pipe with steam jacket is controlled at the liquid level provided at the end of the connection pipe so as to maintain the solution volume in the polymerization tank of about 28 liters. By adjusting the opening of the valve, the liquid was continuously fed to the flash tank through a double pipe inner tube heated with 10 kg / cm ² steam. Immediately after the liquid level control valve, a supply port for injecting methanol as a catalyst deactivator is attached, and the hexane solution is injected as a 1.0 vol% hexane diluted solution at a rate of 12 liters / hr. To join. In the transfer into the flash tank, the pressure in the flash tank is 0.04 MPa-G,
The solution temperature and the pressure adjustment valve opening were set so that the temperature of the vapor section in the flash tank was maintained at about 180 ° C.

As a result, an ethylene / 1-octene copolymer was obtained at a production speed of about 3.7 kg / hr. The MFR (190 ° C., 2.16 kg) of the obtained ethylene-octene copolymer was 1.
The density was 3 g / 10 min and the density was 908 kg / m ³ .

  A multilayer film was produced by the same molding method as in Example 1 except that the ethylene / 1-octene copolymer produced in Production Example 2 was used for the adhesive layer. Table 1 shows the measurement results of the physical properties of the ethylene / 1-octene copolymer produced in Production Example 2 and the physical properties of the multilayer film.

(Comparative Example 1)
A multilayer film was produced in the same manner as in Example 1 except that Prime Polymer Evolve SP0540 was used as the ethylene copolymer. The respective physical property values and measurement results are shown in Table 1.

[Comparative Example 2]
A multilayer film was produced in the same manner as in Example 1 except that Prime Polymer Ultzex 1020L was used as the ethylene copolymer. The respective physical property values and measurement results are shown in Table 1.

Claims (2)

A surface comprising an adhesive layer made of an ethylene copolymer that simultaneously satisfies the following requirements (I) to (IV), obtained by copolymerizing ethylene and an α-olefin having 4 to 10 carbon atoms: Protective adhesive film.
(I) The melt flow rate (MFR) at a load of 2.16 kg at 190 ° C. is in the range of 0.10 to 50 g / 10 min.
(II) The density (D) is in the range of 860 to 930 kg / m ³ .
(III) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is in the range of 1.50 to 3.00.
(IV) In the elution curve obtained by temperature rising elution fractionation (TREF), the ratio (H) of the peak height (H) having the strongest peak intensity to the width (W) at half the height of the peak (H / W) and density (D) satisfy any of the following relational expressions (Eq-1) to (Eq-3) according to the MFR value of requirement (I).
[When 0.10 ≦ MFR ≦ 1.00]
0.0163 × D-14.00 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.21
... (Eq-1)
[If 1.00 <MFR ≦ 10.0]
0.0163 × D-14.02 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.30
... (Eq-2)
[If 10.0 <MFR ≦ 50]
0.0163 × D-14.10 ≦ Log ₁₀ (H / W) ≦ 0.0163 × D-13.40
... (Eq-3) The adhesive film for surface protection according to claim 1, wherein the copolymer further satisfies the following requirement (V).
(V) The intrinsic viscosity [[η] (dl / g)] measured in decalin at 135 ° C. and the melt flow rate (MFR) satisfy the following relational expression (Eq-4).
−0.21 × Log ₁₀ MFR + 0.16 ≦ Log ₁₀ [η] ≦ −0.21 × Log ₁₀ M
FR + 0.31 (Eq-4)