JPH1080972A - Release body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a release body with a filler layer formed of a highly heat- resistant resin. SOLUTION: This release body consists of a base, a resin layer containing an ethylene monopolymer or an ethylene/α-olefin copolymer A which satisfies requirements (a)-(d) as described and a release agent layer. The adhesive strength between the base and the resin layer is set to 50g/15mm width or more. The polymer has (a) a density of 0.86-0.97g/cm<3> , (b) a melt flow rate of 0.01-100g/10min, (c) a molecular weight distribution (Mw/Mn) of 1.5-5.0, and (d) a composition distribution parameter Cb of 2.00 or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a release paper used for pressure-sensitive adhesive sheets, adhesive sheets, synthetic resin films and casting film formation, and a release paper used as a base material of a pressure-sensitive adhesive tape.

[0002]

2. Description of the Related Art A release paper is formed by providing a release agent layer on a base material such as paper. In order to improve the coating properties and release performance of the release agent, a so-called release paper is provided between the base material and the release agent layer. In this case, a filler layer is interposed. In such a sealing layer,
Usually, inexpensive, high-pressure low-density polyethylene is used alone, or high-density polyethylene, which is a homopolymer of ethylene obtained using a Ziegler-based catalyst, and a copolymer of ethylene and another α-olefin. A mixture of a chain low-density polyethylene and a high-pressure polyethylene is used.

[0003]

In recent years, particularly in the production of release paper, the step of forming a release agent layer has been shortened for the purpose of further cost reduction. The step of forming the release agent layer generally includes a step of applying a release agent and a step of drying. To shorten the time, the drying step needs to be performed in a shorter time. Therefore, it is desired to increase the drying temperature. However, when the drying temperature is increased, there is a problem that a substance having a low melting point, such as a high-pressure low-density polyethylene used in the filling layer, is melted during the drying step, and many pinholes are generated. . In order to solve this problem, a method has been adopted in which a high-pressure polyethylene is blended with a linear low-density polyethylene or a high-density polyethylene having a higher melting point. However, these materials also melt when the drying temperature is equal to or higher than the melting point, and have insufficient heat resistance. Therefore, pinholes may be generated, and further cost reduction cannot be achieved.

[0004] The present invention has been made to solve the above problems, and has as its object to provide a peeled body in which a sealing layer is made of a resin having high heat resistance.

[0005]

Means for Solving the Problems As a result of intensive studies for the above-mentioned objects, the present inventors have found that despite having a narrow molecular weight distribution, they have a relatively broad composition distribution, low molecular weight components and non-molecular weight components. The above object has been achieved by using a resin containing an ethylene homopolymer or an ethylene / α-olefin copolymer having a low content of a crystalline component as a filler layer.

The exfoliated body of the present invention comprises:
A resin layer containing an ethylene homopolymer or an ethylene / α-olefin copolymer (A) satisfying the requirement (d), and a release agent layer, and adhesion between the base and the resin layer; The strength is not less than 50 g / 15 mm width. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (d) Composition distribution parameter Cb is 2.00 or less

At this time, the ethylene homopolymer or the ethylene / α-olefin copolymer (A) contains at least an organic cyclic compound having at least a conjugated double bond and
It is preferably obtained by (co) polymerizing ethylene or ethylene and an α-olefin in the presence of a catalyst containing a group IV transition metal compound. further,
It is desirable that the ethylene homopolymer or the ethylene / α-olefin copolymer (A) satisfies the following requirements (d) to (f). (D) The composition distribution parameter Cb is 1.08 to 2.0. (E) There are substantially a plurality of peaks in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method. (F) Orthodichlorobenzene soluble content X (wt%) at 25 ° C, density d and melt flow rate (MFR)
Satisfies the following relationship. (A) When d−0.008 log MFR ≧ 0.93 X <2.0 (b) When d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) )
² + 2.0

Alternatively, the ethylene homopolymer or ethylene / α-olefin copolymer (A) according to claim 1 is
Ligand having cyclopentadienyl skeleton and Periodic Table No.
Ethylene homopolymer or ethylene / α-olefin copolymer (A2) obtained by polymerization in the presence of at least one catalyst containing a Group IV transition compound and satisfying the following requirements (d) and (e): ) Is desirable. (D) Composition distribution parameter Cb is 1.01 to 1.2 (e) Substantially one peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method

Further, the resin layer is formed of the ethylene homopolymer or the ethylene / α-olefin copolymer (A).
And another ethylene-based (co) polymer (B). In that case, in the composition, the ethylene homopolymer or the ethylene / α-olefin copolymer (A) is 95 to 50% by weight, and the other ethylene (co) polymer (B) is 5 to 50% by weight. % Is desirable.

[0010]

(Resin layer)

<Component (A)> In the exfoliated body of the present invention, a specific resin containing the component (A) is used in a resin layer serving as a sealing layer. In the ethylene homopolymer or ethylene / α-olefin copolymer of the component (A), the α-olefin has 3 to 20, preferably 3 to 12 carbon atoms.
Are preferred. For example, propylene, 1-butene,
Examples thereof include 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, and 1-dodecene. In addition, the content of these α-olefins,
30 mol% or less in total, preferably 3 to 2 in the copolymer
Desirably, it is selected in the range of 0 mol%.

The ethylene homopolymer or ethylene / α-olefin copolymer (A) in the present invention has a density of 0.86 to 0.97 g / cm ³ . Preferably 0.90-
0.94 g / cm ³ , more preferably 0.91 to 0.93 g
/ Cm ³ . If the density is less than 0.86 g / cm ³ , it is too soft, resulting in poor heat resistance and poor anti-blocking properties. If it exceeds 0.97 g / cm ³ , it is too hard.
The tear strength, impact drop strength, etc., decrease. The melt flow rate (hereinafter referred to as MFR) of the component (A) is 0.01 to 100 g / 10 minutes, and more preferably 0.1 to 100 g / 10 minutes.
The range is 1 to 100 g / 10 min, more preferably 0.2 to 50 g / 10 min, and even more preferably 0.5 to 40 g / 10 min.
If the MFR is less than 0.01 g / 10 min, the processability (drawdown property, etc.) will be poor, and if it exceeds 100 g / 10 min, the strength will be weak.

The molecular weight distribution Mw / Mn of the component (A) is:
It is in the range of 1.5 to 5.0. It is more preferably in the range of 1.5 to 4.5, further preferably in the range of 1.8 to 4.0, and more preferably in the range of 2.0 to 3.5. Mw /
If Mn is less than 1.5, the formability is poor, and if it exceeds 5.0, the mechanical strength such as impact resistance is poor. The molecular weight distribution (Mw / Mn) is obtained by calculating the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC) and calculating the ratio (Mw / Mn). Desired.

The composition distribution parameter (Cb) of the component (A) of the present invention must be 2.00 or less. 1.08 ~
It is more preferably 2.00, more preferably 1.10 to 1.80, and more preferably 1.15 to 1.50. If the composition distribution parameter (Cb) is larger than 2.00, blocking tends to occur, heat sealing properties are poor, and low molecular weight or high branching components are oozed out onto the resin surface, resulting in hygienic problems. It is. If it is smaller than 1.08, the heat resistance tends to be poor. The composition distribution parameter (Cb) is measured as follows. A sample was dissolved by heating at 135 ° C. in orthodichlorobenzene (ODCB) to which an antioxidant had been added to a concentration of 0.2% by weight.
After being transferred to a column filled with diatomaceous earth (Celite 545), it is cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the copolymer sample is deposited on the Celite surface. Next, the column temperature is raised stepwise to 120 ° C. in steps of 5 ° C. while flowing ODCB at a constant flow rate through the column on which the sample is deposited. Then, a solution containing an eluted component corresponding to each temperature is collected. After cooling this solution, methanol was added,
After the sample is precipitated, it is filtered and dried to obtain an eluted sample at each temperature. The weight fraction and the degree of branching (the number of branches per 1000 carbon atoms) of each of the separated samples are measured. The degree of branching is determined by measuring with ¹³ C-NMR.

For each fraction collected at 30 ° C. to 90 ° C. by such a method, the branching degree is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, and the correlation is approximated to a straight line by the least square method,
Create a calibration curve. The correlation coefficient of this approximation is large enough.
The value obtained from this calibration curve is defined as the degree of branching of each fraction. Note that, for a fraction collected at an elution temperature of 95 ° C. or higher, this correction is not performed because a linear relationship is not always established between the elution temperature and the degree of branching.

Next, the weight fraction w _i of each fraction is determined by the change amount (b _i) of the branching degree b _i at an elution temperature of 5 ° C.
Obtaining the relative concentration c _i is divided by -b _i-1), by plotting the relative concentration against the branching degree to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation. Cb = (Σc _j・ b _j ² / Σc _j・ b _j ) / (Σc _j・ b _j /
Σc _j ) where c _j and b _j are the relative density and branching degree of the j-th section, respectively. The composition distribution parameter Cb is 1.0 when the composition of the sample is uniform, and the value increases as the composition distribution spreads.

Many proposals have been made for a method of expressing the composition distribution of the ethylene / α-olefin copolymer. For example, in Japanese Patent Application Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (log normal distribution) with respect to the number of branches of each of the separated samples obtained by solvent separation of the sample. , The ratio between the weight average branching degree (Cw) and the number average branching degree (Cn). The accuracy of this approximation calculation decreases when the number of branches and the cumulative weight fraction of the sample deviate from the lognormal distribution, and when a commercially available LLDPE is measured, the correlation coefficient R2 is considerably low, and the accuracy of the value is not sufficient. Also,
The method of measuring Cw / Cn and the method of numerical processing are different from those of Cb of the present invention.
The value of w / Cn is much larger than Cb.

The above component (A) comprises a Ziegler catalyst,
Although it may be produced using a known catalyst such as a Phillips catalyst, those prepared by the following two embodiments are particularly preferable. One of them is that, in the presence of a catalyst containing at least an organic cyclic compound having a conjugated double bond and a transition metal compound of Group IV of the periodic table, ethylene is homopolymerized, or ethylene is mixed with α-α having 3 to 20 carbon atoms. Those obtained by copolymerizing with an olefin are preferred. Among these, an ethylene homopolymer or an ethylene / α-olefin copolymer (hereinafter, referred to as component (A1)) satisfying the following requirements (a) to (f) is particularly preferable. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.5 to 5.0 (d) ) The composition distribution parameter Cb is 1.08 to 2.0. (E) Substantially plural peaks of the elution temperature-elution amount curve by the continuous heating elution fractionation method (f) Orthodichlorobenzene solubility at 25 ° C Quantity X (wt%), density d and melt flow rate (MFR)
Satisfies the following relationship: (a) When d−0.008 log MFR ≧ 0.93, X <2.0 (b) When d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300-d + 0.008logMFR)
² + 2.0

The other is the following (a) to (b) obtained in the presence of a ligand having a cyclopentadienyl skeleton and at least one catalyst containing a transition compound of Group IV of the periodic table.
It is an ethylene homopolymer or an ethylene / α-olefin copolymer (hereinafter, referred to as component (A2)) satisfying the requirement of (e). (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10 min (c) Molecular weight distribution (Mw / Mn) 1.5 to 5.0 (d) ) The composition distribution parameter Cb is 1.01 to 1.2. (E) There is substantially one peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method.

Here, as shown in FIG. 1, the component (A1) is a special novel compound having a plurality of peaks substantially in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method (TREF). Ethylene homopolymer or ethylene α-
As shown in FIG. 2, the component (A2) has substantially one peak in an elution temperature-elution amount curve obtained by the same continuous heating elution fractionation method (TREF). At least one containing a ligand having a cyclopentadienyl skeleton and a transition metal compound belonging to Group IV of the periodic table.
Is a typical metallocene-based ethylene homopolymer or ethylene-α-olefin copolymer obtained in the presence of various catalysts, wherein the components (A1) and (A2) are clearly distinguished. .

<< Component (A1) >> In the component (A1),
The molecular weight distribution (Mw / Mn) is in the range of 1.5 to 5.0, preferably 1.5 to 4.5, more preferably 1.8 to 4.0, and more preferably 2.0. It is desirable to be in the range of 0 to 3.5. In the component (A1), the composition distribution parameter Cb is more preferably from 1.08 to 2.00, even more preferably from 1.10 to 2.00.
It is desirable to be in the range of 1.80, more preferably 1.15 to 1.50.

In the present invention, the special ethylene homopolymer or ethylene / α-olefin copolymer (A1) is
As described above, (e) continuous heating elution fractionation (TRE)
There are a plurality of peaks in the elution temperature-elution amount curve obtained in F). It is particularly preferred that the plurality of peak temperatures be between 85 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body.

The method of measuring TREF is as follows. First, a sample is added to ODCB to which an antioxidant (for example, butylhydroxytoluene) is added so that the sample concentration becomes 0.05% by weight, and the mixture is heated and dissolved at 135 ° C. 5 ml of this sample solution is injected into a column filled with glass beads, cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, O
While flowing DCB at a constant flow rate, the column temperature was raised to 50 ° C. /
The sample is sequentially eluted while heating at a constant rate of hr.
At this time, the concentration of the sample eluted in the solvent is continuously detected by measuring the absorption of asymmetrical stretching vibration of methylene at a wave number of 2925 cm ^-1 with an infrared detector. From this value, the concentration of the ethylene / α-olefin copolymer in the solution is quantitatively analyzed to determine the relationship between the elution temperature and the elution rate.
According to the TREF analysis, a change in the elution rate with respect to a temperature change can be continuously analyzed with a very small amount of sample, so that a relatively fine peak which cannot be detected by the fractionation method can be detected.

This component (A1) is composed of the amount X (% by weight) of the ODCB-soluble component at 25 ° C., the density d and the MF
The relationship of R is that the values of d and MFR are d−0.008 log
When MFR ≧ 0.93, X is less than 2% by weight, preferably less than 1% by weight, and when d−0.008 log MFR <0.93, X <9.8 × 10 ³ × (0.9300 −d + 0.008 log MFR)
² + 2.0 Preferably, X <7.4 × 10 ³ × (0.9300−d + 0.008 log MFR)
² +1.0 More preferably, X <5.6 × 10 ³ × (0.9300−d + 0.008 log MFR)
It is desirable to satisfy the relationship of ² +0.5.

The amount X of the ODCB-soluble component at 25 ° C. is measured by the following method. 0.5 g of the sample is heated at 135 ° C. for 2 hours in 20 ml of ODCB to completely dissolve the sample and then cooled to 25 ° C. This solution is
After standing at 5 ° C. overnight, the mixture is filtered through a Teflon filter to collect a filtrate. The filtrate is measured for absorption peak intensity near the wave number 2925 cm ^-1 of asymmetric stretching vibration of methylene using an infrared spectrometer, and the sample concentration is calculated from a previously prepared calibration curve. From this value, the ODCB-soluble content at 25 ° C. is determined.

The ODCB-soluble component at 25 ° C. is a component having a high degree of branching and a low molecular weight contained in the ethylene / α-olefin copolymer. It is desirable that this content be small, since this may cause problems and blocking of the inner surface of the molded article. The amount of ODCB solubles is affected by the comonomer content and molecular weight. Therefore, the fact that the density and the amounts of MFR and ODCB-soluble component, which are indicators, satisfy the above relationship indicates that the uneven distribution of α-olefin contained in the whole copolymer is small.

The ethylene homopolymer or ethylene.
Since the α-olefin copolymer (A) has narrow molecular weight distribution and composition distribution, it has high mechanical strength, heat sealability,
It is a polymer that is excellent in anti-blocking properties and the like and has good heat resistance. This component (A1) is preferably polymerized with the following catalysts a1 to a4. a1: a compound represented by the general formula Me ¹ R ¹ _p R ² _q (OR ³ ) _r X ¹⁴ _-pqr . (In the formula, Me ¹ represents zirconium, titanium, or hafnium, R ¹ and R ³ each represent a hydrocarbon group having 1 to 24 carbon atoms or a trialkylsilyl group, and R ² represents a 2,4-pentanedionato ligand. Or a derivative thereof, a benzoylmethanato ligand, a benzoylacetonato ligand or a derivative thereof, X ¹ represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r each represent 0 ≦ p <
4, an integer satisfying a range of 0 ≦ q <4, 0 ≦ r <4, and 0 ≦ p + q + r ≦ 4. A2) A compound represented by the general formula Me ² R ⁴ _m (OR ⁵ ) _n X ² _zmn . (In the formula, Me ² is an element in Groups I to III of the periodic table, R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom (provided that X ² is a hydrogen atom In the case of, Me ² represents a group III element of the periodic table), z represents the valence of Me ² , and m and n are each 0.
It is an integer satisfying the range of ≦ m ≦ z, 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z. A3) An organic cyclic compound having a conjugated double bond. a4: Modified organic aluminum oxy compound and / or boron compound containing Al-O-Al bond.

Each of these catalyst components will be described in detail. The catalyst component a1 has the general formula Me ¹ R ¹ _p R ² _q (O
In the formula of the compound represented by R ³ ) _r X ¹⁴ _-pqr , Me ¹ represents zirconium, titanium, or hafnium, and a plurality of compounds may be used, but zirconium having excellent weather resistance of the copolymer is contained. Is particularly preferred. The hydrocarbon group having 1 to 24 carbon atoms of R ¹ and R ³ preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group And an aralkyl group such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, and a neofuyl group. These may have branches.

Examples of the compounds represented by the general formula of the above-mentioned catalyst component a1 include tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorodichloroconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tribubutoxy. Monochlorodizirconium, dibutoxydichlorozirconium, tetrabutoxytitanium, tetrabutoxyhafnium and the like can be mentioned, and particularly, a Zr (OR) ₄ compound such as tetrapropoxyzirconium and tetrabutoxyzirconium is preferable. No problem.
Specific examples of the 2,4-pentanedionato ligand or a derivative thereof of R ² include tetra (2,4-pentanedionato) zirconium, tri (2,4-pentanedionato) chloride zirconium, Di (2,4-pentanedionato) dichloride zirconium, (2,4-pentanedionato) trichloride, di (2,4-pentanedionato) diethoxide zirconium, di (2,4-pentanedionato) Di-n-propoxide zirconium, di (2,4-pentanedionato) di-n-butoxide zirconium, di (2,4-pentanedionato) dibenzyl zirconium, di (2,4-pentanedionio) Nato) zineofyl zirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato)
Diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxide zirconium, di (2,4
-Pentanedionato) di-n-butoxide zirconium, di (benzoylacetonato) dioxide zirconium, di (dibenzoylacetonato) di-n-propoxide zirconium, di (benzoylacetonato) di-n- Butoxide zirconium and the like.

The catalyst component a2 has the general formula Me ² R
^In the formula of the compound represented by ⁴ _m (OR ⁵ ) _n X ² _zmn , Me ² represents an element in Groups I to III of the periodic table, and is represented by lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum, or the like. is there. R4 and R ⁵ are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms,
More preferably, it is 1 to 8, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group; an alkenyl group such as a vinyl group and an allyl group; a phenyl group, a tolyl group, and a xylyl group. And aralkyl groups such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group and a neofuyl group. These may have branches. X ² represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine and bromine. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like.

Examples of the compound represented by the general formula of the catalyst component a2 include organic lithium compounds such as methyllithium and ethyllithium; organic magnesium compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride and ethylmagnesium chloride; Organic zinc compounds such as zinc and diethyl zinc; organic boron compounds such as trimethyl boron and triethyl boron; trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, tridecyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, and ethyl aluminum sesqui Organic aluminum such as chloride, diethylaluminum ethoxide and diethylaluminum hydride Derivatives such as a compound such as an iron compound.

The organic cyclic compound having a conjugated double bond of the catalyst component a3 includes one cyclic ring having two or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds.
Or a cyclic hydrocarbon compound having at least 2 and having a total carbon number of 4 to 24, preferably 4 to 12; wherein the cyclic hydrocarbon compound is partially a hydrocarbon residue of 1 to 6 (typically , An alkyl group having 1 to 12 carbon atoms or an aralkyl group)
A cyclic hydrocarbon compound having one or more rings having two or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds, and having a total carbon number of 4 to 2
4, an organosilicon compound having a cyclic hydrocarbon group which is preferably 4 to 12;
Organosilicon compounds substituted with 6 hydrocarbon residues or alkali metal salts (sodium or lithium salts) are included. Particularly preferably, those having a cyclopentadiene structure in any of the molecules are desirable.

The preferred compounds include cyclopentadiene, indene, azulene and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Further, a compound obtained by bonding (crosslinking) these compounds via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) is also preferably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A _L SiR _4-L wherein A represents the above-mentioned cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group, a propyl group. Alkyl groups such as methoxy, ethoxy, propoxy and butoxy groups; aryl groups such as phenyl groups; aryloxy groups such as phenoxy groups; aralkyl groups such as benzyl groups. And represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms or hydrogen, and L represents 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Specific examples of the organic cyclic hydrocarbon compound of the component a3 include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, and 4,7- C5-C24 cyclopolyene or substituted cyclopolyene such as dimethylindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene, monocyclopentadienylsilane, biscyclopentadiene Examples include enylsilane, triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.

The modified organoaluminum oxy compound containing an Al-O-Al bond of the catalyst component a4 and / or the boron compound is obtained by reacting an alkylaluminum compound with water to form a modified organoaluminum oxy compound usually called aluminoxane. Is usually obtained in the molecule.
It contains 100, preferably 1 to 50 Al-O-Al bonds. The modified organoaluminum oxy compound may be linear or cyclic. As the boron compound, triethylaluminum tetra (pentafluorophenyl) borate (triethylammonium tetra (pentafluorophenyl) borate, dimethylanilinium tetra (pentafluorophenyl) borate (dimethylaniliniumtetra (pentafluorophenyl) borate), Butylammonium tetra (pentafluorophenyl) borate, N, N-dimethylammonium tetra (pentafluorophenyl) borate, N, N-dimethylammonium tetra (pentafluorophenyl) borate and the like.

The reaction between the organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferred. The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) is usually 0.25 / 1 to 1.2 /
1, and preferably 0.5 / 1 to 1/1.

The catalyst components a1 to a4 may be used by mixing and contacting them as they are. However, it is preferable that the catalyst components are supported on an inorganic carrier and / or a particulate polymer carrier (a5). Examples of the inorganic carrier and / or the particulate polymer carrier (a5) include carbonaceous materials,
Examples include metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof, thermoplastic resins, thermosetting resins, and the like. Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Specifically, SiO ₂ , Al ₂ O ₃ , MgO, Zr
O ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, Th
O _{2 and the} like or a mixture thereof, and SiO ₂ —Al
₂ O ₃ , SiO ₂ -V ₂ O ₅ , SiO ₂ -TiO ₂ , SiO _2-
V ₂ O ₅ , SiO ₂ —MgO, SiO ₂ —Cr ₂ O _{3 and the} like. Among these, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable. Further, as the organic compound, any of a thermoplastic resin and a thermosetting resin can be used. Specifically, particulate polyolefin, polyester, polyamide, polyvinyl chloride, polymethyl (meth) acrylate,
Examples include polystyrene, polynorbornene, various natural polymers, and mixtures thereof.

The above-mentioned inorganic carrier and / or particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are treated with an organic aluminum compound or a modified organic aluminum oxy compound containing an Al—O—Al bond. Can be used as the component a5 after the contact treatment.

<< Component (A2) >> In the case of the ethylene homopolymer or ethylene / α-olefin copolymer component (A2) using a metallocene catalyst, the molecular weight distribution is 1.
The range is from 5 to 5.0, preferably from 1.5 to 4.5, and more preferably from 1.8 to 3.5. In the component (A2), the composition distribution parameter is 1.01 to 1.2, preferably 1.02 to 1.0.
18, more preferably in the range of 1.03 to 1.16.

Ethylene homopolymer or ethylene / α-olefin copolymer (A
2) a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton and, if necessary, a cocatalyst;
It is obtained by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst containing an organoaluminum compound and a carrier.

The ethylene homopolymer or ethylene.
The cyclopentadienyl skeleton of the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, which is a catalyst for producing the α-olefin copolymer (A2), is cyclopentadienyl. And substituted cyclopentadienyl groups. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 10 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. And a substituted cyclopentadienyl group having at least one substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents may be bonded to each other to form a ring.

Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. Specific examples include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Group, n-butyl group,
Alkyl groups such as isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group and decyl group; cycloalkyl groups such as cyclopentyl group and cycloalkyl group; phenyl group and tolyl And an aralkyl group such as a benzyl group and a neofuyl group. Among these, an alkyl group is preferable. Preferred examples of the substituted cyclopentadienyl group include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n-hexylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1,3 Specific examples include a -n-butylmethylcyclopentadienyl group and a 1,3-n-propylmethylethylcyclopentadienyl group. As the substituted cyclopentadienyl group of the present invention, among these, a cyclopentadienyl group substituted by an alkyl group having 3 or more carbon atoms is preferable, and a 1,3-substituted cyclopentadienyl group is particularly preferable. When the substituents, that is, the hydrocarbons are bonded to each other to form one or more rings, examples of the substituted cyclopentadienyl group include an indenyl group and a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group). A substituted indenyl group, a naphthyl group, a hydrocarbon group having 1 to 8 carbon atoms (such as an alkyl group)
A substituted naphthyl group substituted with a substituent such as
Preferred examples include a substituted fluorenyl group substituted by a substituent such as a hydrocarbon group (e.g., an alkyl group) of No. 8 to 8 and the like.

Examples of the transition metal of the transition metal compound belonging to Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton include zirconium, titanium, and hafnium, with zirconium being particularly preferred. The transition metal compound generally has 1 to 3 ligands having a cyclopentadienyl skeleton, and when having 2 or more ligands, they may be bonded to each other by a crosslinking group. In addition, examples of such a crosslinking group include an alkylene group having 1 to 4 carbon atoms, an alkylsilanediyl group, and a silanediyl group.

Typical examples of the ligands other than those having a cyclopentadienyl skeleton in the transition metal compounds belonging to Group IV of the periodic table include hydrogen and carbon atoms having 1 to 20 carbon atoms.
(Alkyl group, alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, methalkyl group, metaaryl group and the like.

The following are specific examples of these. As dialkyl metallocenes, bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) ) Hafnium dimethyl, bis (cyclopentadienyl) hafnium diphenyl and the like. As the monoalkyl metallocene, bis (cyclopentadienyl)
Examples include titanium methyl chloride, bis (cyclopentadienyl) titanium phenyl chloride, bis (cyclopentadienyl) zirconium methyl chloride, and bis (cyclopentadienyl) zirconium phenyl chloride. In addition, monocyclopentadienyl titanocene such as pentamethylcyclopentadienyl titanium trichloride, pentaethylcyclopentadienyl titanium trichloride), and bis (pentamethylcyclopentadienyl) titanium diphenyl may be used.

Examples of the substituted bis (cyclopentadienyl) titanium compound include bis (indenyl) titanium diphenyl or dichloride, bis (methylcyclopentadienyl) titanium diphenyl or dichloride, dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentane. Examples of the dienyl titanium compound include bis (1,2-dimethylcyclopentadienyl) titanium diphenyl or dichloride, bis (1,2-diethylcyclopentadienyl) titanium diphenyl or dichloride or other dihalide complex, silicon, amine or Examples of the carbon-linked cyclopentadiene complex include dimethylsilyldicyclopentadienyltitanium diphenyl or dichloride, methylenedicyclopentadienylthiene. Iodonium diphenyl or dichloride, and other dihalide complexes.

As the zirconocene compound, pentamethylcyclopentadienyl zirconium trichloride,
Pentaethylcyclopentadienyl zirconium trichloride, bis (pentamethylcyclopentadienyl)
Examples of zirconium diphenyl and alkyl-substituted cyclopentadiene include bis (ethylcyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dimethyl, bis (n-butylcyclopentadienyl) zirconium dimethyl, and haloalkyl or dihalide thereof. Examples of the complex, dialkyl, trialkyl, tetraalkyl or pentaalkylcyclopentadiene include bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (1,2-dimethylcyclopentadienyl) zirconium dimethyl, and dihalide complexes thereof, silicon Examples of the carbon-linked cyclopentadiene complex include dimethylsilyldicyclopentadienylzirconium dimethyl or dihalide, methylenedicyclopentane. Examples thereof include dienyl zirconium dimethyl or dihalide, and methylene dicyclopentadienyl zirconium dimethyl or dihalide.

Still other metallocenes include bis (cyclopentadienyl) hafnium dichloride, bis (cyclopentadienyl) hafnium dimethyl, bis (cyclopentadienyl) vanadium dichloride and the like.

Other examples of the transition metal compound belonging to Group IV of the periodic table of the present invention include a ligand having a cyclopentadienyl skeleton represented by the following chemical formula and other ligands and transition metal atoms having a ring structure. And those that form

Embedded image In the chemical formula, Cp is a ligand having the cyclopentadienyl skeleton, X is hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an arylsilyl group, an aryloxy group, an alkoxy group, an amide group, a silyloxy group, or the like. And Y is Si
R ₂ , CR ₂ , SiR ₂ SiR ₂ , CR ₂ CR ₂ , CR = C
R, a divalent group selected from the group consisting of SiR ₂ CR ₂ , BR ₂ , and BR, Z is —O—, —S—, —NR—, —PR— or OR, SR, NR ₂ , and PR ₂ 2 shows a divalent neutral ligand selected from the group. However, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group, a silyl group, a halogenated alkyl group, a halogenated aryl group, or Y,
Two or more R groups from Z or from both Y and Z form a fused ring system. M represents a transition metal atom of Group IV of the periodic table.

Examples of the compound represented by the above chemical formula include (t-butylamido) (tetramethylcyclopentadienyl) -1,2-ethanediylzirconium dichloride and (t-butylamido) (tetramethylcyclopentadienyl). ) -1,2-ethanediyl titanium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyl zirconium dichloride, (methylamide) (tetramethylcyclopentadienyl) -1,2-ethanediyl Titanium dichloride,
(Ethylamide) (tetramethylcyclopentadienyl) methylenetan dichloride, (t-butylamide)
Dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, (t-butylamido) dimethyl (tetramethylcyclopentadienyl) silanezirconium dibenzyl, (benzylamido) dimethyl (tetramethylcyclopentadienyl) silane titanium dichloride, Phenylphosphido) dimethyl (tetramethylcyclopentadienyl) silanetitanium dichloride.

As the co-catalyst in the present invention, a co-catalyst capable of effectively using the above-mentioned transition metal compound of Group IV of the periodic table as a polymerization catalyst or balancing ionic charges in a catalytically activated state can be used. Say. Examples of the co-catalyst used in the present invention include benzene-soluble aluminoxane, benzene-insoluble organic aluminum oxy compound, boron compound, lanthanide salts such as lanthanum oxide, and tin oxide of the organic aluminum oxy compound. Of these, aluminoxanes are most preferred.

The catalyst may be used by being supported on an inorganic or organic compound carrier. The carrier is preferably a porous oxide of an inorganic or organic compound. In particular,
SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O
_{3, CaO, ZnO, BaO,} ThO 2 and the like or mixtures _{thereof, SiO 2 -Al 2 O 3,} SiO 2 -V 2
_{O 5, SiO 2 -TiO 2,} SiO 2 -MgO, SiO 2 -
Cr ₂ O _{3 and the} like.

Examples of the organic aluminum compound include trialkyl aluminum such as triethyl aluminum and triisopropyl aluminum; dialkyl aluminum halide; alkyl aluminum sesquihalide; alkyl aluminum dihalide; alkyl aluminum hydride; and organic aluminum alkoxide.

<< Production Method >> The method for producing the ethylene homopolymer or the ethylene / α-olefin copolymer (component (A)) of the present invention is carried out in the presence of the catalyst in the presence of a gas phase polymer substantially free of a solvent. Produced by a legal method, slurry polymerization method, solution polymerization method, etc., with oxygen, water, etc. substantially turned off,
In the presence of an inert hydrocarbon solvent exemplified by aliphatic hydrocarbons such as butane, pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane and alicyclic hydrocarbons such as methylcyclohexane. Or manufactured in the absence. The polymerization conditions are not particularly limited, but the polymerization temperature is usually 15 to 350 ° C, preferably 20 to
To 200 ° C, more preferably 50 to 110 ° C,
In the case of the low-to-medium pressure method, the polymerization pressure is usually from normal pressure to 70 kg / cm.
^The pressure is ² G, preferably normal pressure to 20 kg / cm ² G, and in the case of the high-pressure method, it is usually desirable to be 1500 kg / cm ² G or less. The polymerization time is usually 3 minutes to 10 hours, preferably 5 minutes to
About 5 hours is desirable. In the case of the high pressure method, usually 1 minute to 30 minutes
Minutes, preferably about 2 to 20 minutes. In addition, the polymerization is not only a one-stage polymerization method, but also a hydrogen concentration, a monomer concentration,
There is no particular limitation on a multi-stage polymerization method of two or more stages in which polymerization conditions such as polymerization pressure, polymerization temperature, and catalyst are different from each other.

In the ethylene / α-olefin copolymer of the present invention, if the catalyst component at the time of polymerization does not substantially contain halogen such as chlorine, the resulting polymer does not contain these halogens, and It has excellent stability and hygiene, and is suitable for food, hygiene, and medical applications.

<Component (B)> In addition to the above-mentioned component (A), other ethylene-based (co) polymers (components) It is desirable to mix (B)). As such another ethylene-based (co) polymer, high-pressure polyethylene is suitable. Examples of such a high-pressure polyethylene include ethylene polymers obtained by a high-pressure radical polymerization method, such as ethylene homopolymer (low-density polyethylene: B1) having a density of 0.91 to 0.94 g / cm ³ , and ethylene. And vinyl ester copolymer (B2) and copolymer of ethylene with an α, β-unsaturated carboxylic acid or a derivative thereof (B3).

The above (B1) low-density polyethylene (hereinafter, referred to as “B1”)
LDPE) has an MFR of 0.05 to 50 g / 10
Min, preferably in the range of 0.1 to 30 g / 10 min. Within this range, the melt tension of the composition is in an appropriate range, and extrusion lamination molding and the like are easy. The L
The DPE has a density of 0.91 to 0.94 g / cm ³ , preferably 0.912 to 0.935 g / cm ³ , and more preferably 0.9.
It is selected in the range of 12 to 0.930 g / cm ³ . The molecular weight distribution (Mw / Mn) is 3.0 to 12, preferably 4.0.
0 to 8.0. The LDPE is produced by a known high-pressure radical polymerization method, and may be any of a tubular method and an autoclave method.

The (B2) ethylene / vinyl ester copolymer is produced by a high-pressure radical polymerization method and comprises ethylene as a main component, vinyl propionate, vinyl acetate,
It is a copolymer with vinyl ester monomers such as vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. Among them, particularly preferred is vinyl acetate. A copolymer comprising 50 to 99.5% by weight of ethylene, 0.5 to 50% by weight of a vinyl ester and 0 to 49.5% by weight of another copolymerizable unsaturated monomer is preferred. Further, the vinyl ester content is selected in the range of 3 to 20% by weight, particularly preferably 5 to 15% by weight. The MFR of these copolymers is selected in the range of 0.1 to 50 g / 10 minutes, preferably 0.3 to 30 g / 10 minutes.

Representative copolymers of the above (B3) copolymers of ethylene and α, β-unsaturated carboxylic acids or derivatives thereof include ethylene / (meth) acrylic acid or its alkyl ester copolymer. Is mentioned. These comonomers include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, and n-butyl acrylate. N-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and the like. Of these, particularly preferred are alkyl esters of (meth) acrylic acid such as methyl and ethyl. Particularly, the content of the (meth) acrylate is 3 to 20% by weight, preferably 5 to 20% by weight.
-15% by weight. MFR of these copolymers
Is 0.1 to 30 g / 10 min, preferably 0.2 to 20 g
/ 10 minutes. In the exfoliated body of the present invention,
The most important component that imparts good heat resistance is the above-mentioned component (A). By mixing this component (B), the extrudability is improved, and the resin layer is melted on the substrate industrially. It becomes easier to form by molding. When the component (A) and the component (B) are mixed, the mixing ratio is preferably such that the component (A) is 50% by weight or more by weight.
Further, it is desirable that (A) / (B) be in the range of 95 to 50/5 to 50.

Other olefin polymers can be added to the resin layer of the present invention as long as the essence of the invention is not impaired. For example, a linear low-density polyethylene by a Ziegler method, a propylene homopolymer, a propylene-based copolymer obtained by copolymerizing propylene and ethylene, butene-1, etc. (any of random and block copolymers are possible).
Ethylene / α-olefin copolymer rubber is exemplified.
Examples of the ethylene / α-olefin copolymer rubber include ethylene / propylene copolymer rubber and ethylene / propylene / diene copolymer rubber having a density of 0.86 to 0.91 g / cm ³ . The ethylene-propylene rubber is mainly composed of a random copolymer (EPM) containing ethylene and propylene as main components and a diene monomer (dicyclopentadiene, ethylidene norbornene, etc.) added as a third component. Random copolymer (EPDM) and the like can be mentioned. In addition, if necessary,
Organic or inorganic fillers, tackifiers, antioxidants,
Anti-fogging agents, organic or inorganic pigments, dispersants, nucleating agents, foaming agents, flame retardants, crosslinking agents, UV inhibitors, lubricants such as (un) saturated fatty acid amides and metal salts of (un) saturated higher fatty acids Can be added to such an extent that the properties of the present invention are not essentially impaired. Among these additives, lubricants, tackifiers and inorganic fillers are preferably used for further improving workability. Lubricants include oleamide, stearamide, erucamide,
And fatty acid amides such as stearic acid monoglyceride, stearic acid diglyceride, oleic acid monoglyceride, oleic acid diglyceride, etc., and polyethylene glycol adducts thereof. Examples of the inorganic filler include light and heavy calcium carbonate, talc, silica, zeolite, magnesium carbonate, feldspar and the like. Examples of the tackifier include tackifiers such as polybutene, castor oil derivatives, sorbitan fatty acid esters, rosin and rosin derivatives, petroleum resins and hydrogenated products thereof, and rubbers. These tackifiers can be blended in the range of 0.5 to 20 parts by weight. As the pigment, carbon black, titanium white, etc., and various commercially available colorant masterbatches are suitably used.

Further, additives for obtaining appropriate slip properties, antistatic properties and antifogging properties can be added.
Specifically, sorbitan monooleate, sorbitan monolaurate, sorbitan monobehenate, sorbitan monostearate and the like as sorbitan fatty acid esters;
As glycerin fatty acid esters, glycerin monooleate, glycerin monostearate, glycerin monolaurate, glycerin monobehenate, etc .; as polyglycerin fatty acid esters, diglycerin monolaurate, diglycerin monostearate, diglycerin monooleate, tetraglycerin Other than monooleate, tetraglycerin monostearate, hexaglycerin monolaurate, hexaglycerin monooleate, decaglycerin monolaurate, decaglycerin monostearate, decaglycerin monooleate, etc., fatty acid esters of polyhydric alcohols and ethylene thereof Oxide adducts, higher fatty acid amides and their ethylene oxide adducts, higher fatty acid alkanolamides, and the like, but are not limited thereto. Not.

[Substrate] The substrate is appropriately selected depending on the application and is not limited, but generally, paper, woven fabric, or nonwoven fabric is applied. As paper, high quality paper, kraft paper,
Examples include glassine paper, inorganic fiber mixed paper, and synthetic resin mixed paper. [Release Agent Layer] Conventionally used release agents are used as the release agent, and examples thereof include silicone (addition reaction type, condensation reaction type), and silicone / alkyd copolymer.

The filling layer is formed on one side or both sides of the substrate depending on the type of the peeled body, and the thickness thereof may be the same or different, and preferably 7 μm or more on one side.
10-30 micrometers is more preferable. A method for forming the filling layer is not limited, but a melt extrusion molding method is preferable. The resin temperature during extrusion is generally 28
0-350 ° C. However, in the case of using a so-called ozone treatment method in which the ozone of the molten resin discharged from the T-die is blown, the temperature is preferably 200 to 350 ° C. If these conditions are not satisfied, generally, the adhesion between the resin layer and the substrate tends to decrease. In order to further improve the adhesiveness, the substrate may be subjected to a surface treatment such as a preheat treatment, a corona treatment, a flame treatment, and a UV treatment. In the peeled body of the present invention,
It is necessary that the adhesive strength between the substrate and the resin layer is 50 g / 15 mm width or more. If the width is less than 50 g / 15 mm, there is a possibility that the resin may be peeled off from the base material and the resin layer at a predetermined position in the release agent layer.

[0064]

〔Test method〕

 Density: Based on JIS K6760. MFR: Based on JIS K6760.

Molecular weight distribution Mw / Mn: Using a GPC apparatus (Waters 150 type) and using an OD of 135 ° C. as a solvent.
CB was used. The column used was GMHHR-H (S) from Tosoh. It was based on a calibration curve method using a PS standard sample. NMR: GX-270 manufactured by JEOL Ltd. was used. ODCB at 135 ° C. was used as the solvent. Neck-in (NI): The molding conditions of the extruder were set to a film thickness of 30μ.
m, take-off speed 60 m / min, laminating on the substrate,
Difference (m) between the width (W) of the laminate film and the die width (W ₀ )
m) was measured. NI = W ₀ -W drawdown (DD): the 30rpm rotation speed of the extruder, when gradually increased take-up speed was measured up to take-off speed of the laminate film is not broken. Heat-resistant pinhole property: A4 size test piece was cut out from the laminated sample and measured at each temperature (130, 1
(35, 140, 145, 150 ° C.), left for 1 minute in an oven maintained at room temperature, returned to room temperature, and painted with water containing a pigment and a surfactant. If pinholes were formed, fine spots due to pigment appeared on the back of the paper, and the number was counted. In Table 1, 0 items are indicated by ○, 1
３ = 3, × = 4 or more

[Production of Ethylene / α-Olefin Copolymer (A)] Preparation of solid catalyst Purified toluene was added to a catalyst preparation device (No. 1) equipped with an electromagnetic induction stirrer under nitrogen, and then dipropoxydichlorozirconium (Zr 28 g of (OPr) ₂ Cl ₂ ) and 48 g of methylcyclopentadiene were added, and 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the dropwise addition, the reaction system was kept at 50 ° C. and stirred for 16 hours. This solution was used as solution A. Next, the purified toluene was added to another catalyst preparation device with a stirrer (No. 2) under nitrogen, and the above-mentioned A solution and then a 6.4 mol toluene solution of methylaluminoxane were added and reacted. This was designated as solution B. next,
Purified toluene was added to a preparation device with a stirrer (No. 1) under nitrogen, and then silica (Grade # 952, manufactured by Fuji Devison, surface area 30) previously calcined at 400 ° C. for a predetermined time.
(0 m ² / g), 1400 g was added, and then the entire amount of the B solution was added, followed by stirring at room temperature. Then, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This was designated as catalyst C.

Polymerization of Sample Using a continuous fluidized bed gas phase polymerization apparatus, the polymerization temperature was 70
° C., was carried out copolymerization of ethylene and 1-hexene at a total pressure 20kgf / cm ² G. The polymerization was carried out by continuously supplying the catalyst C, and in order to keep the gas composition in the system constant, the polymerization was carried out while continuously supplying each gas to produce an ethylene / 1-hexene copolymer. The physical properties of the ethylene / 1-hexene copolymer were as follows. Density = 0.912 g / cm ³ MFR = 10 g / 10 min Molecular weight distribution (Mw / Mn) = 2.6 Composition distribution parameter Cb = 1.22 TREF peak temperature = 83.5, 96.7 ° C. d−0.008 log MFR = 0.904 ODCB soluble matter (%) = 1.5 <9.8 × 10 ³ × (0.9300−d + 0.008 log
(MFR) ² +2.0

Example 1 80% by weight of the above polymerized ethylene / 1-hexene copolymer was used as the component (A), and the component (B) had an MFR of 7.0 g / 10 min and a density of 0.9.
No. 17 high-pressure method low-density polyethylene, 20% by weight, 0.09% by weight of antioxidant and 0.1% by weight of calcium stearate, and uniformly mixed with a Henschel mixer for about 30 seconds. The mixture was kneaded with an extruder and pelletized to obtain a composition C1. This composition C1 was subjected to an extrusion laminator (made by Modern Machinery, 90 mmφ, die width: 80).
0 mm), using a high-quality paper as a substrate, and a resin temperature of 315 ° C.
And extrusion-laminated with a thickness of 30 μm. Table 1 shows the evaluation results.
Shown in The resin layer had good bite against paper as a substrate, the surface of the paper was well sealed, and exhibited a good heat-resistant pinhole property even at a temperature considered to far exceed the melting point of the composition.

Example 2 A peeled body was manufactured in the same manner as in Example 1 except that kraft paper was used as the substrate. [Example 3] The above ethylene / 1-hexene copolymer was converted to 6
0% by weight, and the component (B) had an MFR of 7.0 g / 10 m.
in, high-pressure low-density polyethylene with a density of 0.917
A composition C2 was prepared in the same manner as in Example 1 except that the amount was 0% by weight, and a peeled body was produced.

Comparative Example 1 In place of the ethylene / 1-hexene copolymer of Example 3, 60% by weight of a linear low-density polyethylene using a Ziegler catalyst having an MFR of 9.0 g / 10 min and a density of 0.912 A composition C3 was prepared in the same manner as in Example 3 except that the MFR was 7.0 g / 10 min and the high-pressure low-density polyethylene having a density of 0.917 was 40% by weight as the component (B). A peeled body was manufactured. The heat-resistant pinhole property was inferior. Comparative Example 2 In the same manner as in Example 1, except that instead of the ethylene / 1-hexene copolymer, a high-density polyethylene having an MFR of 9.0 g / 10 min and a density of 0.948 was used. Thus, a composition C4 was prepared to produce a peeled body. The heat-resistant pinhole property was inferior.

[0071]

[Table 1]

[0072]

The exfoliated body of the present invention has excellent heat-resistant pinhole properties and can be used for an adhesive sheet or an adhesive tape coated with a pressure-sensitive adhesive, a heat-sensitive adhesive, a prepreg adhesive or the like. In addition, since the heat resistance is high, the drying step in forming the release agent layer can be performed at a high temperature, so that the process time can be shortened and the cost can be reduced.

[Brief description of the drawings]

FIG. 1 is a graph showing an elution temperature-elution amount curve of the component (A1) by a continuous temperature-elution fractionation method.

FIG. 2 is a graph showing an elution temperature-elution amount curve of the component (A2) by a continuous temperature-elution fractionation method.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Satoshi Maruyama 2-3-2 Yoko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture, Japan Polyolefin Co., Ltd. Kawasaki Research Laboratory

Claims (6)

[Claims] 1. A substrate comprising: a resin layer containing an ethylene homopolymer or an ethylene / α-olefin copolymer (A) satisfying the following requirements (a) to (d): and a release agent layer. And the adhesive strength between the substrate and the resin layer is 50 g /
A peeled body having a width of 15 mm or more. (A) Density 0.86 to 0.97 g / cm ³ (b) Melt flow rate 0.01 to 100 g / 10
(C) Molecular weight distribution (Mw / Mn) is 1.5 to 5.0 (d) Composition distribution parameter Cb is 2.00 or less 2. The presence of a catalyst in which the ethylene homopolymer or ethylene / α-olefin copolymer (A) contains at least an organic cyclic compound having a conjugated double bond and a transition metal compound belonging to Group IV of the periodic table. 2. The exfoliated product according to claim 1, wherein the exfoliated product is obtained by (co) polymerizing ethylene or ethylene with an α-olefin. 3. The method according to claim 1, wherein the ethylene homopolymer or the ethylene / α-olefin copolymer (A) comprises
The peeled body according to claim 2, which satisfies the requirement (f). (D) The composition distribution parameter Cb is 1.08 to 2.0. (E) There are substantially a plurality of peaks in an elution temperature-elution amount curve obtained by a continuous heating elution fractionation method. (F) Orthodichlorobenzene soluble content X (wt%) at 25 ° C, density d and melt flow rate (MFR)
Satisfies the following relationship. (A) When d−0.008 log MFR ≧ 0.93 X <2.0 (b) When d−0.008 log MFR <0.93 X <9.8 × 10 ³ × (0.9300−d + 0.008 log MFR) )
² + 2.0 4. The ethylene homopolymer or ethylene / α-olefin copolymer (A) contains at least one kind of a ligand having a cyclopentadienyl skeleton and a transition compound belonging to Group IV of the periodic table. An ethylene homopolymer or an ethylene / α-olefin copolymer (A) satisfying the following requirements (d) and (e) obtained by polymerization in the presence of a catalyst:
The exfoliated body according to claim 1, wherein the exfoliated body is (2). (D) Composition distribution parameter Cb is 1.01 to 1.2 (e) Substantially one peak of the elution temperature-elution amount curve by the continuous heating elution fractionation method 5. The resin layer according to claim 1, wherein the ethylene homopolymer or ethylene / α-olefin copolymer (A) according to claim 1 and another ethylene-based (co) polymer (B) A) a release body comprising the composition described in (1). 6. The composition according to claim 1, wherein the ethylene homopolymer or the ethylene / α-olefin copolymer (A) is 95 to 5%.
0% by weight, other ethylene-based (co) polymer (B) 5 to 5
The exfoliated body according to claim 5, wherein the amount is 0% by weight.