JP2002265892A - Substrate for adhesive tape, adhesive tape and can- sealing tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate which is used for an adhesive tape, generates no poisonous gas such as chlorine gas, is scarcely tacky, and has the same flexibility as that of polyvinyl chloride tape. SOLUTION: This substrate for the adhesive tape comprises at least one of layers each comprising a propylene polymer [I] satisfying conditions comprising (1) a mesopentad fraction (mmmm) of 0.2 to 0.6 and (2) a racemi-pentad fraction (rrrr)/(1-mmmm) of <=0.1, and the substrate for the adhesive tape has at least one of layers each comprising 1 to 99 wt.% of the propylene polymer [I] and 99 to 1 wt.% of an olefinic polymer [II].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flexible pressure-sensitive adhesive tape substrate, a pressure-sensitive adhesive tape obtained by applying a pressure-sensitive adhesive to the pressure-sensitive adhesive tape substrate, and a sealing tape.

[0002]

2. Description of the Related Art Since cellophane adhesive tapes using cellophane as a tape base material have been commercially available, adhesive tapes have been developed in which an adhesive is applied to a base material for an adhesive tape such as paper, polyvinyl chloride, or polyolefin. It has been used for various applications. In recent years, the production volume of adhesive tapes has rapidly increased, and new application fields such as industrial use and medical use as well as consumer use have been developed. At present, the types and applications of pressure-sensitive adhesive tapes put into practical use include packaging and bundling pressure-sensitive adhesive tapes, office and household pressure-sensitive adhesive tapes, bonding pressure-sensitive adhesive tapes, coating masking pressure-sensitive adhesive tapes, surface protection pressure-sensitive adhesive tapes, and sealing pressure-sensitive adhesive tapes. Adhesive tape, anticorrosion / waterproof adhesive tape, electrical insulating adhesive tape, electronic equipment adhesive tape, medical / sanitary material adhesive tape, identification / decorative adhesive tape, label adhesive tape, sealing tape, other specific applications And so on,
Many types of adhesive tapes have been developed and commercialized. 2. Description of the Related Art Conventionally, cans containing sweets and the like are sealed using tape to prevent moisture in the can and to prevent the lid from falling off. Since the edge of the can lid usually protrudes, the sealing tape needs to follow this unevenness, and if the shape of the can is a complex shape such as a polygon such as a square or a rectangle, the can In order to adhere tightly to the tape, further flexibility is required for the sealing tape. For this reason, conventionally, a can tape having a soft vinyl chloride resin excellent in flexibility as a base material has been frequently used. However, due to recent environmental problems, tapes based on vinyl chloride resin require special management (eg, incineration in a controlled incinerator or burying in a controlled dump site) for disposal after use. Thus, alternatives have been desired. Alternatives include cost and flexibility.
Tapes using a polyolefin such as polyethylene or polypropylene as a base material have been studied. Since the can tape is peeled off by the consumer when the can is opened and is discarded as garbage, most of the can tape is incinerated in an unmanaged state mixed with general garbage.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in a pressure-sensitive adhesive tape base material, has a low risk of generating toxic gases such as chlorine gas, has a low stickiness, and has a low tackiness. It is an object of the present invention to provide a pressure-sensitive adhesive tape substrate having the same flexibility, and a pressure-sensitive adhesive tape and a sealing tape using the substrate.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that at least one layer made of a specific propylene polymer or a specific propylene polymer and an olefin-based The present inventors have found that a base material for a pressure-sensitive adhesive tape having at least one layer made of a resin composition containing a polymer can achieve the object, and have completed the present invention. That is, according to the present invention, [1] the following (1) and (2) (1) the mesopentad fraction (mmmm) is 0.2 to 0.6 (2) the racemic pentad fraction (rrrr) 1-mm
mm) and at least one layer of a propylene polymer [I] satisfying [rrrr / (1-mmmm)] ≦ 0.1. And (2) the following (1) and (2) (1) the mesopentad fraction (mmmm) is 0.2 to 0.6; (2) the racemic pentad fraction (rrrr) and (1-mm)
mm) and [rrrr / (1-mmmm)] ≦ 0.1, a resin composition containing 1 to 99% by mass of a propylene polymer [I] and 99 to 1% by mass of an olefin polymer [II]. The present invention provides a pressure-sensitive adhesive tape substrate having at least one layer comprising Further, the present invention provides an adhesive tape and a sealing tape in which an adhesive is applied to these adhesive tape substrates.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The base material for an adhesive tape of the present invention is a base material (a) for an adhesive tape having at least one layer composed of a specific propylene polymer [I], or a specific propylene polymer [I]. And a substrate (b) for an adhesive tape having at least one layer composed of a resin composition containing olefin polymer [II]. Specific propylene polymer [I]
Is a propylene polymer satisfying the following (1) and (2). (1) The mesopentad fraction (mmmm) is 0.2 to 0.6. (2) The racemic pentad fraction (rrrr) and (1-mm)
mm) and [rrrr / (1-mmmm)] ≦ 0.1 In the propylene polymer [I], the mesopentad fraction (mmmm) is preferably from 0.3 to 0.6, and more preferably from 0.4 to 0.4. 5 is more preferred. The relationship between the racemic pentad fraction (rrrr) and (1-mmmm) is [rrrr / (1-mmmm)
mm)] ≦ 0.08, [rrrr /
(1-mmmm)] ≦ 0.06 is more preferable, and it is particularly preferable that [rrrr / (1-mmmm)] ≦ 0.05. When the propylene polymer [I] satisfies the above relationship, the obtained adhesive tape substrate has an excellent balance between the amount of the sticky component and the low elastic modulus. That is, the elastic modulus is low, the flexibility is excellent (also called softness), the sticky component is small, and the surface properties are small (for example, the transfer of the sticky component to bleed or other products is small).
Also has the advantage of being superior. Propylene polymer [I]
When the mesopentad fraction (mmmm) of the above is less than 0.2, stickiness is caused, and when it exceeds 0.6, the elastic modulus is undesirably high. [Rrrr / of propylene polymer [I]
(1-mmmm)] exceeds 0.1, it causes stickiness. Note that the mesopentad fraction (mmmm fraction) used in the present invention refers to A. Zambelli (A. Zamb)
elli) et al., "Macromolecules,
6, 925 (1973) ",
It is a meso fraction in a pentad unit in a polypropylene molecular chain measured by a signal of a methyl group in a ¹³ C-NMR spectrum. When this is increased, it means that stereoregularity is increased. Similarly, the racemic pentad fraction (rrrr fraction) is a racemic fraction in pentad units in a polypropylene molecular chain. [Rrrr / (1-
mmmm)] is an index obtained from the above-mentioned fraction in pentad units, and is an index indicating the uniformity of the stereoregularity distribution of the propylene polymer. As this value increases, the stereoregularity distribution broadens, and high stereoregularity PP (polypropylene) like conventional polypropylene produced using existing catalyst systems
And atactic PP (APP), which means that stickiness increases and transparency decreases. Note that ¹³
The measurement of the C-NMR spectrum was carried out by A. Samberg (A.
Zambellli) et al.
les, 8, 687 (1975) ", according to the following apparatus and conditions.

Apparatus: JNM-EX40 manufactured by JEOL Ltd.
Type 0 ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / ml Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10000 times As the propylene polymer [I], in addition to the requirements (1) and (2),

(3) It is preferable that the intrinsic viscosity [η] measured in tetralin at 135 ° C. is 1.0 to 3.0 deciliter / g. Among them, more preferably, it is 1.0 to 2.5 deciliter / g, and particularly preferably, it is 1.2 to 2.2 deciliter / g. If the intrinsic viscosity [η] is less than 1.0 deciliter / g, stickiness may occur. On the other hand, if it exceeds 3.0 deciliters / g, the flowability may be reduced and the moldability may be poor. Further, the above (1) and (2)
In addition to the requirements of (3) and (4), the amount of the component (W25) eluted at 25 ° C.
0-100 mass% is preferable, and 30-100
% By mass is more preferable, 50 to 100% by mass is particularly preferable, and 60 to 100% by mass is most preferable. W25 refers to the amount (mass) of a component that is eluted without being adsorbed by the packing material at a TREF column temperature of 25 ° C. in an elution curve determined by temperature-raising chromatography under the operating method, apparatus configuration, and measurement conditions described in Examples. %). W25 is an index indicating whether or not the propylene polymer is soft. When this value is increased, it means that the component having a low elastic modulus is increased and / or the non-uniformity of the stereoregularity distribution is widened. In the present invention,
If W25 is less than 20%, flexibility may be lost, which is not preferable.

[0008] The propylene polymer [I] preferably further satisfies any of the following requirements. The molecular weight distribution (Mw / Mn) measured by the gel permeation (GPC) method is 4 or less, more preferably 3.
It is 5 or less, particularly preferably 3 or less. Molecular weight distribution (M
If (w / Mn) exceeds 4, stickiness may occur. Note that the above Mw / Mn is determined by a gel permeation chromatography (GPC) method described in Examples. When the melting endothermic amount ΔH by DSC measurement is 30 J / g or less, flexibility is excellent and preferable. ΔH is an index indicating whether the material is soft or not, and as this value increases, the elastic modulus increases,
It means that the softness is reduced. The melting point (Tm) and the crystallization temperature (Tc) may or may not be present. However, it is preferable that the resin does not have softness or has a low value, particularly, Tm is 100 ° C. or less. Note that ΔH, Tm, and Tc are determined by DSC measurement described in Examples.

The propylene polymer [I] may be any as long as it satisfies the above (1) and (2), and a comonomer other than propylene is copolymerized in an amount of 2% by mass or less as long as the object of the present invention is not impaired. May be used.
Examples of the comonomer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-hexene.
Examples thereof include octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. In the present invention, one or more of these can be used. The method for producing the propylene polymer [I] used in the present invention includes:
A method of polymerizing or copolymerizing propylene using a metallocene catalyst obtained by combining (A) a transition metal compound forming a crosslinked structure via two crosslinking groups and (B) a cocatalyst is preferable. Specifically, the general formula (I)

[0010]

Embedded image

[Wherein M is a group 3 to 10 of the periodic table or La
E represents a tanthanoid metal element ¹And E^TwoIs it
Substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, heterocyclopentadienyl group,
Telocyclopentadienyl group, amide group, phosphide
Ligand selected from the group consisting of a group, a hydrocarbon group and a silicon-containing group
And A¹And A^TwoTo form a crosslinked structure via
And they may be the same or different
X represents a σ-binding ligand, and when there are a plurality of Xs,
A plurality of X may be the same or different, and other X,
E¹, E^TwoAlternatively, it may be crosslinked with Y. Y is Lewis salt
A plurality of Ys are the same or different
Other Y, E¹, E^TwoOr cross-linked with X
May be, A¹And A^TwoIs the two that binds the two ligands
A divalent crosslinking group, a hydrocarbon group having 1 to 20 carbon atoms,
A halogen-containing hydrocarbon group having a prime number of 1 to 20, a silicon-containing group,
Germanium-containing groups, tin-containing groups, -O-, -CO-,
-S-, -SO_Two-, -Se-, -NR¹-, -PR¹
-, -P (O) R¹-, -BR¹-Or-AlR¹-
And R¹Is a hydrogen atom, a halogen atom, a carbon number of 1 to 20
A hydrocarbon group or a halogen-containing hydrocarbon having 1 to 20 carbon atoms
Denote radicals, which may be the same or different
Good. q is an integer of 1 to 5 and represents ((valence of M) -2).
And r represents an integer of 0 to 3. Transition metallization represented by
Compound (A), and the transition metal compound or the component (A).
Capable of forming an ionic complex by reacting with derivatives of
Selected from (B-1) and aluminoxane (B-2)
In the presence of a polymerization catalyst containing the co-catalyst component (B),
A method of polymerizing or copolymerizing pyrene is exemplified.

A specific example of the transition metal compound represented by the general formula (I) is (1,2′-dimethylsilylene)
(2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium Dichloride, (1,2′-dimethylsilylene) (2,
1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,5
-Benzoindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-di-i-propylindenyl) ) Zirconium dichloride, (1,2′-dimethylsilylene) (2,
1'-dimethylsilylene) bis (4-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-
Dimethylsilylene) bis (5,6-benzoindenyl)
Zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis ( 3-
Methylindenyl) zirconium dichloride, (1,
2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2
1'-isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride , Etc. and those obtained by substituting zirconium in these compounds with titanium or hafnium.

Next, the component (B-1) of the component (B) includes triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, Examples thereof include methyl tetraphenylborate (tri-n-butyl) ammonium and benzyltetraphenylborate (tri-n-butyl) ammonium. (B-1) may be used alone, or two or more kinds may be used in combination. On the other hand, as the aluminoxane of the component (B-2),
Methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and the like are mentioned. These aluminoxanes may be used alone or in a combination of two or more. As the polymerization catalyst, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B).

As the organoaluminum compound of the component (C), trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutyl Aluminum hydride,
Examples thereof include diethyl aluminum hydride and ethyl aluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more. Here, in the polymerization of propylene, at least one of the catalyst components can be used by being supported on a suitable carrier.

The polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Legitization is particularly preferred. The polymerization temperature is usually -100 to 2
At 50 ° C., the usage ratio of the catalyst to the reaction raw material is preferably such that the raw material monomer / component (A) (molar ratio) is 1 to 10
^8, it is preferable that the particular 100 to 10 ^5. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is usually
Normal pressure to 20 MPa (gauge).

The olefin polymer [II] contained in the resin composition forming the base material (b) for an adhesive tape of the present invention includes a polypropylene resin other than the propylene polymer [I], and a propylene-ethylene copolymer. Coalesce, propylene-ethylene-diene copolymer, polyethylene resin, ethylene / α-olefin copolymer, ethylene-vinyl acetate copolymer and the like. Examples of the polypropylene resin other than the propylene polymer [I] include homopropylene,
Propylene-ethylene random copolymer, SPP (syndiotactic polypropylene), propylene-ethylene-butene terpolymer, and the like. Examples of the polyethylene resin include LDPE (low density polyethylene), LLDPE (linear low density polyethylene) having 4, 6 or 8 carbon atoms, metallocene LLDPE, EVA
(Ethylene-vinyl acetate copolymer), EMMA (ethylene-methyl methacrylate copolymer), EEA (ethylene-ethyl acrylate copolymer), EMA (ethyl methacrylate), EMAA (ethylene-methyl acrylate copolymer) And ethylene ionomer. These may be used alone or in combination of two or more. This resin composition is composed of 1 to 99% by mass of a propylene polymer [I] and 99 to 1% by mass of an olefin polymer [II]. Preferably, it is composed of 10 to 80% by mass of the propylene polymer [I] and 90 to 20% by mass of the olefin polymer [II]. More preferably, it is composed of 25 to 75% by mass of the propylene polymer [I] and 75 to 25% by mass of the olefin polymer [II]. Particularly preferably, it is composed of 40 to 75% by mass of the propylene polymer [I] and 60 to 25% by mass of the olefin polymer [II].

The resin composition forming the base (b) for an adhesive tape of the present invention comprises 1 to 99% by mass of a propylene polymer [I] and 99 to 1% by mass of an olefin polymer [II], and optionally Various additives used according to the dry blend using a Henschel mixer or the like, a single or twin screw extruder,
It is melt-kneaded using a Banbury mixer or the like. Various additives used as desired include ultraviolet absorbers, HALS (hindered amine light stabilizers),
Lubricants, antioxidants, antiblocking agents, nucleating agents, petroleum resins, antibacterial agents, antistatic agents, coloring agents, heat stabilizers, release agents, antifogging agents, inorganic fillers such as talc and calcium carbonate, glass fibers and Reinforcing agents such as carbon fiber, flame retardants,
Silicone, thermoplastic elastomer, and the like.
In addition, these additives are used as a base material (a) for an adhesive tape having at least one layer composed of a propylene polymer [I].
Can also be added.

As the coloring agent, known dyes, inorganic pigments and organic pigments can be used without any particular limitation. Dyes include azo dyes, anthraquinone dyes, azoic dyes, naphthol dyes, triphenylmethane dyes, polymethine dyes, metal complex dyes, metal-containing dyes, reactive dyes, direct dyes, bisazo dyes, trisazo dyes, sulfur dyes, sulfur vat dyes Dyes, vat dyes, indigoid dyes, ice dyes, mordant dyes, acidic mordant dyes, fluorescent brighteners, complex dyes, organic solvent-soluble dyes, basic dyes, pigment resin dyes (pigment resin color), and the like. Examples of inorganic pigments include mica-like iron oxide, lead white, lead red, silver vermilion, ultramarine, navy blue, cobalt oxide, titanium dioxide, titanium dioxide coated mica, strontium chromate, titanium yellow, titanium black, zinc chromate, iron black, and molybdenum red. , Molybdenum white, litharge, lithopone, emerald green, guinea green, cobalt blue and the like. Examples of the organic pigment include β-naphthol-soluble azo pigment, β-naphthol-insoluble azo pigment, β-oxynaphthoic acid-based azo dye, naphthol AS-based soluble azo pigment, naphthol AS-based insoluble azo pigment, and acetoacetarylide-based soluble azo pigment. , Acetoacetarylide-based insoluble azo pigment, pyrazolone-based azo pigment, naphthol AS-based non-condensable azo pigment, acetoacetarylide-based condensable azo pigment, phthalocyanine blue, dye lake, isoindolinone,
Quinacridone, dioxazine violet, perinone,
Perylene, azulene and the like can be mentioned. The base material for an adhesive tape of the present invention comprises a single layer having only a layer composed of a propylene polymer [I] or a layer composed of a resin composition containing a propylene polymer [I] and an olefin polymer [II]. It may have a layered structure or a multilayered structure having at least one of these layers. The adhesive tape base material having a multilayer structure has two or more layers, and preferably has three to ten layers, and more preferably three to five layers.

Layers other than the layer composed of the propylene polymer [I] or layers other than the layer composed of the resin composition containing the propylene polymer [I] and the olefin-based polymer [II] are formed by adding propylene to these layers. It can be formed by blending a polypropylene resin other than the polymer [I], a polyethylene resin, or a thermoplastic elastomer, or by using such a polypropylene resin or a polyethylene resin. Also in this case, the various additives described above can be added. Examples of the polypropylene-based resin and the polyethylene-based resin other than the propylene polymer [I] include those similar to those exemplified for the olefin-based polymer [II]. As thermoplastic elastomers, thermoplastic elastomers include EPR (ethylene / propylene rubber elastomer), HSBR (hydrogenated-styrene / butadiene rubber elastomer), SEPS (styrene / ethylene / propylene / styrene elastomer), SIPS
(Styrene / isoprene / styrene elastomer).

The substrate for an adhesive tape of the present invention can be produced by a known sheet forming method (belt process, calender forming method, knife coating method, T-die extrusion forming method, inflation forming method, cast forming method). . The thickness of the base material for an adhesive tape of the present invention is 0.05 to 0.5.
mm, more preferably 0.05 to 0.2 mm, even more preferably 0.05 to 0.15 mm, and 0.05
~ 0.1 mm is particularly preferred. The pressure-sensitive adhesive tape or canned tape of the present invention is obtained by applying a pressure-sensitive adhesive to the surface of a substrate for a pressure-sensitive adhesive tape and laminating a pressure-sensitive adhesive layer. As an adhesive,
Acrylic adhesive, natural rubber adhesive, styrene / isoprene block copolymer (SIS), styrene / butadiene rubber (SBR), isoprene rubber (IR), polyisobutylene (PIB), isobutylene-isoprene rubber (IIR), etc. And a mixture of the natural rubber-based pressure-sensitive adhesive and the synthetic rubber-based pressure-sensitive adhesive described above.
Among these, acrylic adhesives and natural rubber-based adhesives are preferably used because of their high cohesiveness.
These adhesives may be used alone or in combination of two or more.

The thickness of the pressure-sensitive adhesive layer is usually about 5 to 100 μm, preferably 10 to 50 μm. If the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the desired adhesive strength cannot be obtained, and there is a possibility that the pressure-sensitive adhesive tape or the sealing tape may easily float or peel off. The thickness of the adhesive layer is 100μ
If it exceeds m, the adhesive strength is so strong that the releasability when removing the tape is poor, and the adhesive may remain on the adherend. As a method of applying the pressure-sensitive adhesive to the base material, a method generally used conventionally, for example, a flow en method, a roll coater method, a reverse coater method, a doctor blade method, or the like can be used. If necessary, a back surface treatment layer may be formed on the surface of the substrate opposite to the surface on which the pressure-sensitive adhesive layer is formed. This back surface treatment layer can be formed by applying a release agent. Examples of the release agent include long-chain alkyl-based, silicone-based, and fluorine-based release agents.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Production Example 1 Production of Propylene Polymer (P1) (1) Synthesis of Complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride Synthesis (1,2'-dimethylsilylene) (2,
3.0 g (6.97 mmol) of lithium salt of 1'-dimethylsilylene) -bis (indene) was dissolved in 50 ml of THF and cooled to -78 ° C. 2.1 ml (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise, and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, 50 ml of ether was added, and the mixture was washed with a saturated ammonium chloride solution. After liquid separation, the organic phase was dried, and the solvent was removed. 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was removed. I got (Yield 8
Next, 3.04 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above was placed in a Schlenk bottle under a nitrogen stream. 5.88 mmol) and 50 ml of ether. Cool to -78 ° C and n-BuLi
(Hexane solution 1.54M) in 7.6 ml (11.7
(mmol), and the mixture was stirred at room temperature for 12 hours. The solvent was distilled off, and the obtained solid was washed with 40 ml of hexane to convert the lithium salt into an ether adduct.
06 g (5.07 mmol) was obtained (yield 73%). The result of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) is: δ 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.
10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (q, 4H, methylene), 6.2-7.7
(M, 8H, Ar-H). The lithium salt obtained above was dissolved in 50 ml of toluene under a nitrogen stream. After cooling to −78 ° C., a toluene (20 ml) suspension of zirconium tetrachloride (1.2 g, 5.1 mmol) previously cooled to −78 ° C. was added dropwise. After the addition, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off.
The obtained residue was recrystallized from dichloromethane to give 0.9 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1. 3
3 mmol) was obtained (yield 26%). ^{1 H-NMR (90MHz, CDCl} 3) results of measurement by the,: δ 0.0 (s, 18H , trimethylsilyl), 1.02,1.12 (s, 12H, dimethylsilylene), 2.51 (dd , 4H, methylene), 7.1-7.6
(M, 8H, Ar-H).

(2) Polymerization of Propylene In a stainless steel autoclave having a stirrer and having an internal volume of 10 liters, 4 liters of n-heptane, 2 mmoles of triisobutylaluminum, and 2 mmoles of methylaluminoxane (manufactured by Albemarle) were obtained as described above. (1,
2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl)
2 micromoles of zirconium dichloride were charged sequentially. Then, after introducing 0.06 MPa (gauge) of hydrogen, the temperature was raised to 60 ° C., and the total pressure was 0.8.
Propylene gas was introduced up to MPa (gauge).
During the polymerization, propylene was supplied by a pressure regulator so that the total pressure became 0.8 MPa (gauge). Polymerization temperature 60 ° C
After conducting polymerization for 30 minutes, the content is taken out and dried under reduced pressure to obtain a propylene polymer (P1).
I got Table 1 shows the results obtained by the “method for evaluating resin properties of propylene polymer” shown below.

<Method for Evaluating Resin Properties of Propylene Polymer> (1) Measurement of [η] The measurement was performed at 135 ° C. in a tetralin solvent using a VMR-053 automatic viscometer manufactured by Rigo Co., Ltd. (2) Measurement of Pentad Fraction It was measured by the method described in the text of the specification. (3) Measurement of melt flow rate (MFR) 230 ° C., load 21.1 according to JIS K7210
Measured at 8N. (4) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn was measured by an apparatus described below.

GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C. Flow rate: 1.0 Milliliter / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0)

(5) DSC measurement Differential scanning calorimeter (manufactured by Perkin-Elmer, DSC-
Using 7), melt 10 mg of the sample at 220 ° C. for 3 minutes in a nitrogen atmosphere, and then reduce the temperature to 1 ° C./min to −40 ° C., and set the crystallization temperature to the crystallization temperature. : Tc. Furthermore, at −40 ° C., 3
After holding for 1 minute, the melting endotherm obtained by raising the temperature at 10 ° C./minute was defined as ΔH. The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as melting point: Tm. (6) Elevated Temperature Separation Chromatograph The amount W25 (% by mass) of the component eluted without being adsorbed by the filler at the TREF column temperature of 25 ° C. in the elution curve was determined as follows. (A) Operation method A sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on a filler. Thereafter, the column was heated at a rate of 40 ° C./hour to 135
The temperature was raised to ℃ to obtain an elution curve. (B) Apparatus configuration TREF column: Silica gel column (4.6 mm x 150 mm) manufactured by GL Sciences Flow cell: 1 mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Wave number: 3. 1μm column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: within ± 0.2 ° C.

Production Example 2 [Production of Propylene Polymer (P2)] (1) Preparation of Magnesium Compound A glass reactor equipped with a stirrer having an internal volume of about 6 liters was sufficiently replaced with nitrogen gas, and then ethanol was added to the reactor.
30 g, 16 g of iodine and 160 g of metallic magnesium were charged, heated with stirring, and reacted under reflux conditions until hydrogen gas was not generated from the inside of the system to obtain a solid reaction product. The reaction solution containing the solid product was dried under reduced pressure to obtain a magnesium compound. (2) Preparation of solid catalyst component (A) 160 g of the magnesium compound (not pulverized) obtained in the above (1) and purified heptane 80 were placed in a glass reactor having an internal volume of 5 liters which had been sufficiently purged with nitrogen gas. Milliliter, 24 milliliters of silicon tetrachloride and 23 milliliters of diethyl phthalate were charged, the system was maintained at 80 ° C, 770 milliliters of titanium tetrachloride was added with stirring, and the mixture was reacted at 110 ° C for 2 hours. Washed with purified heptane at 90 ° C. Further, after adding 1220 ml of titanium tetrachloride and reacting at 110 ° C. for 2 hours, it was sufficiently washed with purified heptane to obtain a solid catalyst component (A).

(3) Gas phase polymerization of propylene In a polymerization tank having an internal volume of 200 liters, 6.0 g / h of the solid catalyst component obtained in the above (2), 0.2 mol / h of triisobutylaluminum (TIBA), 1-allyl-3,4
-Dimethoxybenzene (ADMB) 0.012 mol / h, cyclohexylmethyldimethoxysilane (CHMD)
(MS) 0.012 mol / h, propylene 37 kg / h, and polymerization was performed at 70 ° C. and 2.8 MPa (gauge) to produce a propylene polymer. The obtained propylene powder was added to 2,5-dimethyl-2,5-di- (t
-Butyl peroxy) -hexane, and the following additive formulation was performed, and a single screw extruder (manufactured by Tsukada Juki Seisakusho, Ltd.):
TLC (Model 35-20) for extrusion granulation to produce pellets. Table 1 shows the results obtained for the obtained pellets (P2) by the above-mentioned "Method for evaluating resin properties of propylene polymer".

(Additive formulation) Phenolic antioxidant: Ciba Specialty Chemicals, Irganox 1010; 1,000 pp
m Phosphorus antioxidant: P-EPQ, manufactured by Clariant Co .;
500 ppm-Neutralizing agent: calcium stearate; 500 ppm-Neutralizing agent: DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd .; 500p
pm

Production Example 3 [Production of propylene polymer (P3)] 400 ml of heptane and triisobutylaluminum were placed in a stainless steel autoclave having an internal volume of 1 liter.
0.5 mmol, and 2 μmol of dimethylanilinium (pentafluorophenyl) borate, and (tertiary-butylamido) dimethyl (tetramethyl-η) produced in the same manner as in Example 1 of JP-A-3-16388.
A catalyst component obtained by preliminarily contacting 1 micromol of ⁵ -cyclopentadienyl) silanetitanium dichloride in toluene for 5 minutes was added. Here, 0.03 MPa of hydrogen (gaug
After introducing e), propylene gas was introduced to a total pressure of 0.8 MPa (gauge), and propylene was supplied by a pressure regulator so that the pressure during polymerization was constant. Polymerization temperature 70 ° C
After polymerization for 1 hour, the content was taken out and dried under reduced pressure to obtain a propylene polymer (P3). "Method for evaluating resin properties of propylene polymer" was performed, and the obtained results are shown in Table 1.

[0031]

[Table 1]

Example 1 The following additives were formulated into the propylene polymer (P1) obtained above, and a single screw extruder (TLC 35, manufactured by Tsukada Juki Seisakusho) was used.
-20) and extruded to produce P1 pellets. (Additive formulation)-Phenolic antioxidant: Ciba Specialty Chemicals, Irganox 1010; 500 ppm-Phosphorus antioxidant: Ciba Specialty Chemicals, Irgafos 168; 1,000 ppm

The obtained pellets of P1 were extruded from a T-die of an extruder (PO-65, manufactured by Placo) and molded at a molding temperature of 250 ° C. and a drawing speed of 4 m / min to produce a raw sheet. . Further, the raw sheet was subjected to a corona treatment, the surface tension was adjusted to 420 μN / cm, and then a rubber-based pressure-sensitive adhesive was applied to produce a can tape. Table 2 shows the results of evaluation by the following “Evaluation method for properties for base material for adhesive tape and sealing tape”.

<Method for Evaluating Properties of Base Material for Adhesive Tape and Sealing Tape> (1) Tensile Modulus The base material before applying the pressure-sensitive adhesive was determined according to JIS K71.
13 was measured by a tensile test. Crosshead speed: 50 mm / min Load cell: 100 kg Measurement direction: machine direction (MD direction) (2) Evaluation of tape A rectangular can (100 mm × 200 m) was measured using an automatic sealing machine.
(m × 200 mm) and a 100 mm × 200 mm area was sealed to evaluate the characteristics. Regarding the workability, も の indicates that workability was good, and X indicates that workability was poor. About the floating (corner part, straight part)
が な い indicates no lifting, and x indicates that lifting was confirmed. Regarding the terminal peeling, the case where there was no peeling or misalignment was evaluated as ○, and the case where the peeling or floating occurred was evaluated as x. In addition,
In Comparative Example 2, since the surface to which the adhesive was not applied was sticky and the tape was entangled with the canister, the canning operation could not be performed.

Example 2 70% by mass of the pellets of P1 obtained above were mixed with 30 parts of polypropylene E-304GP (propylene homopolymer, melt index = 3) (denoted by 304 in Table 2) manufactured by Idemitsu Petrochemical Co., Ltd. % By mass and extruded and granulated with a single screw extruder (TLC35-20, manufactured by Tsukada Juki Seisakusho) to produce pellets as a resin composition for extrusion molding. Using the pellets, a raw sheet and a sealing tape were produced in the same manner as in Example 1, and the same evaluation was performed. Table 2 shows the results of these evaluations. Example 3 Three extruders similar to those used in Example 1 were used, and polypropylene F-744NP manufactured by Idemitsu Petrochemical Co., Ltd. (propylene random copolymer, melt index = 7) was obtained from the T die of each extruder. (In Table 2, 7
44), a layer consisting of the pellets of P1 obtained above and a layer consisting of polypropylene F-744NP were extruded, and these layers were sequentially laminated at a thickness ratio of 1/8/1. And a canned tape having the following formula: Table 2 shows the results of these evaluations.

Example 4 In Example 3, the layer made of P1 pellets was replaced with P1
Example 3 except that the pellets of Example 3 were changed to a layer composed of pellets (same pellets as in Example 2) obtained by blending 70% by mass of polypropylene pellets and 30% by mass of polypropylene E-304GP manufactured by Idemitsu Petrochemical Co., Ltd. In the same manner, a raw sheet and a sealing tape were produced. Table 2 shows the results of these evaluations. Example 5 In Example 1, the layer composed of P1 pellets was replaced with P1
Except that 100 parts by weight of pellets were mixed with 10 parts by weight of a master batch of white colorant (shown as white M / B in Table 2) (PEX197101 WHITE) manufactured by Tokyo Ink. A raw sheet and a canned tape were produced in the same manner as in Example 1. Table 2 shows the results of these evaluations.

Example 6 In Example 3, the layer made of P1 pellets was replaced with P1
Except that 100 parts by weight of pellets were mixed with 10 parts by weight of a master batch of white colorant (shown as white M / B in Table 2) (PEX197101 WHITE) manufactured by Tokyo Ink. In the same manner as in Example 3, a raw sheet and a sealing tape were produced. Table 2 shows the results of these evaluations. Comparative Example 1 A raw sheet and a can tape were produced in the same manner as in Example 1 except that the P2 pellets obtained above were used instead of the P1 pellets. Table 2 shows the results of these evaluations. Comparative Example 2 A raw sheet and a can tape were produced in the same manner as in Example 1 except that the P3 pellets obtained above were used instead of the P1 pellets. Table 2 shows the results of these evaluations.

[0038]

[Table 2]

[0039]

According to the present invention, there is little danger of generating toxic gases such as chlorine gas, and there is little stickiness.
A substrate for an adhesive tape having the same flexibility as polyvinyl chloride can be obtained.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C08L 23/00 C08L 23/00 23/12 23/12 F term (reference) 4F071 AA15 AA15X AA20 AA28X AA33X AA76 AH19 BB02 BB04 BB06 BB09 BC01 4F100 AK03A AK03B AK07A AK07B AL05A AL05B AN00G AR00C AR00D BA02 BA03 BA04 BA07 BA10C BA10D CA16C CA16D CB05C CB05D GB90 JA06A JA06B JA20A JA20B JK13 JL00 JL11C JL11D YY00A YY00B 4J002 BB03X BB06X BB07X BB12W BB14X BB15X GJ01 4J004 AA04 AA05 AA06 AA10 AB01 CA04 CC02 CC03 DB01 EA01 FA08 4J100 AA02P AA02Q AA03P AG04Q AL03Q CA01 CA04 DA41 FA10 JA05

Claims (8)

[Claims] 1. The following (1) and (2) (1) a mesopentad fraction (mmmm) is 0.2 to 0.6 (2) a racemic pentad fraction (rrrr) and (1-mm)
mm) and at least one layer of the propylene polymer [I] satisfying [rrrr / (1-mmmm)] ≦ 0.1. 2. The propylene polymer [I] further satisfies the following (3) (3): intrinsic viscosity [η] measured in tetralin at 135 ° C. is 1.0 to 3.0 deciliter / g. The substrate for an adhesive tape according to claim 1, which is a propylene polymer. 3. A propylene polymer which further satisfies the following (4) (4) a component amount (W25) eluted at 25 ° C. or lower in temperature rising chromatography (W25) of 20 to 100% by mass. The base material for an adhesive tape according to claim 1 or 2, which is a united product. 4. The propylene polymer [I] is polymerized using a metallocene catalyst comprising a transition metal compound having a crosslinked structure via two crosslinking groups and a cocatalyst. 3. The substrate for an adhesive tape according to any one of 3. 5. The following (1) and (2) (1) a mesopentad fraction (mmmm) is 0.2 to 0.6 (2) a racemic pentad fraction (rrrr) and (1-mm)
mm) and [rrrr / (1-mmmm)] ≦ 0.1, a resin composition containing 1 to 99% by mass of a propylene polymer [I] and 99 to 1% by mass of an olefin polymer [II]. A substrate for an adhesive tape, comprising at least one layer comprising: 6. The pressure-sensitive adhesive tape substrate according to claim 1, wherein the pressure-sensitive adhesive tape substrate has a multilayer structure. 7. A pressure-sensitive adhesive tape, wherein a pressure-sensitive adhesive is applied to at least one surface of the pressure-sensitive adhesive tape base material according to any one of claims 1 to 6. 8. A can tape having a pressure-sensitive adhesive applied to at least one surface of the pressure-sensitive adhesive tape substrate according to any one of claims 1 to 6.