JPH0819300B2 - Composition for bonding polyolefin resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention has excellent adhesiveness to a polyolefin resin and heat stability, and is suitable for use as a hot melt adhesive, heat sealability-imparting agent, etc. It is about.

[Conventional technology]

Conventionally, hot melt adhesives, heat sealability-imparting agents, etc. have been based on ethylene / vinyl acetate copolymer-based adhesives, styrene / isobutylene / styrene block copolymers, styrene / butadiene / styrene block copolymers, etc. Rubber-based adhesives are used.

[Problems to be solved by the invention]

However, ethylene / vinyl acetate copolymer-based adhesives, which are the mainstream of conventional hot melt adhesives, have poor adhesiveness to polyolefin resins such as polyethylene resin and polypropylene resin. Rubber-based adhesives based on styrene / isobutylene / styrene block copolymers, styrene / butadiene / styrene block copolymers, etc. have excellent adhesiveness to polyolefin resins, but have poor heating stability and large viscosity changes. There was a problem.

An object of the present invention is to provide a composition for adhering a polyolefin resin for solving the above conventional problems.

Another object of the present invention is to provide a composition for bonding a polyolefin resin, which has excellent adhesiveness to a polyolefin resin and excellent heat stability.

Another object of the present invention is to provide a composition for bonding a polyolefin resin, which can be used as a hot melt adhesive, a heat-sealability-imparting agent or the like.

[Means for solving problems]

The present invention provides a propylene comprising (A) a repeating unit (a) derived from propylene, a repeating unit (b) derived from ethylene, and a repeating unit (c) derived from an α-olefin having 4 to 20 carbon atoms. (I) 40 to 90 mol% of repeating units (a) derived from propylene, and (b) repeating units derived from ethylene
Is 2 to 40 mol%, and the repeating unit (c) derived from the above α-olefin is 10 to 40 mol%, and c /
The molar ratio of (b + c) is in the range of 0.1 to 0.9, and (ii) the intrinsic viscosity [η] measured at 135 ° C in decalin is
(Iii) 30 to 70% by weight of a low-crystalline propylene random copolymer having a crystallinity in the range of 5 to 40% as measured by X-ray diffractometry, in the range of 0.1 to 7 dl / g, (B) ) A composition for adhering a polyolefin resin, which comprises 70 to 30% by weight of a tackifier.

(A) Low-Crystalline Propylene-based Random Copolymer The low-crystalline propylene-based random copolymer of the component (A) used in the present invention has a propylene component (a repeating unit (a) derived from propylene) of 40 to 90. Mol%, preferably 50 to 80 mol%, more preferably 50 to 70 mol%, the ethylene component (repeating unit (b) derived from ethylene) is 2 to 40 mol%, preferably 5 to 30 mol%, more preferably Is 10 to 20 mol% and an α-olefin component having 4 to 20 carbon atoms (4 to 4 carbon atoms).
The repeating unit (c)) derived from 20 α-olefins is
It is in the range of 10 to 40 mol%, preferably 15 to 35 mol%, more preferably 15 to 30 mol%.

As the α-olefin having 4 to 20 carbon atoms, butene-1, pentene-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, heptene-1, octene-1, nonene-1 , Decene-1, dodecene-1, tetradecene-1, octadecene-1 and the like having 18 or less carbon atoms are preferable, and those having 4 to 10 carbon atoms are particularly preferable.

When the propylene component in the component (A) is more than 90 mol%, the melting point is high and the performance as a hot melt adhesive is not sufficient. When the propylene component is less than 40 mol%, the melting point and crystallinity are low, and the stickiness and blocking property are increased. In addition, the ethylene component in component (A) is 40 mol%
If it becomes larger, the polymer becomes non-uniform and the performance as a hot melt adhesive becomes insufficient. 2 ethylene components
If it is less than mol%, the melting point and crystallinity are high and the performance as a hot melt adhesive is not sufficient. Further, when the content of the α-olefin component in the component (A) is more than 40 mol%, the melting point and the crystallinity are low, and the stickiness and blocking property are increased. The above α-olefin component is 10
If it is less than mol%, the melting point and crystallinity are high and the performance as a hot melt adhesive is not sufficient.

The molar ratio c / (b + c) of the ethylene component (b) and the α-olefin component (c) is 0.1 to 0.9,
Preferably 0.3 to 0.8, more preferably 0.5 to 0.7
It is a range. If the above molar ratio is larger than 0.9, the melting point and crystallinity are high, and the performance as a hot melt adhesive is insufficient. Even if the above molar ratio is less than 0.5, the melting point and crystallinity are high, and the performance as a hot melt adhesive is not sufficient. Here, the composition of the copolymer is determined from the infrared absorption spectrum of the press film.

The intrinsic viscosity [η] of the low crystalline propylene random copolymer as the component (A) measured in decalin at 135 ° C. is 0.1.
To 7 dl / g, preferably 0.2 to 5 dl / g. This characteristic value is a scale showing the molecular weight of the propylene random copolymer as the component (A), and by combining with other characteristic values, it serves to provide the random copolymer having the above-mentioned excellent properties.

The crystallinity of the low crystalline propylene random copolymer of the component (A) measured by X-ray diffraction is 5 to 40.
%, Preferably 10 to 30%. This characteristic value is a measure indicating that the propylene random copolymer of the component (A) has excellent tensile properties, and by combining with other characteristic values, it is useful for providing the random copolymer having the above-mentioned excellent properties. ing. The crystallinity is determined by X-ray diffraction measurement of a press sheet having a thickness of 1.5 mm 20 hours after the molding.

The melting point of the low crystalline propylene random copolymer of the component (A) measured by a differential scanning calorimeter [hereinafter referred to as DSC
It may be abbreviated as "melting point"], and is preferably in the range of 0 to 100 ° C, preferably 10 to 90 ° C. The low melting point measured by DSC means that the propylene random copolymer as the component (A) has a high crystallinity and a high melting point, which is conventionally known, and The propylene random copolymer, which is crystalline and has no melting point, is clearly distinguished from the propylene random copolymer, which shows that it is a propylene random copolymer having a low melting point. The melting point, in combination with other property values, serves to provide the copolymer with the above-mentioned excellent properties. Here, the DSC melting point is obtained by measuring a press sheet having a thickness of 0.1 mm after a lapse of 20 hours after molding from 0 to 200 ° C. at a temperature rising rate of 10 ° C./min, and the maximum endothermic peak is Tm.

In the propylene random copolymer of the component (A), an acetone / n-decane mixed solvent (volume ratio 1
The amount of soluble components (W ₁ % by weight) in 1/1) is 6.5 × [η] ^−1.0 % by weight or less, for example, 0.1%, based on the weight of the copolymer.
× [η] ^{−1.0 to} 6.5 × [η] ^−1.0 % by weight, preferably
0.2 × [η] ^{−1.0 to} 6.0 × [η] ^−1.0 % by weight, particularly preferably 0.3 × [η] ^{−1.2 to} 5.5 × [η] ^−1.0 % by weight (here, η] is a numerical value of the intrinsic viscosity of the copolymer, which is a value excluding the dimension). This characteristic value is a measure showing the content of the low molecular weight polymer component in the propylene random copolymer as the component (A), and is a measure showing the breadth of the composition distribution and the molecular weight distribution of the copolymer, and has been known from the past. The propylene random copolymer present has a large amount of acetone / n-decane mixed solvent soluble components, which is inferior in surface non-adhesiveness and causes a large blocking property. This characteristic value in the propylene random copolymer as the component (A) is useful for providing the copolymer having the above-mentioned excellent properties by combining with other characteristic values.

The soluble content of the copolymer in the above mixed solvent is measured and determined by the following method. That is, 1 g of the copolymer sample, 0.05 g of 2,6-di-tert-butyl-4-methylphenol and 50 ml of n-decane were placed in a 150 ml flask equipped with a stirring blade, and 12
Dissolve on 0 ° C. oil bath. After dissolution, the mixture is allowed to cool naturally at room temperature for 30 minutes, and then 50 ml of acetone is added in 30 seconds, followed by cooling on a 10 ° C water bath for 60 minutes. A solution in which the precipitated copolymer and low molecular weight polymer component are dissolved is separated by filtration with a glass filter, and the solution is dried at 10 mmHg and 150 ° C. until a constant weight is obtained,
The weight is measured, and the soluble amount of the copolymer in the mixed solvent is calculated and determined as a percentage with respect to the weight of the sample copolymer. In the measuring method, stirring is continuously performed from the time of dissolution to immediately before filtration.

In the low crystalline propylene random copolymer as the component (A), the amount soluble in boiling methyl acetate [W ₂ % by weight]
Is 10% by weight or less based on the weight of the copolymer, for example
It is desirable to be in the range of 0.01 to 10% by weight, preferably 0.01 to 9% by weight. This characteristic value is a measure showing the content of the low molecular weight polymer component in the propylene random copolymer as the component (A), and is a measure showing the breadth of the composition distribution and the molecular weight distribution of the copolymer, and has been proposed in the past. The propylene-based random copolymer present has a large amount of boiling methyl acetate-soluble content, is inferior in surface non-adhesiveness, and is a cause of large blocking property. The boiling methyl acetate soluble content is measured by the following method. That is, put a strip sample of about 1mm x 1mm x 1mm into a cylindrical glass filter, extract it with a Soxhlet extractor for 7 hours with a reflux frequency of about 1/5 minutes, and extract the residue to a vacuum dryer (vacuum degree 10mmHg The weight is obtained by drying until a constant weight is obtained in the following), and the boiling methyl acetate-soluble content weight is obtained from the weight difference from the original sample. The boiling methyl acetate-soluble content (W ₂ ) is obtained as a percentage of the boiling methyl acetate-soluble content with respect to the original sample weight.

The low crystalline propylene random copolymer (A) has a molecular weight distribution (W / n) measured by gel permeation chromatography (GPC) of, for example, 10 or less, preferably 3 to 10, particularly preferably 4 to A range of 8 is desirable. The GPC measurement method is as follows. That is, Waters (150C-ALC / GPC)
Is measured using a Toyo Soda (GMH type) column at 140 ° C. using o-dichlorobenzene as a solvent.

As described in Japanese Patent Application No. 61-85121, a method for producing a low-crystalline propylene random copolymer as the component (A) is a high-concentration compound containing magnesium, titanium, halogen and an electron donor as essential components. Copolymerizing propylene, ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of a catalyst formed from a stereoregular titanium catalyst component, an organoaluminum compound catalyst component, and an electron donor catalyst component. Can be manufactured by.

The above-mentioned highly active and highly stereoregular solid titanium catalyst component used for the production of the component (A) contains magnesium, titanium, halogen and an electron donor as essential components, and has a magnesium / titanium (atomic ratio) of Greater than 1, preferably 3 to 50, particularly preferably 6 to 30, halogen / titanium (atomic ratio) is preferably 4 to 100, particularly preferably 6 to 40, electron donor / titanium (molar ratio) is preferred. It is preferably in the range of 0.1 to 10, particularly preferably 0.2 to 6. Its specific surface area is preferably 3 m ² / g or more, more preferably 40 m ² / g
Above, more preferably 100 m ² / g to 800 m ² / g.
The solid titanium catalyst component has an average particle size of, for example, 1 to
200μ, preferably 3 to 100μ, particularly preferably 6
To 50μ, the geometric standard deviation of the particle size distribution is, for example, less than 2.1, preferably 1.9 or less, more preferably 1.7.
The following is desirable.

Titanium catalyst components that are all satisfied under such conditions include, for example, a method of preparing a catalyst after forming a magnesium compound having an average particle size and particle size distribution, more preferably a shape in the range as described above, Alternatively, it can be obtained by a method in which a liquid magnesium compound and a liquid titanium compound are brought into contact with each other to form a solid catalyst having the above-mentioned particle properties. Such a method is disclosed in, for example, JP-A-55-135102, JP-A-55-135103, and JP-A-55-135103.
56-811, 56-67311, 58-83006, etc.

As the magnesium compound used for preparing the titanium catalyst component, magnesium oxide, magnesium hydroxide,
Hydrotalcite, magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, alkoxymagnesium halide, allyloxymagnesium halide, magnesium dihalide, organomagnesium compound, organomagnesium compound and electron donor, halosilane, alkoxysilane, silanol, aluminum A reaction product with a compound or the like can be exemplified. The organoaluminum compound that may be used to prepare the titanium catalyst component may be selected from the organoaluminum compounds that can be used in the olefin polymerization described later. Further, examples of the halogen-containing silicon compound which may be used for the preparation of the titanium catalyst component include tetrahalogenated silicon, alkoxyhalogenated silicon, alkylhalogenated silicon and halopolysiloxane.

Examples of titanium compounds used in the preparation of the titanium catalyst component include titanium tetrahalides, alkoxy titanium halides, allyloxy titanium halides, alkoxy titanium, allyloxy titanium, and the like, particularly titanium tetrahalide, especially titanium tetrachloride. Is preferred.

Electron donors that can be used to prepare the titanium catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids,
Oxygen-containing electron donors such as ethers, acid amides, and alkoxysilanes of acid anhydrides, ammonia, amines, nitriles,
A nitrogen-containing electron donor such as isocyanate can be used.

The preferred organometallic compound catalyst component used for producing the component (A) is an organoaluminum compound, and a compound having at least one Al-carbon bond in the molecule can be used. ) General formula R ¹ _m Al (OR ² )
_n H _p X _q (where R ¹ and R ² are usually carbon atoms of 1 to 15
Hydrocarbon groups containing one, preferably one to four, may be the same or different from each other. X is halogen, m is 0 <m ≦
3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦ q <3
Of the formula ( ¹ ) and (m + n + p + q = 3), and (ii) the general formula M ¹ AlR ¹
₄ (herein, M ¹ is Li, Na, K and R ¹ is the same as the above) and a complex alkylated product of a Group 1 metal and aluminum.

The organoaluminum compound belonging to the above (i) is represented by the general formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably a number of 1.5 ≦ m ≦ 3). General formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above. X is halogen,
m is preferably 0 <m <3), the general formula R ¹ _m AlH _3-m
(Wherein R ¹ is the same as above, m is preferably 2 ≦ m <3), the general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above. X Is halogen, 0 <m ≦ 3, 0 ≦ n <3, 0
≦ q <3, and m + n + q = 3).

The compounds belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ and L
Examples thereof include iAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use trialkylaluminum, or a mixture of trialkylaluminum and alkylaluminum halide or aluminum halide.

Examples of the electron donor catalyst component used for producing the component (A) include amines, amides, ethers, ketones, nitriles, phosphines, stibines, arsines, phosphoramides and esters. , Thioethers, thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, organic acids, and amides of metals belonging to Group 4 but not Group 1 of the periodic table. And salt.

The low crystalline propylene random copolymer as the component (A) can be produced in an inert hydrocarbon solvent in the presence of a catalyst formed from the titanium catalyst component, the organometallic compound catalyst component and the electron donor catalyst component. , Or by copolymerizing propylene, ethylene and an α-olefin having 4 to 20 carbon atoms in the absence of a solvent. In this case, it is particularly preferable to employ a method in which the copolymerization reaction is carried out under the condition that the copolymer produced in an inert hydrocarbon solvent is dissolved.

The proportion of propylene, ethylene and the α-olefin having 4 to 20 carbon atoms to be copolymerized is 40 to 90 mol%, preferably 40 to 80 mol%, in a molar ratio of propylene.
More preferably 40 to 70 mol%, ethylene is 0.1 to 20 mol%, preferably 1 to 15 mol%, more preferably 3 to 15 mol%, and the number of carbon atoms is 4 to 20.
It is desirable that the α-olefin of 10 to 50 mol%, preferably 20 to 50 mol%, more preferably 30 to 45 mol%.

In this case, 100 to 100,000 g, preferably 150 to 20,000 g, and more preferably 200 to 10,000 g of propylene, ethylene and α-olefin having 4 to 20 carbon atoms are copolymerized per 1 g of titanium catalyst component of the catalyst. Is desirable.

When an inert solvent is used in the copolymerization, the titanium catalyst component in the inert solvent is preferably 0.001 to 500 mmol, particularly 0.005 to 200 mmol, in terms of titanium atom. Al / Ti (atomic ratio) is 0.1 to 1000, especially 0.5
It is preferable to use it in such a ratio that it will be from 500 to 500. Further, the catalyst component may be supported on the component,
It may be used in addition to a part of the components, or may be added to the polymerization system in a free state. In any case, the catalyst component is 0.1 to 200 mol per mol of titanium atom, especially
It may be present in an amount of 0.2 to 50 mol.

As the inert hydrocarbon solvent used in the copolymerization, propane, butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene, etc. Of aliphatic hydrocarbons, alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, ethyl chloride, ethylene chloride, chlorobenzene Examples thereof include halogenated hydrocarbons, and among them, aliphatic hydrocarbons, particularly aliphatic hydrocarbons having 4 to 10 carbon atoms are preferable.

The copolymerization temperature can be appropriately selected, preferably about 20 to about 200 ° C., more preferably about 50 to about 180 ° C., the pressure can also be appropriately selected, and atmospheric pressure to about 100 kg / cm ² , preferably atmospheric pressure to It is preferable to carry out under a pressurized condition of about 50 kg / cm ² .

The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the ratio of the catalyst component used, but it is most effective to add hydrogen to the polymerization system.

(B) Tackifier The tackifier as the component (B) used in the present invention is a solid amorphous polymer and is usually used as a tackifier resin in the fields of adhesive tapes, paints, hot melt adhesives and the like. The following resins can be listed according to the difference in the source of the polymerized monomers. For example, C ₄ fraction, C ₅ fraction obtained by cracking petroleum, naphtha, etc., a mixture thereof or any fraction thereof, for example, isoprene and 1,3-pentadiene in the C ₅ fraction are used as main raw materials. Aliphatic hydrocarbon resin; aromatic hydrocarbon resin mainly composed of styrene derivative and indene in C ₉ fraction obtained by decomposition of petroleum, naphtha, etc .;
Aliphatic / copolymerized from any fraction of C ₄ and C ₅ fractions and C ₉ fraction
Aromatic copolymerized hydrocarbon resin; Alicyclic hydrocarbon resin obtained by hydrogenating aromatic hydrocarbon resin; Synthetic terpene hydrocarbon resin having a structure containing aliphatic, alicyclic and aromatic compounds; in turpentine oil -Based hydrocarbon resins made from α, β-pinene as a raw material; indene-based hydrocarbon resins made from indene and styrenes in coal tar-based naphtha; low-molecular-weight styrene-based resins; and rosin-based hydrocarbon resins And so on.

Among these tackifiers (B), alicyclic hydrocarbon resins obtained by hydrogenating an aliphatic hydrocarbon resin and an aromatic hydrocarbon resin are preferable because they have good compatibility with the component (A), and further softening. The point (ring and ball method) is 70 to 150 ° C, preferably 80 to 140 ° C, and the hydrogenation rate to the aromatic nucleus is 8
An alicyclic hydrocarbon resin of 0% or more, preferably 85% or more is particularly preferable.

(C) Composition The composition for adhering a polyolefin resin according to the present invention comprises a low crystalline propylene random copolymer of the above-mentioned component (A) 30.
To 70% by weight, and a tackifier of component (B) 70 to 30
% By weight. In addition to these essential components, the composition for bonding a polyolefin resin of the present invention may further contain a wax or a plasticizer as a viscosity modifier. Such a polyolefin resin bonding composition can be obtained by melting and mixing the above components.

The polyolefin resin bonding composition of the present invention has good adhesiveness to polyolefin resins such as polyethylene resin and polypropylene resin, excellent thermal stability, is easy to handle, and has good hot melt adhesiveness and heat sealability. Are better. These properties are superior to those of the component (A) or the component (B) alone.

Therefore, the polyolefin resin bonding composition of the present invention is suitable as a hot melt adhesive, for example, a diaper hot melt adhesive used for bonding a water-absorbent nonwoven fabric (cotton) and a polyethylene film, an optical disk plate hot melt adhesive, and the like. It is also suitable as a heat-sealability-imparting agent for α-olefin polymers and copolymers such as ethylene polymers and copolymers, propylene polymers and copolymers.

The composition for adhering a polyolefin resin of the present invention is suitable as a hot melt adhesive and a heat sealability-imparting agent, but it can also be used for other applications for adhering a polyolefin resin.

〔The invention's effect〕

According to the present invention, a low crystallinity propylene random copolymer and a tackifier are used as components, so that the hot melt adhesive has excellent adhesiveness and thermal stability to a polyolefin resin, and has little hue change, and heat sealability. A composition for adhering a polyolefin resin, which is suitable as an imparting agent or the like, can be obtained.

〔Example〕

 Examples of the present invention will be described below.

Example 1 <Preparation of titanium catalyst component> 4.76 g (50 mmol) of anhydrous magnesium chloride, 25 ml of decane
And 2-ethylhexyl alcohol 23.4 ml (150 mmol)
Was heated at 130 ° C for 2 hours to form a uniform solution, and 1.11 g (7.5 mmol) of phthalic anhydride was added to this solution.
Stirring and mixing are performed at 0 ° C. for another hour to dissolve phthalic anhydride in the above homogeneous solution. The homogeneous solution thus obtained is cooled to room temperature and then poured into 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C dropwise over 1 hour. After the injection was completed, the temperature of this mixed solution was raised to 110 ° C over 4 hours, and when it reached 110 ° C, 2.68 ml (12.5 mmol) of diisobutyl phthalate was added, and the mixture was maintained at the same temperature for 2 hours with stirring. To do. After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was resuspended in 200 ml of TiCl ₄ , and then the reaction was carried out again at 110 ° C. for 2 hours by heating. After the reaction was completed, the solid part was collected again by hot filtration, and 110
Rinse thoroughly with decane and hexane until no free titanium compound is detected in the washing solution.

The composition of the catalyst component synthesized by the above manufacturing method was 3.1 wt% titanium, 56.0 wt% chlorine, 17.0 wt% magnesium, and 20.9 wt% diisobutylphthalate.

<Polymerization> Using a continuous polymerization reactor with an internal volume of 200 l, dehydrated and purified hexane is 100 l / Hr, ethylene is 1.0 kg / Hr, and propylene is
6.4 kg / Hr, butene-1 was supplied at 7.4 kg / Hr, and hydrogen was supplied so that the gas phase concentration in the polymerizer was 46 mol%, while the above catalyst component was converted to titanium atoms to 2.3 mmol / Hr, Isobutylaluminum (115 mmol / Hr) and diphenyldimethoxysilane (13.8 mmol / Hr) were supplied at the ratios, and the copolymerization was performed under the conditions of a polymerization temperature of 70 ° C., a polymerization pressure of 6 kg / cm ² , and a residence time of 1 Hr.

The physical properties of the resulting propylene / ethylene / butene-1 copolymer (PEB-1) were as follows: propylene content (a) 64 mol%,
Ethylene content (b) 15mol%, butene-1 content (c) 21mol%, intrinsic viscosity [η] = 0.48dl / g, crystallinity = 16%, Tm = 62 ° C, acetone / n-decane mixed solvent Soluble content = 5.3 wt%.

PEB-1 40 wt% and alicyclic hydrocarbon resin "HILETS T-1115" (manufactured by Mitsui Petrochemical Co., Ltd., trade name, softening point 115 ° C, Cardner hue 4) 60% by weight oil at 200 ° C The mixture was placed in a vessel equipped with a stirrer set in a bath and kneaded at 600 rpm for 2 hours to obtain a composition.

After coating this composition on polyethylene terephthalate film (PET) with a thickness of 30 μm, MFR _{190 ° C.} = 2.0
A linear low-density polyethylene film with a density of 0.920 g / cm ³ or a biaxially stretched polypropylene film with a density of 0.920 g / cm ³ is laid on top of this, and heat sealed under the conditions of 120 ° C, 3 kg / cm ² and 10 seconds to obtain the adhesive strength. An evaluation sample was obtained. The physical properties of the sample were evaluated by the following methods. The results are shown in Table 1.

(1) Melt viscosity _{180 ° C.} (cps): Measured with a Brookfield viscometer.

(2) Softening point (° C): measured by ring & ball method.

(3) Viscosity retention rate (%): 180 ° C., 48 hr, melt viscosity _{180 ° C.} after standing in air was measured with a Brookfield viscometer to determine the ratio with the initial melt viscosity _{180 ° C.}

(4) Adhesive force: Measurement temperature: 23 ° C. Peeling method: T-type peeling Peeling speed: 300 mm / min (5) Hue: Visual judgment Examples 2 and 3 PEB-1 used in Example 1 and blending of tackifier Example 1 was repeated except that the composition was changed. The results are shown in Table 1.

Examples 4 and 5 Propylene-ethylene-butene-1 copolymerization was carried out by the same polymerization method as in Example 1 except that the gas phase concentration of the hydrogen in the polymerization vessel was changed to 36 mol% in the polymerization method shown in Example 1. A combination (PEB-2) was obtained. The physical properties of the obtained PEB-2 are as follows: propylene content (a) 63 mol%, ethylene content (b) 17 mol%, butene-1 content (c) 20 mol%, intrinsic viscosity [η] = 0.63d
L / g, crystallinity = 14%, Tm = 58 ° C., acetone / n-decane mixed solvent soluble content = 6.3 wt%.

The physical properties of the composition were evaluated in the same manner as in Examples 2 and 3. The results are shown in Table 1.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 except that the composition of PEB-2 used in Example 4 and the tackifier were changed.

The physical properties of the composition are shown in Table 1, but the melt viscosity becomes too high and the processability during coating is poor.

Comparative Example 2 Instead of PEB-1 used in Example 1, a styrene / isobutylene / styrene block copolymer “Califlex TR” was used.
-1107 "(manufactured by Shell Chemical Co., Ltd., trade name) was used to obtain a composition in the same manner as in Example 2.

The physical properties of the composition are shown in Table 1, but the viscosity retention in an atmosphere of 180 ° C. is low, and the heating stability is poor.

Claims (3)

[Claims] 1. A repeating unit (a) derived from propylene (A), a repeating unit (b) derived from ethylene, and a repeating unit (c) derived from an α-olefin having 4 to 20 carbon atoms. A propylene-based random copolymer, wherein (i) the repeating unit (a) derived from propylene is 40 to 90 mol%, and the repeating unit (b) derived from ethylene.
Is 2 to 40 mol%, and the repeating unit (c) derived from the α-olefin is 10 to 40 mol%, and c /
The molar ratio of (b + c) is in the range of 0.1 to 0.9, and (ii) the intrinsic viscosity [η] measured at 135 ° C in decalin is
(Iii) 30 to 70% by weight of a low crystalline propylene random copolymer having a crystallinity in the range of 5 to 40% as measured by X-ray diffractometry, in the range of 0.1 to 7 dl / g, (B) ) A composition for adhering a polyolefin resin, which contains 70 to 30% by weight of a tackifier. 2. An α-olefin having 4 to 20 carbon atoms is butene-1, pentene-1, hexene-1, 4-methylpentene-1, 3-methylpentene-1, heptene-.
The composition for adhering a polyolefin resin according to claim 1, which is one or more selected from 1, octene-1, nonene-1, decene-1, dodecene-1, tetradecene-1, and octadecene-1. Stuff. 3. The tackifier is an aliphatic hydrocarbon resin, an aromatic hydrocarbon resin, an aliphatic / aromatic copolymer hydrocarbon resin, an alicyclic hydrocarbon resin, a synthetic terpene hydrocarbon resin, or a terpene. The polyolefin resin adhesive according to claim 1 or 2, which is one or more selected from the group consisting of hydrocarbon resins, coumarone-indene hydrocarbon resins, low molecular weight styrene resins and rosin hydrocarbon resins. Composition.