JPS61108647A - Crystalline random propylene copolymer composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which can form a laminated sheet having excellent low-temperature heat sealing properties and high strength when laminated on the surface of a crystalline PP substrate, containing a crystalline random propylene copolymer and a random 1-butene copolymer. CONSTITUTION:The titled compsn. contains a crystalline random propylene copolymer (A) composed of a major portion of propylene and a minor portion of an alpha-olefin other than propylene and a random 1-butene copolymer (B) composed of ethylene and 1-butene. Component B is composed of 1-50mol% of the ethylene component and 99-50ml% of the 1-butene component and has an intrinsic viscosity eta of 0.5-6dl/g (at 135 deg.C in decalin), a m.p. Tm of 30-130 deg.C as measured with a different scanning calorimeter, crystallinity of 1-60% as measured by X-ray diffraction, a boiling methyl acetate soluble content W1 of 2wt% or below and a content W2 of an acetone/n-decane solvent mixture (1:1 by volume) solubles at 10 deg.C of less than 5X[eta]<-1.2>wt%.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a crystalline polypropylene composite laminate that can be laminated on the surface of a crystalline polypropylene base material to form a polypropylene composite laminate with improved heat sealability. The present invention relates to a propylene random copolymer composition.

[Conventional technology]

Crystalline polypropylene film has excellent mechanical properties such as tensile strength, rigidity, surface hardness, and impact strength, optical properties such as gloss and transparency, and food hygiene properties such as non-toxicity and odorlessness, so it is suitable for packaging. It is especially widely used in the field of food packaging.

However, a single layer polypropylene film has the disadvantage that the temperature at which it can be heat-sealed is high and the appropriate temperature range is narrow.

In order to improve the heat sealability of this polypropylene film, several methods have already been proposed in which a low melting point resin is laminated on one or both sides of a crystalline polypropylene film.

For example, JP-A-55-65552 discloses a propylene random copolymer consisting of an ethylene/propylene random copolymer containing propylene as a main component and a propylene/α-olefin random copolymer containing propylene as a main component. A method of laminating a composition to a crystalline polypropylene film is disclosed. Also, JP-A-55-9166
Publication No. 5 discloses that a propylene random copolymer composition consisting of an ethylene/propylene random copolymer containing propylene as a main component and a 1-butene/ethylene random copolymer containing 1-butene as a main component is crystalline. A method of laminating polypropylene film is disclosed. Furthermore, JP-A-54-106585 discloses ethylene-propylene random copolymers containing propylene as the main component, 1-butene/ethylenically unsaturated monomer copolymers containing 1-butene as the main component, and A method of laminating a propylene random copolymer composition comprising a molecular weight thermoplastic resin to a crystalline polypropylene film is disclosed.

Furthermore, the above-mentioned Japanese Patent Application Publication No. 55-91665 (Japanese Patent Application No. 53-1)
65137) and the above-mentioned JP-A-54-106585 (
U.S. Patent No. 4,230,767, which was filed in the U.S. by claiming priority to Japanese Patent Application No. 13932/1983, discloses the above-mentioned ethylene-propylene random copolymer mainly composed of propylene and 1-butene. The propylene random copolymer composition may include an embodiment in which a propylene random copolymer composition including a composition consisting of a 1-butene/propylene copolymer as a main component is laminated on a crystalline polypropylene film. is disclosed. However, no specific example of the above-mentioned aspect is shown, and the above-mentioned JP-A-54-1
As specified in No. 06585, this embodiment only shows an example in which a low molecular weight thermoplastic resin is also used in combination.

Although the heat-sealability of the propylene film in the laminates obtained by these methods is improved, the heat-sealable temperature is still quite high, and the applicable temperature range is also narrow, so it is still difficult to say that the heat-sealability is sufficient. Furthermore, it was difficult to say that the heat seal strength was sufficient.

In addition, in order to develop antistatic properties in these polypropylene composite laminates, a method of subjecting them to low-temperature heat treatment for several days is usually adopted, but in that case, the heat sealing temperature will rise rapidly, etc. There was a drawback. In this way, in the field of packaging applications using polypropylene films, polypropylene composite films that lower the heat-sealing temperature, widen the heat-sealable range of 9q degrees, have excellent heat-sealing strength, and have a small increase in the heat-sealable temperature due to heat treatment are being developed. is strongly requested.

[Problem that the invention seeks to solve]

The present inventors have discovered a crystalline propylene random copolymer that can be laminated on at least one side of a crystalline polypropylene base material layer to form a polypropylene composite laminate with excellent low-temperature heat-sealability and heat-seal strength. Research was conducted with the aim of developing a combined composition. As a result, it consists of a crystalline propylene random copolymer mainly composed of propylene and a 1-butene-based random copolymer having specific properties, mainly composed of 1-butene and with a low content of low molecular weight polymer components. A polypropylene composite laminate in which a crystalline propylene random copolymer composition is laminated on at least one side of a crystalline propylene base layer can be heat-sealed from a relatively low temperature, and has a wide heat-sealable temperature range; It has been discovered that the heat sealing strength is excellent, and the upper limit of the heat sealable flt2 temperature by heat treatment is also small.

Therefore, an object of the present invention is to provide a crystalline propylene random material that can be laminated on at least one side of a crystalline polypropylene base material layer to form a polypropylene composite laminate having excellent low-temperature heat-sealability and heat-sealing strength. An object of the present invention is to provide a copolymer composition.

The above objects and further objects and advantages of the present invention will become more apparent from the following description.

[Means for Solving the Problems] and [Operations] According to the present invention, (1) a crystalline propylene random copolymer consisting of propylene and an α-olefin other than propylene and having propylene as its main component, and ( 11) A 1-butene-based random copolymer consisting of ethylene and 1-butene, and the following items: (A) The composition is 1 to 50 mol% of the ethylene component and 50 to 99 mol% of the 1-butene component. (B) Intrinsic viscosity measured at 135°C in decalin [
η] is in the range of 0.5 to 6 cll/g, (
C) Differential scanning calorimeter; the melting point (T
m) is in the range of 30 to 130°C, (D)
Crystallinity measured by X-ray diffraction method is 1 to 60
(E) Soluble content in boiling methyl acetate CW, weight%
] is within the range of 2% by weight or less, (F) 10℃
Acetone/n-decane mixed solvent (volume ratio 1/1)
) soluble content [W2wt%] is 5×[η]″″1°2
There is provided a crystalline propylene random copolymer, l1LJ&, characterized in that it contains a 1-butene-based random copolymer that satisfies the following:

The crystalline propylene random copolymer (i) constituting the crystalline propylene random copolymer composition of the present invention is a crystalline random copolymer consisting of propylene and an α-olefin other than propylene, and containing propylene as a main component. It is a polymer. The content of propylene component in the crystalline propylene random copolymer is usually 99 to 85 mol%.
, preferably in the range of 98 to 90 mol%, and the content of α-olefin components other than propylene is usually in the range of 1 to 15 mol%, preferably 2 to 10 mol%. The α-olefin other than propylene constituting the crystalline propylene random copolymer includes ethylene,
Examples include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, etc.
It is acceptable even if it is a mixed component of seeds or more. The crystalline propylene random copolymer (i) usually has an intrinsic viscosity [η] of 1.5 to 4 when measured in decalin at 135°C.
, preferably in the range of 1.7 to 3.5 dl/g, the melting point (Tm) measured by differential scanning calorimetry.
is usually 120°C to 155°C, preferably 12
The crystallinity, measured by X-ray diffraction, is usually in the range of 35 to 60%, preferably 35 to 50%.

The 1-butene-based random copolymer (ii) constituting the crystalline propylene random copolymer composition of the present invention is a 1-butene-based random copolymer containing 1-butene as a main component.

The composition (A) of the 1-butene-based random copolymer is 1-
The butene component is 50 to 99 mol%, preferably 60 to 99 mol%, and the ethylene component is 50 to 50 mol%.
, preferably in the range of 1 to 40 mol%. In addition,
The 1-butene-based random copolymer may contain a small amount of other a-olefin components such as propylene, if necessary. When the content of the 1-butene component in the 1-butene random copolymer composition became less than 50 mol% and the ethylene content exceeded 50 mol%, the crystalline propylene random copolymer composition was laminated. The polypropylene composite laminate begins to block, its scratch resistance decreases, and the temperature at which it can be heat-sealed increases significantly during heat treatment. Also, 1
- When the content of the butene component is greater than 99 mol% and the content of the ethylene component is less than 1 mol%, the heat sealing temperature of the polypropylene composite laminate becomes high and the heat sealing strength also decreases.

The intrinsic viscosity [η] of the 1-1-butene-based Langum copolymer measured in decalin at 135°C is 0.5 to 6 dl/g.
, preferably in the range of 1 to 5 dl/g. Part 1
- When the intrinsic viscosity of the butene-based copolymer is greater than 6 dl/g, it becomes difficult to reduce the thickness of the heat seal layer of the polypropylene composite laminate in which the crystalline propylene random copolymer composition is laminated. If it is less than .5 dI/g, the heat-sealing strength of the composite laminate decreases, and the heat-sealable temperature increases due to heat treatment (as measured by a differential scanning calorimeter of the 1-butene-based random copolymer). The melting point [Tm] is 30 to 130℃
, preferably in the range of 40 to 120'C. The melting point of the 1-butene-based random copolymer is 1
When the temperature is higher than 30°C, the heat sealing temperature of the polypropylene composite laminate in which the crystalline propylene random copolymer composition is laminated becomes high, and the heat sealing strength and t
When the temperature drops below 30°C, the polypropylene composite laminate begins to block and its scratch resistance decreases, and furthermore, the temperature at which it can be heat-sealed increases significantly due to heat treatment. . Here, the DSC melting point is the thickness of 0 after 20 hours of molding.
．． One side of the press sheet was measured from 0 to 200°C at a heating rate of 10”C/min, and the maximum endothermic peak was determined as Tm.
And so.

The degree of crystallinity (D) of the 1-butene-based random copolymer measured by X-ray diffraction is in the range of 1 to 60%, preferably 1 to 55%. When the degree of crystallinity of the 1-butene-based random copolymer is greater than 60%, the heat sealing temperature of the polypropylene composite laminate in which the crystalline propylene random copolymer composition is laminated becomes high, and the heat sealing strength also increases. If it becomes less than 1%, the polypropylene composite laminate begins to block, the scratch resistance decreases, and furthermore, the heat sealing temperature increases due to heat treatment. The crystallinity is 1.5 in the thickness 20 hours after molding.
It was determined by X-ray diffraction measurement of a press sheet of mm.

The amount of the 1-butene-based random copolymer soluble in boiling methyl acetate [W3% by weight] (E) is 2% by weight or less, for example 0.01 to 2% by weight, preferably 0.02 to 1% by weight.
, particularly preferably in the range of 0.03 to 0.5% by weight. Further, the amount of the 1-butene-based random copolymer soluble in boiling methyl acetate [W1% by weight] is, for example, the general formula 0%. is 0.03≦W1≦0.015a+0.4 [in the formula,
a indicates the content (mol %) of the ethylene component in the 1-butene copolymer. ] It is preferable that it is in the range represented by. When the boiling methyl acetate soluble content of the 1-butene-based random copolymer exceeds 2% by weight, the polypropylene composite laminate laminated with the crystalline propylene random copolymer composition will be blocked. In addition, the scratch resistance decreases, and furthermore, the temperature at which heat sealing is possible due to heat treatment increases significantly. The boiling methyl acetate soluble content was measured by the following method. i.e. 1mm x 1
A strip sample of about mm x 1 mm was placed in a cylindrical lath filter, extracted with a Soxhlet extractor for 7 hours with a reflux frequency of about 15 minutes at a time, and the extracted residue was dried in a vacuum dryer (vacuum level 10 n + 11 Hg or less). The sample was dried to a constant weight and its weight was determined, and the weight of the boiling methyl acetate soluble content was determined from the weight difference with the original sample.

The boiling methyl acetate soluble content [W1] was determined as the percentage of the boiling methyl acetate soluble weight to the weight of the original sample.

The amount of the 1-butene-based random copolymer soluble in acetone/n-decane mixed solvent (volume ratio 1/1) at 10'C [W2% by weight] (F) is based on the weight of the copolymer. based on less than 5×[η]−1°2% by weight, e.g. O01
×[η]-1-2 to 5×[η)-1'2% by weight, preferably 0°2×[η]-1°2 to 4.5×[η]-1°
2% by weight, particularly preferably O83×[η]-1.2~
4X(η) - 1°2 (Here, [η] is the value of the intrinsic viscosity of the copolymer, excluding Damenoyon.) The 1-butene-based random copolymer When the amount of the soluble portion in the acetone/n-decane mixed solvent at 10°C during coalescence is larger than 5x(η)-1゛2, the propylene composite laminate in which the crystalline propylene random copolymer composition is laminated becomes blocking. In addition, the scratch resistance decreases, and the temperature at which heat sealing is possible due to heat treatment increases.The amount of soluble content of the copolymer in the acetone/n-decane mixed solvent is measured by the following method. That is, in a 150 ml flask with stirring blade material, 1 g of copolymer sample, 2.6-
Not-tert-butyl-4-methyl 7-ethyl, 50ml
Add n-decane and dissolve on a 120°C oil bath.

After dissolution, the mixture is allowed to cool naturally at room temperature for 30 minutes, then 50 ml of acetone is added over 30 seconds, and the mixture is cooled on a 10° C. water bath for 60 minutes. A solution containing the precipitated copolymer and low molecular weight polymer component was filtered and separated using a glass filter, and the solution was
It was dried at 0 mmHg and 150'C until it reached a constant weight, its weight was measured, and the amount of the copolymer soluble in the mixed solvent was calculated and determined as a percentage of the weight of the sample copolymer. In the above measurement method, stirring was carried out continuously from the time of dissolution to just before passing.

The 1-butene-based random copolymer is the above-mentioned (A
A more preferable copolymer satisfies the binding factor expressed by the characteristic values of ) to F), and also satisfies the following (G) to L).

The yield point stress (G) of the 1-butene-based random copolymer measured by the method of JIS K7113 is 1 to 20.
0 kg/cm2, preferably 2 to 180 kg/cm
2, and the stress at break (H) measured by the method of JIS K7113 is 3 to 1000 kg/a
m2, preferably in the range of 5 to 800 kg/cto2, and the elongation at break (I) measured by JIS K7113 (7) method is 300% or more, preferably 350 kg/cto2.
It ranges from 1000% to 1000%.

The characteristic values of the stress at yield (G), stress at break (H), and elongation at break CI, ) were measured according to the tensile test method of JIS K7113. In other words, the sample is JIS
JIS K7113 punched from a 1 mm thick press sheet molded using K6758 after 19 hours of molding.
Measurements were made using a No. 2 test piece of No. 2 in an atmosphere of 25° C. at a tensile speed S Omm/1 oin after 20 hours of forming the press sheet. 20 if the yield point does not clearly appear.
% elongation stress was taken as the yield point stress.

In addition, JIS K6 of the 1-butene-based random copolymer
The torsional rigidity (J) measured by the method of 745 is for example 5 to 3000 kg/am2, preferably 1
It ranges from 0 to 2000 kg/am2. The torsional rigidity is determined by the thickness 1 molded according to JIS K6758.
Vertical 64 mm punched from a press sheet 9 days after molding
Using a strip-shaped test piece with a width of 635 mm and a width of 635 mm, the value was measured 10 days after the press sheet was formed and 5 seconds after loading at a twist angle of 50 to 60 degrees in an atmosphere of 25°C.

The Young's modulus (K) of the 1-butene-based random copolymer measured by the method of JIS K7113 is usually 10 to SO00 kg/cm", preferably 20 to 4.
000 kg/am''.The Young's modulus (K) of the 1-butene-based random copolymer is expressed by the relationship with the content b of the ethylene component bmol%.The Young's modulus is It was measured by the same tensile test method as in (G), () () and (I) above.

The standard deviation value σ(L) of the 1-butene content of the 1-butene-based random copolymer is usually 0.6a mol% or less, preferably 0.4a mol% or less (in the formula, a is the (Indicates the mol% content of ethylene component in the dobutene-based random copolymer). The standard deviation value σ is a measure showing the randomness of the 1-butene-based random copolymer, and is
A copolymer that satisfies characteristic value (L) in addition to K) or K) exhibits better physical properties. The standard deviation value σ of the 1-butene-based random copolymer of the present invention was calculated and determined by the following formula based on the composition distribution of the copolymer. The composition distribution of the copolymer was measured using an extraction column fractionation method in which the extraction temperature was changed in steps of 5°C from 0 to 130°C using p-xylene solvent. For extraction, 2 p-xylene was added to 10 g of copolymer sample.
Extraction was performed using 1 for 4 hours.

σ=[L"0(ball-x)2f(x)dxl'/"where; is the average content of 1-butene in the copolymer (mol%)
, X represents the 1-butene content (mol %), and f(x) represents the differential weight fraction of the component having the 1-butene content x (mol %).

The 1-butene-based random copolymer (subject) may be made of, for example, (a) a magnesium compound, a titanium compound, a diester, and optionally a no\lodene compound (if the magnesium compound or titanium compound contains 710 den atoms, (b) an organoaluminum compound catalyst component; (b) an organoaluminum compound catalyst component;
) an organosilicon compound catalyst component having a Si-○-C bond, in the presence of a catalyst formed from about 20 to about 200
6 catalytic acid content, copolymerization conditions, which can be obtained by copolymerizing 1-butene and ethylene at a temperature of °C;
Details such as the manufacturing conditions of the pond are described in the patent application specification with the title of the invention [1-butene-based random copolymer] filed by the applicant on the same date as this application, so this method The 1-butene-based random copolymer can be produced according to the method. During manufacturing, characteristics (A) ~
The measurement and determination method for (F) can be easily carried out by selecting and determining the catalyst and polymerization conditions experimentally in advance so as to satisfy these characteristics (A) to (F) in accordance with the detailed explanation already given. .

The blending ratio of the crystalline propylene random copolymer (i) and the 1-butene random copolymer (ii) constituting the crystalline propylene random copolymer composition of the present invention is (i)/(ii) ) 5/95 to 90/10 in weight ratio
, preferably in the range of 10/90 to 85/15.

The crystalline propylene random copolymer composition of the present invention comprises the crystalline propylene random copolymer (i) and the above 1
-Butene-based random copolymer (1;) may be the only two components, or may be a composition containing other polymers in addition to the two components. In addition to the above polymer components, the crystalline propylene random copolymer composition also contains a heat stabilizer, a weather stabilizer, a nucleating agent, a lubricant, a slip agent, an antistatic agent,
There is no problem in adding anti-blocking agents, anti-fogging agents, pigments, dyes, etc. The blending ratio is appropriate within a range that does not impair the low-temperature heat-sealability and heat-seal strength of the polypropylene composite laminate.

The crystalline propylene random copolymer composition of the present invention can be prepared by uniformly mixing the above-mentioned components using a tumbler, a Henschel mixer, etc. After mixing, the composition is further extruded using an extruder. The mixture may be kneaded using a Banbury mixer, Nigu, roll, or the like.

The crystalline propylene langum copolymer composition of the present invention includes:
A polypropylene composite laminate is formed by laminating one or both surfaces of a substrate made of crystalline polypropylene. The crystalline polypropylene serving as the base material layer includes, in addition to a crystalline propylene homopolymer, a crystalline propylene/α-olefin random copolymer whose main component is propylene, such as a crystalline propylene/α-olefin random copolymer with an ethylene content of 0.1 to 5 mol% propylene-ethylene random copolymer, a propylene-ethylene random copolymer with a dithitone content of 0.1 to 4 mol% and a 1-butene content of 0.1 to 5 mol%.
1-butene random copolymer, 1-butene content is 0.
Examples include propylene/1-butene random copolymers containing 1 to 5 mol%. The intrinsic viscosity of the crystalline polypropylene measured in decalin at 135°C [
η] is usually in the range of 1.5 to 4 cl l /g, preferably 1.7 to 3.5 dl/g, and its
The degree of crystallinity measured by line diffraction is usually in the range of 50 to 70%, preferably 55 to 70%. The base material layer made of crystalline propylene may be in an unstretched state, or may be in a horizontally or biaxially stretched state.

The following method can be exemplified as a method for producing a polypropylene composite laminate by laminating the crystalline propylene langum copolymer composition of the present invention on one or both sides of the base material layer made of the crystalline polypropylene. .

(1) A base material made of crystalline polypropylene and the crystalline propylene random copolymer composition are laminated by co-pressing, and if necessary, further longitudinal stretching and/or
Or a method of applying horizontal axis stretching separately or simultaneously.

(2) The crystalline propylene random copolymer composition is extruded and laminated in a molten state on the surface of a crystalline polypropylene base material that has been unstretched, -axially stretched, or biaxially stretched, and the base material is in an unstretched state. In some cases, a method of further performing single-stretching or biaxial stretching as necessary. In addition, when the base material is in a stretched state, a method of extruding and laminating in the same manner and then further stretching in the same direction or in a cross direction as the base material as necessary.

(3) A method of laminating a film of the crystalline propylene random copolymer composition on the surface of a substrate made of crystalline polypropylene using an adhesive.

The polypropylene composite laminate formed by laminating the crystalline propylene random copolymer of the present invention on one or both sides of a substrate made of crystalline propylene may have any shape, such as a laminated film or a laminated sheet. Examples include laminated packaging bags, laminated containers, and molded bodies that provide heat-sealing properties.

As is clear from the above-mentioned examples of the lamination method, the base material layer made of crystalline polypropylene constituting the propylene composite laminate can be in an unstretched state, a -axially stretched state, or a biaxially stretched state. The layer made of the crystalline propylene random copolymer may be either in an unstretched state, a pongee-stretched state, or a biaxially stretched state. Further, the base material layer made of crystalline polypropylene and the layer made of the crystalline propylene random copolymer of the polypropylene composite laminate may be configured in any combination of the above states.

The thickness of the base material layer made of crystalline polypropylene constituting the polypropylene composite laminate is arbitrary and not particularly limited, but the thickness of the heat seal layer made of the crystalline propylene random copolymer composition is generally 0. .1 to 5
0μ, preferably in the range of 0°5 to 30μ. When the polypropylene composite laminate is a composite laminate film or a composite laminate sheet, the thickness of the base layer made of crystalline polypropylene is 5 to 200μ, preferably 10μ.
The thickness of the heat seal layer made of the crystalline propylene random copolymer composition is usually 0.1 to 50μ, preferably 0.5 to 30μ.
is within the range of

〔Effect of the invention〕

A polypropylene composite laminate formed by laminating a layer made of the crystalline propylene random copolymer of the present invention on one or both sides of a base material made of crystalline polypropylene has excellent heat-sealability and heat sealability at low temperatures. It has excellent strength, has an improved heat-sealable temperature range, and has excellent scratch resistance and blocking resistance. Therefore, the polypropylene composite laminate is suitable for packaging daily necessities and miscellaneous goods such as food packaging and clothing packaging by utilizing these characteristics.

〔Example〕

Next, the present invention will be specifically explained using examples. In addition, in the examples, each evaluation item was evaluated according to the following method.

(1) Heat-sealing strength The surfaces of the polypropylene composite film on which the crystalline propylene random copolymer composition is laminated are stacked together and heat-sealed using five sealing bars for 1 second at a pressure of 2 kg/am2 at each temperature. After that, it was left to cool. A test piece with a width of 15 mm was cut from this sample, and the strength was measured when the heat-sealed portion was peeled off at a crosshead speed of 200 mm/min. Further, after the polypropylene composite film was left in an air atmosphere at 50° C. for one week, the value measured by the above method was taken as the heat seal strength after heat treatment.

(2) The surfaces of the scratch-resistant polypropylene composite film on which the crystalline propylene random copolymer composition is laminated are stacked together and rubbed together 15 times using a 5 kg iron block as a load. It was measured by the method of 1), and the difference (Δ haze) from the haze of the sample before rubbing was determined.

(3) Blocking resistance Evaluated according to ASTM D1893. Cut the polypropylene composite film into 10C1111 pieces with a length of 15 cm, overlap the surfaces on which the crystalline propylene random copolymer composition is laminated, place a load of 10 kg between two glass plates, and heat in air at 50°C. Leave it open. Samples were taken out after 1 day and 7 days, and the peel strength was measured using a universal testing machine, and the peel strength per 1 cm was taken as the blocking value.

(4) Ikg degree so of the film produced according to ASTM D1003
'C Before aging in air oven and knee song 1
The degree of haze was measured after 7 days.

(5) Slip property 50°C of film formed according to ASTM D1894
The coefficient of static friction and the coefficient of dynamic friction were measured before aging in an air oven, and 1 day and 7 days after kneeling.

The preparation methods of the 1-butene-based random copolymers used in the Examples and Comparative Examples of the present invention are shown in Reference Examples 1 to 9, and the resulting 1-butene-based random copolymers are shown in Table 1. Shown all together.

In addition, in the Examples and Comparative Examples of the present invention, the crystalline propylene random copolymer (i) blended in the crystalline dolipropylene and crystalline propylene random copolymer composition used as the base material layer. The properties are shown in Table 2.

Reference Example 1 Preparation of titanium catalyst component (a)> Anhydrous magnesium chloride 4.76 g (50 mmol),
Decane 25ml and 2-ethylhexyl alcohol 22ml
After heating and reacting 3.4 ml (150 mmol) at 130°C for 2 hours to make a homogeneous solution, in this solution: Anhydrous 7
Add 1.114 (7.5 mmol) of tarric acid,
Stirring and mixing is continued for an additional hour at °C to dissolve 7-talic anhydride into the homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped into 200 ml (1.8 mol) of titanium tetrachloride maintained at -20°C over 1 hour. After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and when it reached 110°C, diisobutyl 7 thale) 2.68n+1 (12.5m
mol) and kept under stirring at the same temperature for 2 hours. After the completion of the 2-hour reaction, the solid portion is collected by hot filtration, and after resuspending this solid portion in 200 ml of T i C1, the heating reaction is performed again at 110° C. for 2 rR. After the reaction was completed, the solid portion was collected again by hot filtration, and 110
Wash thoroughly with decane and hexane until no titanium compound is detected in the washing solution. The titanium catalyst component (a) prepared by the above production method is stored as a hexane slurry, and a portion of it is dried for the purpose of examining the catalyst composition. The composition of the titanium catalyst component (,) thus obtained was 3.1% by weight of titanium and 56% by weight of chlorine.
0% by weight, 17.0% by weight of magnesium, and 20.9% by weight of diimbutyl 7-thale.

<Polymerization> 5 f) kg per hour into a 2001 SUS reaction vessel
of 1-butene, 0.18 kg of ethylene, 100 mmo
1 of triethylaluminum, 10 mmol of vinyltriethoxysilane, 0°5%0 in terms of titanium atoms
1 titanium catalyst component (,) was continuously charged, the hydrogen partial pressure in the gas phase was maintained at 1.5 kg/cm2, and the polymerization temperature was set at 70 kg/cm2.
It was kept at °C.

The polymerization liquid was continuously drawn out so that the liquid volume in the reaction vessel was 100 ml, the polymerization was stopped with a small amount of methanol, and unreacted monomers were removed. 9.6 kg of copolymer was obtained per hour, and the results are shown in Table 1.

Reference Example 2-7 Polymerization was carried out in exactly the same manner as in Reference Example 1, except that the amount of ethylene charged was changed to the amount listed in Table 1, and the hydrogen partial pressure was changed as appropriate. The results are shown in Table 1.

Reference Example 8 50 kg of 1-butene, 0.3 kg of ethylene, 200 wol of diethylaluminum chloride 'I'', and 1001IIIlol of titanium trichloride (Toho Titanium Co., Ltd., TAC-131) were continuously added to a 2001 reaction vessel per hour. The gas phase partial pressure of hydrogen was set at 2.7 kg/am2.
The polymerization temperature was maintained at 70°C. The amount of liquid in the reaction pot is 1
The polymerization solution was continuously taken out so that the amount of polymerization was 0.001 methanol per hour, and 101 methanol per hour was added thereto, followed by washing with water to remove unreacted monomers. 7.3 kHz of copolymer was obtained per hour, and the results are shown in Table 1.

Reference Example 9 Polymerization was carried out in exactly the same manner as in Reference Example 8, except that the amount of ethylene charged was changed to the amount listed in Table 1, and the hydrogen partial pressure was changed as appropriate. The results are shown in Table 1.

Examples 1-8 Comparative Examples 1-8 Crystalline propylene random copolymer (i) shown in Table 3
pellets and 1-butene-based random copolymer (ii)
The pellets were mixed for 1 minute in a Henschel mixer at the proportions listed in Table 3, and then the mixture was melt-kneaded in a melt extruder to form a melt of the crystalline propylene random copolymer composition. This composition was mixed at a resin temperature of 2
It was fed into a double layer film gouey at 40°C. On the other hand, the crystalline polypropylene that will become the base material layer shown in Table 3 is melted in another extruder, and is supplied to the two-layer film die at a resin temperature of 240°C, and the crystalline propylene random copolymer composition and Co-extrusion of crystalline polypropylene for the base material layer is performed to form a base material layer (4.0μ) made of the crystalline polypropylene.
and a layer (1) consisting of the crystalline propylene random copolymer
A composite film formed from 0μ) was obtained. Table 3 shows the performance evaluation results of this polypropylene composite film.

Examples 9 to 1] Comparative Example 9 The base crystalline polypropylene shown in Tables 2 and 3 was melted in an extruder, extruded through a T-guid at a resin temperature of 270°C, cooled and solidified into a sheet, and then heated a- By passing the le? ), and was stretched in the longitudinal axis direction to a stretching ratio of t5 to form a uniaxial sheet of crystalline polypropylene.

On one side of this uniaxially stretched sheet of crystalline polypropylene, the crystalline propylene random copolymer composition listed in Table 3, which was melt-kneaded using another extruder, was extruded in a molten state using another T-die at a resin temperature of 250°C. The composite sheet was passed through a continuously heated tenter and stretched in the transverse direction at a stretching ratio of 10 times to form a base material layer (30μ> and A layer (5) consisting of the crystalline propylene random copolymer
A polypropylene composite film was obtained in which the crystalline propylene random copolymer composition layer was laminated, the crystalline polypropylene base layer was biaxially stretched, and the layer made of the crystalline propylene random copolymer composition was uniaxially stretched. Table 3 shows the performance evaluation results of this polypropylene composite film.

Claims (1)

[Scope of Claims] (i) A crystalline propylene random copolymer consisting of propylene and an α-olefin other than propylene and having propylene as its main component, and (ii) a 1-butene-based random copolymer consisting of ethylene and 1-butene. It is a copolymer and has the following items: (A) the composition is in the range of 1 to 55 mol% of the ethylene component and 50 to 99 mol% of the 1-butene component; (B) at 135 ° C. in decalin. Measured limiting viscosity [η]
(C) Melting point [Tm] measured by differential scanning calorimeter is in the range of 30 to 130°C, (D) Measured by X-ray diffraction method. The degree of crystallinity is in the range of 1 to 60%, (E) The amount soluble in boiling methyl acetate [W_1% by weight] is in the range of 2% by weight or less, (F) Acetone/n at 10°C - Decane mixed solvent (
The amount of soluble content [W_2% by weight] to volume ratio 1/1) is 5×[
η〕＾−＾1＾. A crystalline propylene random copolymer composition, characterized in that it contains a 1-butene-based random copolymer that satisfies the following: ^2% by weight or less.