JPS61106648A - Crystalline propylene random copolymer composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which allows heat-sealing characteristics to be improved when laminated on the surface of a crystalline polypropylene substrate, by mixing a crystalline propylene random copolymer with a 1-butene random copolymer having specified properties. CONSTITUTION:A 1-butene random copolymer composed of 1-40mol% of propylene component and 99-60mol% of 1-butene component and having an intrinsic viscosity eta of 0.5-5dl/g (in decalin at 135 deg.C), a m.p. of 50-130 deg.C as measured with a differential scanning calorimeter, a crystallinity of 5-6% as measured by X-ray diffraction, a boiling methyl acetate soluble content of 2wt% or below and a soluble content in a solvent mixture of acetone/n- decane (1:1 by volume) of less than 4X[eta]<-1>,<2>wt%, is prepd. Said copolymer is mixed with a crystalline propylene/alpha-olefin random copolymer mainly composed of propylene to obtain the titled compsn.

Description

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

[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 sheet sealability of this polypropylene film, several methods have already been proposed in which a low melting point resin is laminated on both sides of the crystalline polypropylene film.

For example, JP-A-55-65552 discloses an ethylene/propylene random copolymer containing propylene as the main component and a polymer containing propylene as the main component.
A method of laminating a propylene random copolymer composition comprising a lopylene/α-olefin random copolymer onto a crystalline polypropylene film is disclosed. Furthermore, JP-A-55-91665 discloses a propylene random copolymer 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. A method of laminating a polymer composition to a crystalline polypropylene film is disclosed. Furthermore, JP-A-54-106585 discloses an ethylene/propylene random copolymer containing propylene as a main component, a 1-butene/ethylenically unsaturated monomer copolymer containing 1-butene as a main component, and A method of laminating a propylene random copolymer composition comprising a low molecular weight thermoplastic resin to a crystalline polypropylene film is disclosed. Furthermore, the above-mentioned JP-A-Sho and the above-mentioned JP-A-54-10
U.S. Patent No. 4,230,767, which was filed in the United States by claiming priority to Patent Application No. 6585 (Japanese Patent Application No. 13932/1983), discloses that the above-mentioned ethylene-propylene random copolymer mainly composed of propylene and -1- whose main component is butene
Disclosed is a propylene random copolymer composition that can include an embodiment in which a propylene random copolymer composition that can include a composition comprising a butene-propylene copolymer is laminated on a crystalline polypropylene film. . However, no specific example of the above-mentioned aspect is shown, and as specified in the above-mentioned Japanese Patent Application Laid-Open No. 54-106585,
Regarding this embodiment, only an example in which a low molecular weight thermoplastic resin is further used in combination is shown.

The temperature at which heat sealing is possible is still quite high, and the applicable temperature range is also narrow, so it is still difficult to say that it is sufficient. Furthermore, it could hardly be said that the heat sealing 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 rises considerably, etc. There was a drawback. In this way, in the field of packaging applications using polypropylene films, polypropylene composites that lower the heat-sealing temperature, widen the heat-sealable temperature range, have excellent heat-sealing strength, and have a small increase in the heat-sealable temperature due to heat treatment are used. Film is highly 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 (1) and that the degree of increase in the heat sealable temperature due to heat treatment is also small.

Therefore, an object of the present invention is to provide a crystalline polypropylene base material layer 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 pyrene random copolymer composition.

The above objects as well as many other objects and advantages of the present invention will become more apparent from the following description.

[Means for Solving the Problems] and [Operation] According to the present invention, (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 propylene and 1-butene, and the following items, (A)
The composition is in the range of 1 to 40 mol% of propylene component and 60 to 99 mol% of 1-butene component, <E> Intrinsic viscosity measured at 135°C in decalin [
(C) The melting point [:
(D) The degree of crystallinity measured by X-ray diffraction is in the range of 5 to 60%; CE) The soluble content of boiling methyl acetate [F1 % by weight] is within the range of 2% by weight or less, (F) The amount of soluble content [W3% by weight] in the acetone/n-decane mixed solvent (volume ratio 1/1) at 10°C is 4×[η] A crystalline propylene random copolymer composition is provided, characterized in that it contains an l-butene-based random copolymer that satisfies the following: -1.8% by weight or less.

The crystalline propylene random copolymer (i) constituting the crystalline propylene random copolymer composition of the present invention (c) consists of propylene and an α-olefin other than propylene, and is a crystalline random copolymer containing propylene as a main component. It is a copolymer. 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 1.
The amount of potassium is 15 mol%, preferably in the range of 2 to 10%. Examples of α-olefins other than propylene constituting the propylene random copolymer include 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-pentenato, and these two types A mixture of the above ingredients is also acceptable. The crystalline globylene random copolymer (i) has an intrinsic viscosity [η] of usually 1.5 to 4, preferably 1.7 to 15 dl111, as measured in decalin at 135°C. Melting point [T] measured by differential scanning calorimeter
] is usually 120°C to 155°C, preferably 12°C
The degree of 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 (i1) constituting the crystalline propylene random copolymer composition of the present invention is a propylene/l-butene random copolymer containing 1-butene as a main component.

The composition (A) of the 1-butene-based random copolymer is preferably in the range of 4 to 35 mol%. Note that the 1-butene-based random copolymer may contain other α-olefin components such as low-weight ethylene, if necessary. When the content of the 1-butene component in the 1-butene-based random copolymer is less than 60 mol% and the content of propylene is greater than 40 mol%, the binding propylene random copolymer composition The polypropylene composite laminate in which the polypropylene is laminated tends to block, the scratch resistance decreases, and the heat-sealable temperature increases significantly due to heat treatment. Furthermore, when the content of the 1-butene component is greater than 99 mol% and the content of the propylene component is less than 1 mol%, the heat sealing temperature of the polypropylene composite laminate becomes high.
Heat seal strength also decreases.

The intrinsic viscosity of the 1-butene-based random copolymer measured in decalin at 135°C is 0.5 edt/I.
, preferably in the range of 1 to 5d/11. Part 1
- When the intrinsic viscosity of the butene-based copolymer becomes larger than 6 dl/11, 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. , a, sdl/I becomes smaller, the heat sealing strength of the composite laminate decreases, and the increase in the heat sealable temperature due to heat treatment increases.

The melting point (T m ) of the 1-butene-based random copolymer measured by a differential scanning calorimeter is 50 to 130°C.
, preferably in the range of 60 to 125°C. The melting point of the 1-butene-based random copolymer is 13
When the temperature rises above 0°C, the heat sealing temperature of the polypropylene composite laminate laminated with the crystalline propylene random copolymer composition increases, and the heat sealing strength also decreases. Then, the polypropylene composite laminate is washed one by one so that it blocks.
In addition, the scratch resistance decreases, and furthermore, the temperature at which heat sealing is possible increases due to heat treatment. Here, the DSC melting point is the thickness of 0.1 after 20 hours of molding.
wn press sheet at a heating rate of 10℃/1i from 0 to 2
The temperature was measured up to 00°C, and the maximum endothermic peak was defined as Tm.

The degree of crystallinity (D) of the 1-butene-based random copolymer measured by X-ray diffraction is in the range of 5 to 60%, preferably 10 to 58%.

When the degree of crystallinity of the 1-butene-based random copolymer becomes greater than 60%, the heat sealing temperature of the polypropylene composite laminate laminated with the crystalline propylene random copolymer composition becomes high, and the heat sealing temperature becomes high. When the strength decreases by about 5%, the polypropylene composite laminate begins to block, the scratch resistance decreases, and the heat sealing temperature increases due to heat treatment. Crystallinity is 20 after molding
It was determined by X-ray diffraction measurement of a pressed sheet with a thickness of 1.5 m after the elapse of time.

The soluble content of the 1-butene-based random copolymer in boiling methyl acetate, CF1, is 2% by weight or less, for example, 0.01 to 2% by weight, or 0.02 to 1% by weight. ,
Particularly preferably, it is in the range of 0.03 to 0.5% by weight. In addition, the soluble content Crt weight % in boiling methyl acetate of the 1-butene-based random copolymer] is, for example, expressed by the general formula 0% [wherein α is the propylene component in the 1-butene-based copolymer]. Indicates the content (mol%) of ] is preferable. When the boiling methyl acetate soluble content of the 1-butene-based random copolymer increases by 2% by weight,
A polypropylene composite laminate in which the crystalline propylene random copolymer composition is laminated tends to block, has lower scratch resistance, and further increases the heat-sealable temperature by heat treatment. The boiling methyl acetate soluble content was measured by the following method. Extract for 7 hours with a Soxhlet extractor, dry the extracted residue in a vacuum dryer (vacuum degree 10w x Eg' or less) until it reaches a constant weight, calculate its xf, and calculate the xf from the weight difference with the original sample. The weight of boiling methyl acetate solubles was determined. The boiling methyl acetate soluble content (crt) was determined as the percentage of the boiling methyl acetate soluble weight to the weight of the urine sample.

Amount of the 1-butene-based random copolymer soluble in acetone/n-decane mixed solvent (volume ratio 1/1) at 10'C [W! weight] (F) is 4x[η3-1. based on the weight of the copolymer. ! Less than % by weight, for example 0.
I X l: η]-1°3~4x(η)-1°8% by weight
, preferably 0.2×Cl3-1・-45×[η]
−1°2% by weight, particularly preferably 0.3×[η]−1
It is in the range of °2 to 3 × [da] -1.2 (thereby, [η
] is the numerical value of the intrinsic viscosity of the copolymer, excluding the dimension). When the amount of the 1-butene-based random copolymer soluble in the acetone/n-decane mixed solvent at 10° C. is larger than 4×1.2,
so that the propylene composite laminate in which the crystalline propylene random copolymer composition is laminated blocks;
In addition, the scratch resistance decreases, and furthermore, the temperature at which heat sealing is possible due to heat treatment increases significantly. Copolymer sample II, o, os
Add 2,6-ditart-butyl-4-methylphenol (II) and n-decane (50) and dissolve on an oil bath at 12°O<0>C. After defrosting, the mixture is allowed to cool naturally at room temperature for 30 minutes, then 50-carbon acetone is added for 30 seconds, and the mixture is cooled on a 10° C. water bath for 60 minutes. The solution in which the precipitated copolymer and low molecular weight polymer components were dissolved was filtered and separated using a glass filter, and the solution was heated to a constant weight at 150°C at 1 (JrxHg).
The weight of the copolymer was measured, and the amount of the copolymer soluble in the mixed solvent was determined as a percentage of the sample copolymer's IT. In the above measurement method, stirring was carried out continuously from the time of dissolution to immediately before filtration.

The 1-butene-based random copolymer is the above-mentioned (A
) to p>, and a more preferable copolymer also satisfies the following (G) to Z).

JIS K711 of the l-butene-based random copolymer
The yield point stress (G) measured by method 3 is 9/CI to 50 to 300! , preferably 7o to ao
o y/di, and the stress at break (II) measured by the method of JIS K7113 is 150 to 800kp/aI', preferably 200 to 600k.
sb in the p/cd range, and the elongation at break (i) measured by the method of JIS [7113] is 300% or more, preferably in the range of 350 to 1000%. The characteristic values of the stress at yield point (G), stress at break (H), and elongation at break (7) were measured according to the tensile test method of Its x'r11s. In other words, the sample is JIS 6
2 of JIS z'y11a punched out after 19 hours of molding from a press sheet with a thickness of 1 cm formed by 758.
Using a bone-shaped specimen, the tensile speed was 50 W in an atmosphere of 25°C.
/m1tL was measured 20 hours after forming the press sheet. If the yield point did not clearly appear, 20% elongation stress was taken as the yield point stress.

Moreover, II5 f of the 1-butene-based random copolymer
The torsional rigidity (7) measured by the method of 6745 is usually between 500 and 3000 kg/cd.

It is preferably in the range of SOO to 2500 9/cd. The rigidity of screw 9 was determined using a strip-shaped test piece with a length of 64 m and a width of 635 strips punched 9 days after molding from a press sheet with a thickness of Im formed according to JIS K675B. or 6
The value was measured 5 seconds after loading at a screw angle of 0 degrees.

JIS K711 of the l-butene-based random copolymer
Young's modulus <X> measured by method 3 is usually 10
00 to 600 oko/cds preferably 1100
It is in the range of 1 to 5000 kP/cII.

Furthermore, the Young's modulus (r
) is preferably expressed by 500G-606≧f≧2000-306 in terms of the propylene component content b mol %. Young's modulus was measured by the same tensile test method as in (G), (H), and (i) above.

The standard deviation value σ(L) of the 1-butene content of the 1-butene-based random copolymer is usually α4α mol% or less, preferably 0.3α mol% or less (where α is the 1-butene content). Content of propylene component in random copolymer %
shows. ). The standard deviation value σ is a measure showing the randomness of the 1-butene-based random copolymer, and is a copolymer that satisfies the characteristic value (A) or K)K in addition to the characteristic value (L). (Yes) The standard deviation value σ of the 1-butene-based random copolymer of the present invention, which exhibits excellent round physical properties, was calculated and determined by the following formula based on the composition distribution of the copolymer. The composition distribution of the copolymer was measured by the extraction dust fractionation method in which the extraction temperature was changed in steps of 5°C from 10 to 13 G''C using a p-medium silene solvent, and at a constant temperature. For the extraction, p-xylene 21 was used for copolymer sample 10II, and extraction was performed for 4 hours.

a= [, io= <;-z)! t<z>ds)' Here, D is the average content of 1-butene in the copolymer (mol%
), 2 is 1-butene content (mol%), 7 ('')
indicates the differential weight fraction of the component having a 1-butene content of 2 (mol %).

The l-butene-based random copolymer (II Company, for example (
α) Magnesium formed by reacting with each other a magnesium compound, a titanium compound, a diester and optionally a halogen compound (not necessarily required if the magnesium compound or titanium compound contains a halogen compound) , a highly active titanium catalyst component containing titanium, a halogen, and a hydiester component as essential components, (b) an organoaluminum compound catalyst component, and (c
) an organosilicon compound catalyst component having Si-0-C bonds, in the presence of a catalyst formed from about 20 to about 200
It can be obtained by copolymerizing 1-butene and propylene at a temperature of .degree. For details such as catalyst component copolymerization conditions and other manufacturing conditions, please refer to the patent application filed by the applicant in 1988-1464□:! Since it is described in the specification of No. 91, the l-butene-based random copolymer can be produced by that method. During production, the polymerization conditions for the eight catalysts were experimentally set in advance so as to satisfy these properties (A) to (F), in accordance with the detailed description of the methods for measuring properties (A) to (F). , can be easily done.

The blending ratio of the crystalline propylene random copolymer (i) and the 1-butene random copolymer (i1) constituting the crystalline propylene random copolymer composition of the present invention is (i)/(iD Weight ratio: 5/95 to 90/101
It is preferably in the range of 1 O/9 Q to s s/l s.

The crystalline propylene random copolymer composition of the present invention may consist of only two components, the crystalline propylene copolymer (i) and the 1-butene random copolymer (ii), or may consist of only the two components. The composition may also contain other polymers. 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, an antiblocking agent, an antifogging agent, a pigment, There is no harm in adding 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 constituent components in a tumbler-1V type blender, Henschel mixer, etc. Further, the mixture may be kneaded using an extruder/Kunbury mixer, kneader, roll, or the like.

The crystalline propylene random copolymer composition of the present invention is
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 is not only a crystalline propylene homopolymer but also a crystalline propylene/α-olefin random copolymer containing propylene as a main component, for example, an ethylene content of (Ll to 5). mol% of propylene and ethylene random co] are combined,
Propylene/ethylene/l-butene random copolymer with an ethylene content of 0.1 to 4 mol% and a 1-butene content of 0.1 to 5 mol%, a 1-butene content of a
For example, a propylene/1-butene random copolymer containing 1 to 5 mol % of the copolymer may be used. The intrinsic viscosity of the crystalline polypropylene measured in decalin at 135°C [η
] is usually in the range of L5 to 4 dl/11, preferably 171 to 5 dj/#, and its crystallinity as measured by X-ray diffraction is usually 50 to 70%, preferably 55 to 70%. is within the range of The base material layer made of crystalline propylene may be in an unstretched state or in a -axially or biaxially stretched state.

The crystalline propylene random copolymer composition of the present invention is laminated on one or both sides of the base material layer made of the crystalline polypropylene to produce a polypropylene composite laminate, for example, by the following method.

(i) A method in which a base material made of crystalline polypropylene and the crystalline propylene random copolymer composition are stretched 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 hot rolled (stretched). If the base material is in a uniaxially stretched state, it may be further uniaxially stretched or stretched as needed. A method of further stretching in the same direction as the base material or in a direction crossing the base material.

(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. , laminated packaging bags, laminated containers, and other molded bodies that provide heat-sealing properties.

The crystalline polyester constituting the propylene composite laminate
As is clear from the above-mentioned examples of the lamination method, the base material layer made of 1-propylene may be in an unstretched state, a -axially stretched state, or a biaxially stretched state; Similarly, the layer made of the crystalline propylene random copolymer may be in an unstretched state, a -axially 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 may be arbitrary, and there are no particular limitations, but the thickness of the heat seal layer made of the crystalline propylene random copolymer composition may be arbitrary. 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.
and 70μ), and the thickness of the heat layer 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

[Effects of the Invention] A polypropylene composite laminate formed by laminating a layer consisting of the crystalline propylene random copolymer composition of the present invention on one or both sides of a substrate made of crystalline polypropylene can be heat-sealed at low temperatures. It has excellent heat-sealability and heat-sealing strength, and 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 such 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.

(i1 Heat sealing strength) The surfaces of the polypropylene composite film on which the crystalline propylene random copolymer composition was laminated were placed on top of each other and heat-sealed at each temperature with a pressure of z/cd using a sealer of 5 times for 1 second. After that, it was left to cool.From this sample, 15
Cutting a test piece of cloth, cross head speed 200
The strength when the heat seal i was peeled off was shown at m,/yxss. In addition, after the polypropylene composite film was left in an air atmosphere at 50°C for one week, it was tested by the above method.k-)7-#
Yoyo.

Ta.

(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 15 times with iron blocks 5 and 9 as a load. After that, the sample becomes cloudy. The degree of cloudiness was measured by the method (i), and the difference (Δ degree of cloudiness) from the degree of haze of the sample before rubbing was determined.

(3) Blocking resistance Evaluated according to ASTM D1893. Poly
・Propylene composite film width 10cIL, length 1
It is cut into 5 cm pieces, the surfaces on which the crystalline propylene random copolymer composition is laminated are placed on top of each other, a load of 10 kg is placed between two glass plates, and the pieces are left in an air-open environment at 50°C. Samples were taken out after 1 day and 7 days, and the peel strength was measured using a universal tester, and the peel strength per 1 cIIL was taken as the blocking value.

14) Film formed according to haze ASTAf Dlo03 (
7) The degree of haze was measured before aging in an air open environment at 50° C., and after 1 day and 7 days after aging.

(5) Slip property The static friction coefficient of a film formed according to ASTAf D1894 before aging in an open air at 50°C, 1 day after aging, and 7 days after aging and the method for preparing a dynamic friction random copolymer are shown in Reference Example 1 to The 1-butene-based random copolymer shown in Reference Example 12 and obtained as a result is summarized in Table 1.

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

Reference example! Preparation of titanium catalyst component (α)> Anhydrous magnesium chloride 4.761 (50 mmol)
, Deccan 25sti! ! $'! 2-ethylhexyl alcohol 23.4sd (i50mm01) to 130
After performing a heating reaction at ℃ for 2 hours to obtain a homogeneous solution, phthalic anhydride L111! (7.5 degrees centigrade) was added and stirred and mixed for another 1 hour at 130°C to dissolve phthalic anhydride in the nuclear uniform solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount was dropped over 1 hour into 200 wl (LB mmol) of titanium tetrachloride maintained at -20'C. After charging, the temperature of this liquid mixture was raised to IIQ'C over 4 hours, and when it reached 110°C, 2.68 ml of diisoptylphthalate was added.
(IL5mrnol) was added and the mixture was kept under stirring at the same temperature for 2 hours. After the completion of the 2-hour reaction, the solid part was collected by heating, and this solid part was heated to 200 rd O'l'.
After resuspending 5 frames of 1C14 nitrogen, the reaction was heated again at 110° C. for 2 hours. After the reaction is completed, the solid portion is again collected by hot filtration and thoroughly washed with decane and hexane at 1.110° C. until no free titanium compound is detected in the washing solution. The titanium catalyst component (α) made rigid by the above manufacturing method is stored as a hexane slurry, and a portion of this is dried for the purpose of examining the composition of the melting medium.

The composition of the titanium catalyst component (α) obtained in this way was 20% by weight of titanium, 56.0% by weight of chlorine, and 1% by weight of magnesium.
7. O41% and diisobutyl phthalate 20.9
% by weight.

<Polymerization> Sokg of 1-butene, α5 propylene, 100 mmo L was added to a 200 d SVS reaction vessel for 1 hour.
(D)! J ethyl aluminum, l Ornmo
The hydrogen partial pressure in the gas phase was kept at x, sky/al, and the polymerization temperature was kept at 70°C.

The combined liquid was continuously withdrawn at a time when the liquid volume in the reaction vessel was 10 (l), the polymerization was stopped with a small amount of methanol, and unreacted monomers were removed. 99.2 kg of copolymer was obtained per hour. The results are shown in Table 1.

Reference Example 2-8 Polymerization was carried out in exactly the same manner as in Reference Example 1, except that the amount of propylene 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 9' To a 200/liter reaction vessel, 50-liters per hour was added! -butene,
1. Continuously charge 3rd floor propylene, 200 tnmol of diethylaluminum chloride, and 100 mmol of titanium trichloride (Toho Tetanicum Co., Ltd., TAC-131) to increase the gas phase partial pressure of hydrogen! 5 kir/cr4, and the polymerization temperature was kept at 70°C.

The polymerization solution was continuously drawn out so that the liquid volume in the reaction vessel was 100/1, 100 methanol was added per hour, and then washed with water to remove unreacted monomers. 1 hour fi
7.5 kg of copolymer was obtained and the results are shown in Table 1.

Reference Example 10 Polymerization was carried out in exactly the same manner as in Reference Example 9, except that the amount of propylene 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 11 Catalyst Preparation〉 (viscosity 2QC, 5, (25°C)) was placed in a nitrogen atmosphere with a stainless steel (SUS-32) ball λ8 with a diameter of 15 m, content of 9800 ml, and a stainless steel ball with an inner diameter of 100 ka. 5tys-32) tJ ball cylindrical charge, contact with impact acceleration 7.8G for 100 hours. The obtained solid treated product 109 was suspended in titanium tetrachloride IQ Oml, and after contacting with stirring at 80°C for 2 hours, the solid component was collected by filtration, and the free titanium tetrachloride in the washing liquid was After washing with purified hexane until it becomes undetectable, it is dried to obtain a titanium-containing solid catalyst component. This catalyst component is 20% titanium by weight.
, 66.0% by weight of chlorine, and 5% by weight of ethyl benzoate a
The surface area was 2ooi/11.

Polymerization> 1-butene of 50%, propylene of L6#, Φ-~m of triethylaluminum of 100 mol of triethyl aluminum, 33 mm per hour into a 200% SVS reaction vessel. l of p-1 ruyl acid me2
-0 kg/crI and the polymerization temperature was kept at 70°C.

The polymerization liquid was continuously drawn out so that the liquid volume in the reaction vessel was 100 mm, the polymerization was stopped with a small amount of methanol, and unreacted monomers were removed. 97.4 yu of copolymer was obtained per hour, and the results are shown in Table 1.

Polymerization was carried out in exactly the same manner as in Reference Example 11, except that the hydrogen partial pressure was changed as appropriate. The results are shown in Table 1.

Examples 1 to 9 Comparative Examples 1 to 10 Crystalline propylene random copolymer (i) shown in Table 3
pellets and l-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 this mixture was melt-kneaded in a melt extruder to obtain a melt of the crystalline glopyrene random copolymer composition. It was formed and fed into a two-layer film die at a resin temperature of 240°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 The crystalline polypropylene for the base layer was coextruded to obtain a composite film formed of a base layer (40μ) made of the crystalline polypropylene and a layer (i0μ) made of the crystalline propylene random copolymer.

Table 3 shows the performance evaluation results of this polypropylene composite film.
It was shown to.

Examples 10 to 12 Comparative Example 11 The base crystalline polypropylene shown in Tables 2 and 3 was melted in an extruder, extruded through a T-die at a resin temperature of 270°C, cooled and solidified into a sheet, and then heated with a heating roll. By passing it through, it is stretched in the longitudinal direction so that the stretching ratio is 5 times,
A uniaxial sheet of crystalline polypropylene was formed. On one side of this uniaxially stretched sheet of crystalline polypropylene, the crystalline propylene random copolymer composition listed in Table 3vI, which had been melt-kneaded using another extruder, was extruded in a molten state using another T-die at a resin temperature of 250°C. By laminating the molten films and passing this composite sheet through a continuously heated tenter, the composite sheet is stretched in the transverse direction at a stretching ratio of 10.1 times, thereby forming a base material made of crystalline polypropylene. A layer (30μ) and a layer (5μ) made of the crystalline propylene random copolymer composition are laminated, and the crystalline polypropylene base layer is biaxially stretched, and the layer made of the crystalline propylene random copolymer composition. A polypropylene composite film was obtained in a state where Makotomo Ichigo had been applied. Table 3 shows the performance evaluation results of this polypropylene composite fill.

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 propylene and 1-butene. It is a copolymer, and the following items are met: (A) the composition is in the range of 1 to 40 mol% of the propylene component and 60 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;
(D) The degree of crystallinity measured by X-ray diffraction is in the range of 5 to 60%, (E) The amount of soluble content in boiling methyl acetate [W_1 (F) Acetone/n-decane mixed solvent (at 10°C)
The amount of soluble content [W_2% by weight] in the volume ratio 1/1) is 4×[η]＾-＾1＾・＾2% by weight
1. A crystalline propylene random copolymer composition, comprising: a 1-butene-based random copolymer that satisfies the following.