JPH07188483A - Polyolefin resin composition and production of film or sheet - Google Patents

Abstract

PURPOSE:To obtain a resin composition for calendering by mixing a thermoplastic olefin elastomer obtained by copolymerization of segments of a polymer of e.g. ethylene with segments of an EP rubber, with a polyolefin. CONSTITUTION:This composition comprises 100 pts.wt. thermoplastic olefin elastomer (A) obtained by compolymerization of hard segments comprising a homo- or co-polymer of ethylene, propylene or an alpha-olefin with soft segments comprising an ethylene/propylene rubber, and 10-90 pts.wt. polypropylene, high- density polyethylene, low-density polyethylene, polybutene or a mixture (B) thereof or comprising 100 pts.wt. component A, 10-100 pts.wt. polyropylene, 5-50 pts.wt. styrene copolymer, 10-100 pts.wt. polyethylene and 10-100 pts.wt. polybutene. This composition is excellent in workability in rolling because component (A) having no crosslinking step and can form a film or a sheet of excellent thickness precision at high production rate when calendered.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a calenderable polyolefin resin composition excellent in thickness accuracy and high in productivity at high speed, and a method for producing a film / sheet.

[0002]

2. Description of the Related Art When a film or sheet is produced by calendering, a polyvinyl chloride resin (P), which is a halogen-based resin, is mainly used in terms of cost, processability, and other physical properties.
VC) is widely used. However, PVC
In the case of, since hydrogen chloride gas is generated during combustion such as incineration, from the viewpoint of environmental protection in recent years, it is possible to manufacture sheets, etc. by calendering using an environmentally friendly material that does not generate harmful gas during combustion, such as polyolefin resin. Various studies have been made.

[0003]

However, conventional polyolefin resins are difficult to be calendered due to their easiness of crystallinity, and film / sheets are mainly produced by an extrusion method or an inflation method. It was

[0004] Calendering is widely used because it is excellent in thickness accuracy of films and sheets and can be produced at high speed. However, in calendering, the heat history applied to the resin tends to change intricately due to the large number of rolls and long transport paths. Further, the polyolefin resin has a narrow melting transition temperature range and low resin strength at the time of melting, which makes calendar processing difficult.

From the viewpoint of environmental protection, various methods for producing a film or sheet by calendering using a thermoplastic polyolefin-based elastomer (hereinafter referred to as TPO) have been studied. The mainstream of TPO is a hard segment (hard phase) made of PP and / or PE and a soft segment (soft phase) made of EPDM or EPR. P for these TPOs
There are a cross-linking type in which P and EPDM or EPR are separately polymerized and melt-kneaded in an extruder to cross-link, and a polymerization type in which PP and EPR are copolymerized.

However, in the case of producing a film sheet with both TPOs, an extrusion method is generally used.
Various compositions suitable for a method of producing a film / sheet by a calendering method, which is excellent in thickness accuracy and capable of high-speed production, have been studied, but a composition having practical utility has not yet been reached.

An object of the present invention is that it does not generate harmful gas during combustion, is excellent in environmental protection, has excellent thickness accuracy, and is capable of producing a film or sheet by calendering which enables high-speed production. It is an object of the present invention to provide a polyolefin resin composition and a method for producing a film / sheet using the composition.

[0008]

Means for Solving the Problems The above-mentioned object is that the polymer component in the composition comprises (A) a hard segment as a homopolymer or copolymer of a monomer selected from ethylene, propylene and α-olefins. An olefin thermoplastic elastomer of the type in which the soft segment is made of ethylene / propylene rubber and the hard segment and the soft segment are copolymerized: 100 parts by weight,
(B) Polypropylene, high-density polyethylene, low-density polyethylene or polybutene or a mixture thereof: 1
A polyolefin resin composition comprising 0 to 90 parts by weight and the above-mentioned (A) olefin thermoplastic elastomer: 1
Polyolefin resin composition comprising polypropylene: 10 to 100 parts by weight, styrene-based copolymer: 5 to 50 parts by weight, polyethylene and / or polybutene: 10 to 100 parts by weight with respect to 00 parts by weight. Further, it is achieved by a method for producing a film or sheet by calendering each of the above polyolefin-based resin compositions.

In the TPO of the present invention, the hard segment comprises a homopolymer or copolymer of a monomer selected from ethylene, propylene or α-olefin, the soft segment comprises ethylene-propylene rubber, and the hard segment and the soft segment. Is a copolymerized type.

Unlike the TPO in the present invention, there is a cross-linking type TPO in which PP and EPR are separately polymerized and melt-kneaded and cross-linked by an extruder. In the case of this TPO, since it has an additive that hinders the roll properties, the film / sheet may be adhered to the roll surface of the film / sheet, bleeding to the sheet surface, oxidative deterioration, etc.
In particular, it is difficult to calender a thin film.

In the polymerization type TPO of the present invention,
Unlike the cross-linked TPO, since it does not have a cross-linking step in the production of TPO, it has no additives that hinder the roll properties and has excellent roll properties. Especially the TP of the present invention
As O, those having a ratio of hard segment to soft segment of 60 to 30:40 to 70 are preferable. Further, as commercially available products of TPO suitable for the present invention, for example, R
410E [manufactured by Tokuyama Soda Co., Ltd.], CA12A [Himo
nt Co., Ltd.] and the like.

[0012] Such TPO: 100 parts by weight,
Polypropylene, high density polyethylene, low density polyethylene or polybutene or mixtures thereof: 10-9
0 parts by weight, preferably 30 to 50 parts by weight is blended.
TPO: When the amount of these components mixed with 100 parts by weight is less than 10 parts by weight, the hardness of the film / sheet becomes insufficient, and the smoothness of the roll, the sheet smoothness, the sheet take-up property, and the shrinkage after taking-up are caused. Etc., it is difficult to obtain satisfactory properties, while when it is more than 90 parts by weight, crystallinity becomes strong and calendar processing becomes difficult.

The resulting film
From the viewpoint of the surface smoothness of the sheet, it should be arbitrarily selected from the viewpoints of melt flow rate, flexural modulus, melting point and crystallinity, etc., but random polypropylene is particularly preferable. In this random polypropylene (hereinafter referred to as random PP), the rubber component is added irregularly, so that the stereoregularity of the polymer is disturbed and the crystallinity is relatively low. Therefore, it is possible to improve the calendering processability. is there.

Such a random PP is particularly excellent in transparency and has a melt flow rate (JIS K675).
8) is 0.3 to 30 g / 10 min, more preferably 0.5 to 9 g / 10 min, flexural modulus (JIS K6
758) is 3000 to 30000 kgf / cm ² , more preferably 4000 to 13000 kgf / cm ² , Vicat softening temperature 70 ° C. to 150 ° C. (JISK 6758).
The commercially available products are preferably FS6632 (manufactured by Sumitomo Chemical Co., Ltd.), Hypol B230 (manufactured by Mitsui Petrochemical Industry Co., Ltd.), Nobrene GEB-G5 (manufactured by Mitsui Toatsu Chemical Co., Ltd.), and the like. Can be mentioned.

Especially when polypropylene is used in combination with a styrene copolymer and polyethylene and / or polybutene, polypropylene is added in an amount of 10 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of TPO.
Parts by weight are added. The addition of polypropylene can control the hardness of the film sheet during calendering. Therefore, when the amount of PP added is less than 10 parts by weight, the hardness of the film or sheet becomes insufficient, while when the amount of PP added is more than 100 parts by weight, the crystallinity becomes strong and the calendering becomes difficult. Become.

Further, by adding a styrene-based copolymer together with PP, especially random PP, it is possible to prevent the impact-whitening phenomenon of the film / sheet and to improve the cold impact resistance, and the transparency which the random PP has. Calendering is possible by lowering the crystallinity without deteriorating the crystallinity.

The styrenic copolymer is preferably, for example, a polymer block composed of (a) styrene or a styrene homolog and (b) a conjugated diene, and a hydrogenated block copolymer or a mixture thereof is preferable. is there. Examples of these copolymers include styrene or a homologue of styrene represented by X, and a polymer block composed of a conjugated diene represented by Y, X / Y, X / Y / X, X / Y / Y '...・ ・
And the like are shown as a hydrogenated copolymer.

Examples of such styrene-based copolymers include styrene-based block copolymers and styrene-based graft polymers. Examples of the styrene block copolymer include a hydrogenated styrene-butadiene-styrene copolymer and a hydrogenated styrene-isoprene-styrene block copolymer. Examples of commercially available styrene block copolymers include Kraton G [Shell Chemical Co., Ltd.
Manufactured], Hibler [manufactured by Kuraray Co., Ltd.], Tuftec [manufactured by Asahi Kasei Corporation], Dynaron [Nippon Synthetic Rubber Co., Ltd.]
Made] etc.

Further, as the styrene-based graft copolymer, for example, a copolymer obtained by graft-polymerizing styrene and acrylonitrile onto an olefin-based polymer such as polypropylene serving as a trunk, and as a commercially available product, for example, MODIPER [NOF CORPORATION] Manufactured] and the like.

These styrenic copolymers have the following TPO:
5 to 50 parts by weight is added to 100 parts by weight. If the addition amount of the styrene-based copolymer is less than 5 parts by weight, the above-mentioned addition effect is not sufficient, while if it is more than 50 parts by weight, the roll adhesion becomes strong and the surface smoothness of the sheet deteriorates, and It will be too soft.

Next, in order to increase the fluidity of the resin during calendering and the strength during melting of TPO,
Polyethylene and polybutene, which have good compatibility with PP that is a hard segment in TPO and have a low melting point, are blended. As polyethylene, low density polyethylene excellent in impact strength and transparency or high density polyethylene excellent in mechanical properties and heat stability are particularly suitable, and these can be used alone or in combination. In these polyethylenes, for example, the melting temperature is preferably about 80 to 140 ° C., and the melt flow rate (JIS K675
8) is preferably 0.3 to 30 g / 10 min, more preferably 0.5 to 10 g / 10 min.

As the polybutene, a highly stereoregular crystalline polymer obtained by polymerizing butene-1 as a main monomer using a Ziegler type catalyst is preferable. In these polybutenes, for example, the melting temperature is 70 to 140. ℃ is preferable, and melt flow rate (JIS K675
8) is preferably 0.3 to 30 g / 10 min, more preferably 0.5 to 10 g / 10 min.

Polyethylene and / or polybutene is added in an amount of 10 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of TPO. If the amount of polyethylene and / or polybutene added is less than 10 parts by weight, the hardness of the film / sheet will be insufficient, and if it is more than 100 parts by weight, the crystallinity will be so strong that calendering will be difficult.

The resin composition of the present invention can be used to produce a film or sheet having a thickness of about 50 to 500 μm by a calendering method, and if necessary, an antioxidant, an antistatic agent, or an ultraviolet absorber can be used depending on the difference in application. Agents, pigments and fillers can be optionally added.

The film and sheet obtained by the calendering method of the present invention have a lower specific gravity than general PVC films and sheets, and are harmful gases such as hydrogen chloride gas during combustion such as incineration or fire. It is a material that does not generate heat, is environmentally friendly, and can secure the safety of human life. It also has excellent cold resistance and hardly cracks when impacted. Therefore, the pressing for exhibiting the design of the surface of the film / sheet can be freely performed, the drawing heat resistance is high, and since no plasticizer is added, no adverse effects due to bleeding of the plasticizer such as PVC do not occur.

With respect to the surface scratch of the film / sheet obtained in the present invention, scratches can be prevented by processing a top coat of urethane elastomer or the like.
Further, the film / sheet obtained by the present invention has the above-mentioned characteristics and therefore can be applied to various uses, but is particularly effective as a decorative sheet for industrial materials, for example, a steel / plywood film sheet.

[0027]

【Example】

Examples 1 to 4 and Comparative Examples 1 to 3 Each of the resin compositions shown in Tables 1 and 2 was passed through a roll of the calender body through a Banbury mixer to give a thickness of 0.1.
A sheet having a width of 5 mm and a width of 1000 mm was prepared. The temperature of each roll of the calender body is about 165 to 195 ° C,
Next, the sheet temperature was set to 150 to 180 ° C, and the squeezing roll temperature was set to 65 ° C. The roll characteristics during this calendering were evaluated, and the results are shown in Table 1 and Table 2, respectively. In addition, heat sealability and drawing heat resistance were also evaluated.

Evaluation of roll characteristics Roll lubricity ○: Easy to peel manually from the roll surface △: Peeling from the roll surface by hand slightly slightly ×: Difficult to peel manually from the roll surface Bank condition ○: Roll surface condition to rotate cleanly △: Roll surface condition Slightly rough ×: Roll surface condition Rough sheet smoothness ○: Roll surface smoothness is excellent △: Roll surface smoothness is slightly poor ×: Roll surface smoothness is poor, sheet take-off property ○: Easy to stretch and thin film possible △ : Stretching is difficult and there is a hole in the sheet surface x: Stretching is not possible Shrinking after take-up ○: Stretching is easy and a thin film is possible △: Stretching is difficult and there is a hole in the sheet surface x: Stretching is not possible

Heat-sealing property : Two films were thermocompression-bonded to each other at 140 ° C., and the interlayer adhesive strength of both films was evaluated. ○: Adhesive strength is large △: Adhesive strength is slightly large ×: Adhesive strength is insufficient Squeezing heat resistance : The obtained film is put into oil bath 1
It was dipped in 50 ° C. for 30 seconds and visually evaluated for gloss change and unsqueezed residue. ○: Small change in gloss △: Small change in gloss ×: Large change in gloss

The contents of the polymer components in Tables 1 and 2 are as follows. TPO: CA12A [manufactured by Himont Co., Ltd.] PP: Noblen GEB-G5 [manufactured by Mitsui Toatsu Kagaku Co., Ltd.] PE: Ultozex 1520L [manufactured by Mitsui Petrochemical Industry Co., Ltd.] PB: Bureau P-5040 [Mitsui Sekiyu] Chemical Industry Co., Ltd.] Styrene copolymer: DYNARON [Nippon Synthetic Rubber Co., Ltd.]

[0031]

[Table 1]

From Table 1, when only PP is mixed with TPO as in Example 1, the roll characteristics are not sufficient but calendering is possible, and as in Example 2, P
When PE is used together with P, roll lubricity and heat sealability are improved, and when PB is used together with PP as in Example 3, the removability is good and the shrinkage after the take-up is reduced,
It can be seen that when the styrene-based copolymer is used together with PP and PB as in Example 4, roll lubricity, heat sealability and drawing heat resistance are all excellent.

[0033]

[Table 2]

From Table 2, as in Comparative Example 1, when the blending amount of the styrene-based copolymer is too large, the roll characteristics are poor and the calendering process becomes difficult. It is understood that when only PP and PE are blended and the blending amount is too large, the roll lubricity and the drawing heat resistance are poor.

[0035]

As described above, according to the present invention, the TP can be produced by the calendering method which is excellent in thickness accuracy and enables high-speed production.
A film or sheet mainly containing O can be easily produced, and the film or sheet obtained by the compounding composition of the present invention can be freely pressed to exert its surface design, and the heat When the property is 150 ° C. or less, it is possible to provide a film / sheet which has no gloss and has excellent appearance.

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Claims (6)

[Claims] 1. A polymer component in the composition, wherein (A) the hard segment comprises a homopolymer or copolymer of a monomer selected from ethylene, propylene or α-olefin, and the soft segment comprises ethylene / propylene rubber. And an olefinic thermoplastic elastomer of the type in which a hard segment and a soft segment are copolymerized: 1
A polyolefin resin composition comprising (B) polypropylene, high-density polyethylene, low-density polyethylene, or polybutene or a mixture thereof in an amount of 10 to 90 parts by weight per 100 parts by weight. 2. The polymer component in the composition, wherein (A) the hard segment comprises a homopolymer or copolymer of a monomer selected from ethylene, propylene or α-olefin, and the soft segment comprises ethylene / propylene rubber. And an olefinic thermoplastic elastomer of the type in which a hard segment and a soft segment are copolymerized: 1
Polypropylene: 10 to 100 parts by weight Styrene-based copolymer: 5 to 50 parts by weight Polyethylene and / or polybutene: 10 to 100 parts by weight, based on 00 parts by weight, a polyolefin resin composition. 3. The styrene-based copolymer comprises a polymer block composed of (a) styrene or a styrene homolog and (b) a conjugated diene, and is a hydrogenated block copolymer or a mixture thereof. The polyolefin resin composition according to claim 2, wherein 4. The polymer component in the composition comprises (A) a hard segment consisting of a homopolymer or copolymer of a monomer selected from ethylene, propylene or α-olefin, and a soft segment consisting of ethylene / propylene rubber. And an olefinic thermoplastic elastomer of the type in which a hard segment and a soft segment are copolymerized: 1
A polyolefin resin composition comprising (B) polypropylene, high-density polyethylene, low-density polyethylene or polybutene or a mixture thereof (10 to 90 parts by weight) per 100 parts by weight of a polyolefin resin composition is calendered. Production method. 5. A polymer component in the composition, wherein (A) the hard segment comprises a homopolymer or copolymer of a monomer selected from ethylene, propylene or α-olefin, and the soft segment comprises ethylene / propylene rubber. And an olefinic thermoplastic elastomer of the type in which a hard segment and a soft segment are copolymerized: 1
With respect to 00 parts by weight, polypropylene: 10 to 100 parts by weight Styrene-based copolymer: 5 to 50 parts by weight Polyethylene and / or polybutene: 10 to 100 parts by weight A polyolefin resin composition is calendered. The method for producing a film sheet according to claim 3. 6. The styrene-based copolymer comprises a polymer block composed of (a) styrene or a styrene homolog and (b) a conjugated diene, and is a hydrogenated block copolymer or a mixture thereof. The method for producing a film sheet according to claim 5, wherein