JPH11147981A - Propylene resin film excellent in weatherability and resistance to whitening - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the irregularity occurring in high-speed extrusion of a propylene resin film and improve the fabricability of the film by compounding a propylene-α-olefin copolymer having a specified propylene content and exhibiting a peak at a specified temp. in the thermogram with a benzotriazole- or benzophenone-based ultraviolet absorber and a hindered amine light stabilizer. SOLUTION: A propylene-α-olefin copolymer of 100 pts.wt. is compounded with 0.05-1.5 pts.wt. benzotriazole- and/or benzophenone-based ultraviolet absorber and 0.1-1.0 pt.wt hindered amine light stabilizer and then is sheeted. Pref., the copolymer has a propylene content of 70 wt.% or higher, exhibits a peak at 115-140 deg.C in a thermogram obtd. with a differential thermal scanning meter and side peaks or inflection points between the peak and 30 deg.C, and has as a wt. average mol.wt. of 200,000-700,000. The thickness of the film is pref. 5-400 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a propylene copolymer composition having excellent weather resistance and whitening resistance.
The present invention relates to a film excellent in secondary workability in which the extrusion unevenness phenomenon is improved by high-speed molding. More specifically, the present invention provides a propylene-based resin film suitable as a film for building materials.

[0002]

2. Description of the Related Art A polyvinyl chloride resin blended with a plasticizer has been widely used since it has excellent transparency, secondary workability, whitening resistance and weather resistance. However, the polyvinyl chloride resin has a problem that toxic hydrogen chloride gas is generated during incineration, which causes damage to the incinerator and induces air pollution. Also, halogens in the polyvinyl chloride resin are considered to be a cause of producing highly toxic dioxins during incineration. Furthermore, the plasticizer blended with the polyvinyl chloride resin has problems of leaching and toxicity. For these reasons, the use of polyvinyl chloride resin has recently been regulated. As a method of solving such a disadvantage of the polyvinyl chloride resin, it is conceivable to use a propylene-based resin instead of the polyvinyl chloride resin (for example, JP-A-2-283740, JP-A-3-29-29).
No. 2344). However, the techniques described in these publications relate to shrink films, and the relationship between the main peak in the thermograph of the propylene-α-olefin copolymer used and other peaks or inflection points or the like. It does not disclose the characteristics at all, and furthermore, does not disclose the whitening resistance and the secondary workability of the propylene-based resin film. In addition, Japanese Patent Application Laid-Open No.
No. 82 discloses a laminate having a light-transmitting surface layer made of polypropylene, but does not disclose any specific composition and characteristics of polypropylene used in the surface layer. Also, JP-A-9-76398 discloses that
As a material of the olefin-based resin layer used in the olefin-based resin film for building materials, simply referring to the polypropylene resin, the relationship between the main peak and other peaks or inflection points and characteristics Not disclosed at all.

[0003] Further, in a conventional polypropylene resin, T
-When the film is produced by die molding or extrusion coating molding, the stability of film formation at high speed and the drawdown property are poor. Conventionally, there is an example of this solution in which low-density polyethylene is blended to increase the melt tension of the resin. However, the heat resistance, the rigidity, and the whitening phenomenon of the molded film are inevitable.

[0004]

Accordingly, the present invention provides a propylene-based resin film having weatherability and whitening resistance, improved extrusion unevenness by high-speed molding, and excellent secondary workability. In particular, it is an object of the present invention to provide a film having the same hardness as a substitute for a semi-rigid polyvinyl chloride resin. Still another object of the present invention is to provide a propylene-based resin film that is particularly suitable as a film for building materials.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, they have contained propylene as a component of a propylene-based resin film in an amount of 70% by weight or more and used a differential thermal scanning meter. A peak is observed at 115 to 140 ° C. in the thermogram to be measured.
And at least one sub-peak and / or
Alternatively, a benzotriazole-based ultraviolet absorber and / or a benzophenone-based ultraviolet absorber are added to 100 parts by weight of the propylene-α-olefin copolymer at which the inflection point is observed.
To 1.5 parts by weight and a hindered amine light stabilizer 0.1 to 1.
It has been found that the above object can be achieved by adding 0 parts by weight. Furthermore, they have found that high-speed moldability can be further improved by blending 2 to 25 parts by weight of high melt strength polypropylene with respect to 100 parts by weight of the propylene-α-olefin copolymer. The present invention has been made based on the above novel findings.

That is, the present invention contains 70% by weight or more of propylene, and a peak is observed at 115 to 140 ° C. in a thermogram measured by a differential scanning calorimeter.
Benzotriazole-based UV absorber and / or benzophenone-based propylene-α-olefin copolymer (100 parts by weight) in which at least one sub-peak and / or inflection point is observed between C and the peak. UV absorber 0.
05 to 1.5 parts by weight and hindered amine light stabilizer 0.1 to
The present invention relates to a propylene-based resin film characterized by adding 1.0 part by weight. Further, the present invention is based on 100 parts by weight of the propylene-α-olefin copolymer,
The present invention relates to a propylene-based resin film in which high-speed moldability is further improved by blending 2 to 25 parts by weight of high melt strength polypropylene.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 70% by weight of the propylene resin film of the present invention
The above propylene and α-olefin are copolymerized,
In a thermogram measured by a differential thermal scanner
A peak is observed at 115-140 ° C, and at 30 ° C,
A propylene-α-olefin copolymer in which at least one sub-peak and / or inflection point is observed between these peaks, a benzotriazole-based ultraviolet absorber and / or a benzophenone-based ultraviolet absorber, and a hindered amine-based light It consists of a combination of a stabilizer and, optionally, a high melt strength polypropylene. The carbon number of the α-olefin constituting the propylene-α-olefin copolymer is 2 to 20 (excluding 3), and particularly preferably 2 to 10 (excluding 3). As the α-olefin, specifically, ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 4-
Methylpentene-1,4-methylhexene-1,4,4
-Dimethylpentene-1 and the like can be mentioned as preferred. Of these monomers, particularly, from the viewpoint of copolymerizability and availability, ethylene and butene-
1, pentene-1, hexene-1, heptene-1, octene-1, and 4-methylpentene-1 are preferred. Especially,
Ethylene and butene-1 are preferred.

[0008] If necessary, other polymerizable monomers may be used in combination. Such monomers include:
For example, vinylcycloalkanes such as vinylcyclohexane can be used. The content of propylene in the propylene-α-olefin copolymer is 70% by weight.
It is above, preferably 70 to 97% by weight, particularly preferably 70 to 94% by weight. If the propylene content is less than 70% by weight, the propylene-based resin film becomes not only soft but also sticky, which makes it difficult to handle. Therefore, the content of α-olefin in the propylene-α-olefin copolymer is less than 30% by weight, preferably 3% by weight or more and less than 30% by weight, and more preferably 6% by weight or more. Less than 30% by weight. In particular, when the α-olefin is ethylene and butene-1, the content of ethylene is 1% by weight or more and less than 5% by weight, and the content of butene-1 is
The content of ethylene is preferably 2% by weight or more and less than 15% by weight, and particularly, the content of ethylene is 1% by weight or more and less than 5% by weight, and the content of butene-1 is 5% by weight or more and 15% by weight.
It is preferably less than.

[0009] The propylene-α-olefin copolymer is
One kind may be used alone, or a blend composed of a plurality of kinds of propylene-α-olefin copolymers may be used. Examples of such a blend include, for example, a blend of a propylene-ethylene random copolymer and a propylene-ethylene-butene random copolymer, and a blend of a propylene-ethylene random copolymer and a propylene-butene random copolymer. Blends and the like can be mentioned. In the case of a blend, the content of the α-olefin to be copolymerized is considered based on the blend. Propylene-α-
The weight average molecular weight of the olefin copolymer is preferably 1
Suitably, it is from 100,000 to 900,000, particularly preferably from 200,000 to 700,000. Propylene-α- used in the present invention
The melting point of the olefin copolymer is determined as follows. A film having a thickness of 150 to 200 μm is prepared using a thermocompression molding machine, punched out into a disk shape having a diameter of about 5.5 mm using a puncher, and set in an aluminum pan for Perkin Elmer DSC7. The pan was set on a Perkin Elmer DSC7, kept at 230 ° C for 5 minutes, then cooled at 20 ° C / min to 30 ° C, then kept at 30 ° C for 5 minutes, and raised to 230 ° C at 20 ° C / min. Warm up and obtain a heating thermogram. At this time, a peak having a clear maximum on the endothermic side, and a shoulder (shoulder) simply identified by an inflection point, or a peak that appears as a peak due to a small change of less than 2% of the maximum peak intensity in the thermogram is a peak. Is not considered. Briefly, a peak is detected based on the above-mentioned baseline using a program built in the DSC 7 to determine a melting peak. The strongest peak obtained in this way (hereinafter referred to as the main peak)
According to the invention, it is observed at 115-140 ° C. Preferably, it is observed at 115-135 ° C. If the main peak exists at a temperature higher than 140 ° C., whitening of the film tends to occur.

As an important property of the propylene-α-olefin copolymer of the present invention, one or more further peaks and / or inflection points are observed between 30 ° C. and the temperature of the main peak. That's it. It is preferred that what is observed between 30 ° C. and the temperature of the main peak is a peak rather than an inflection point. The presence of such sub-peaks / inflection points makes the formed film excellent in the secondary workability and whitening resistance, and particularly, in the case where the surface is embossed, the secondary workability is excellent. It is effective to Also, due to the presence of minor peaks / inflection points, the film is
When a tensile test is performed in minutes, there is no yield point in the stress-strain curve. The high melt strength polypropylene preferably used in the present invention has a branching index of less than 1, preferably less than 0.4 (the lower limit is, for example, 0.2).
And a gel which does not include a gel having a strain hardening elongational viscosity, for example, a predominantly isotactic semicrystalline polypropylene. Examples of such high melt strength polypropylene include propylene homopolymer and those made of a random copolymer of propylene and ethylene. Such high melt strength polypropylene can be produced, for example, by the method described in JP-A-62-121704.

Here, the branching index quantifies the degree of long-chain branching, and is defined as [η] _sr / [η] _Lin . Here, [η] _sr is the intrinsic viscosity of the branched polypropylene, and [η] _Lin is the intrinsic viscosity of the linear polypropylene having substantially the same weight average molecular weight. Elongational viscosity is the resistance of a fluid or semi-fluid substance to elongation. The strain hardening elongational viscosity is a property showing a phenomenon that the elongational viscosity increases as the amount of elongation increases. The introduction of long chain branching results in a strain hardening elongational viscosity.
This elongational viscosity can be measured by an apparatus for measuring stress and strain of a sample in a molten state when subjected to tensile strain at a constant speed. The MFR of the propylene-α-olefin copolymer (a mixture of the propylene-α-olefin copolymer and the high melt strength polypropylene when the high melt strength polypropylene is used together) used in the present invention is preferably 0. 0.8 to 18 g / 10 min, preferably 1.5 to 12 g / 10 min.

High melt strength polypropylene optionally used in the present invention
Pyrene is 100 parts by weight of a propylene-α-olefin copolymer.
Parts by weight, preferably 2 to 25 parts by weight.
More preferably, the amount is 5 to 18 parts by weight. High
If the amount of the melt strength polypropylene is less than 2 parts by weight,
Extrusion tension during high-speed molding
It is difficult to improve. On the other hand, high melt strength polypropylene
If the amount of pyrene exceeds 25 parts by weight, the resulting propylene
Tension (MT) with respect to MFR of resin-based resin film
It's too big and it's easy to cut the film by high speed molding
Is not preferred. Compounding high melt strength polypropylene
And the melt tension (MT) of the propylene-based resin film and M
The relationship with FR is 3.45 x MFR^-0.7749≦ MT ≦ 11.32
× MFR ^-0.7854And preferably 4.67 × MFR
^-0.8437≦ MT ≦ 6.60 × MFR^{-0.819 Two}Becomes This function
The person in charge is 3.45 x MFR^-0.7749> In MT, high-speed molding
In this case, extrusion unevenness is likely to occur. On the other hand, MT> 11.32 × MF
R^-0.7854Then, the film is easily cut by high-speed molding.

Here, the MFR of the resin is measured at 230 ° C. by the method described in JIS K7210. The melt tension (MT) of the resin is measured according to an apparatus for measuring MFR shown in JIS K7210. Specifically, after preheating about 5 g of resin in a cylinder at 230 ° C. for 5 minutes, the strand discharged from the capillary at an extrusion speed of 15 mm / min is taken up by a piston at a constant speed of 6.4 m / min, and the pulley is interposed on the way. Read and record the load with a stress gauge via
The average value of the readings between 120 and 180 seconds from the start of the measurement was defined as the melt tension. In the present invention, the melt tension (MT) of the propylene-α-olefin copolymer (a mixture of the propylene-α-olefin copolymer and the high melt strength polypropylene when using a high melt strength polypropylene) is as follows:
Preferably, it is 1 to 10 g, more preferably 1.2 to 8 g. If it is less than 1 g, high-speed molding tends to cause uneven extrusion. If it exceeds 10 g, film breakage tends to occur during high-speed molding.

The benzotriazole-based ultraviolet absorber used in the present invention is preferably a 2- (2-hydroxyphenyl) benzotriazole derivative. The benzotriazole-based ultraviolet absorber is particularly preferably a 2- (2-hydroxyphenyl) benzotriazole derivative having a substituted hydroxyphenyl group, and more preferably an aromatic ring having a hydroxyphenyl group of 3 or more carbon atoms. A 2- (2-hydroxyphenyl) benzotriazole derivative substituted with a branched alkyl group which may contain Examples of such a branched alkyl group include a t-butyl group, a t-amyl group, and a t-amyl group.
-3-20 carbon atoms such as an octyl group, preferably 3-10
And branched alkyl groups having two or more groups. As the aromatic ring which may be optionally contained, for example, an aromatic ring having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, such as a phenyl group or a naphthyl group, is suitable.

Examples of the benzotriazole-based UV absorber suitably used in the present invention include Tinuvin P and Tinuvin manufactured by Ciba Specialty Chemicals.
PS, Tinuvin 320, Tinuvin 326, Tinuvin 327, Tinu
vin 328, Tinuvin 329, Tinuvin 234, Tinuvin 213
, Tinuvin 571, Biosorb 590 from Kyodo Yakuhin, Adeka Stab LA31 from Asahi Denka, and mixtures thereof. On the other hand, the benzophenone-based ultraviolet absorber used in the present invention is preferably 2
-Hydroxybenzophenone derivatives. As the benzophenone-based ultraviolet absorber, specifically, BA
SF Uvinul 1400, Uvinul M40, Uvinul D49, Uvin
ul M49, BioSorb 130 of Kyodo Yakuhin, V24 of Eastman Chemical's PB Siersorb, LS5 of Asahi Denka
Known compounds such as 1 and blends thereof are exemplified.

Among the benzotriazole-based UV absorbers and / or benzophenone-based UV absorbers used in the present invention, benzotriazole-based UV absorbers are preferably used. Above all, UV-absorbing ability and affinity for resin are preferable. From a point of view, of these benzotriazoles, LA31
And Tinuvin 234, Tinuvin 328 and Tinuvin 329 are more preferably used. The amount of the benzotriazole-based UV absorber and / or benzophenone-based UV absorber added is 0.05 to 1.5 parts by weight, preferably 0.2 to 1 part by weight, based on 100 parts by weight of the propylene-α-olefin copolymer. Is appropriate. The amount of UV absorber is 0.05
If the amount is less than part by weight, the effect of shielding ultraviolet rays is insufficient, so that the weather resistance is not sufficient, and the use is very limited. On the other hand, if the amount of the ultraviolet absorber exceeds 1.5 parts by weight, problems such as bleeding will occur, and no improvement in the effect will be seen, and the expensive ultraviolet absorber will be wasted.

The hindered amine light stabilizer used as the light stabilizer in the present invention comprises a hindered amine nitrogen atom and a six-membered heterocyclic ring containing any other atom, preferably nitrogen or oxygen. The atoms may be secondary or tertiary. As the hindered amine-based light stabilizer, it is preferable to use a compound having a secondary hindered amine nitrogen atom and a compound having a tertiary hindered amine nitrogen atom as a mixture. In this case, the weight ratio of the compound having a secondary hindered amine nitrogen atom to the compound having a tertiary hindered amine nitrogen atom is preferably from 10:90 to 90:10,
Particularly preferably, the ratio is 30:70 to 70:30. As the hindered amine light stabilizer, those having a high molecular weight or those capable of grafting to a polymer by a photoreaction are preferable. The high molecular weight hindered amine light stabilizer preferably has a molecular weight of 1,000 or more, particularly preferably 1500 or more (the upper limit is, for example, 8000). Further, the graft type is preferably, for example, one having a benzylidene malonate structure. Specific examples of such hindered amine light stabilizers include Tinuvin 622, Chimassorb 944, and Chimsorb 944 of Ciba Specialty Chemicals.
assorb 119, Tinuvin 770, Tinuvin 765, Tinuvin 14
4, Tinuvin 123, Sanol LS 2626, Asahi Denka ADK STAB LA57, LA62, LA67, LA63, LA68, LA8
2, LA 87, Goodrich UV3034 from Goodrich, VP Sanduvor PR-31 from Clariant, Cyasorb 334 from Cytex
6, Cyasorb UV 500, 3V Chemical Uvasorv HA88,
Hoechst's Hostavin N30, Sigma's Uvasorb HA88,
Great Lakes Uvasil 299, BASF Uvinul 4
049H, Uvinul 4050H, Uvinul 5050H, ChemcoSytec's Dastib 845 and mixtures thereof.

In the present invention, the hindered amine light stabilizer is a propylene-α-olefin copolymer 100
0.1 to 1.0 part by weight, preferably 0.2 to 1.0 part by weight,
Suitably 0.6 parts by weight. When the amount of the ultraviolet absorber is less than 0.1 part by weight, the effect of improving the weather resistance becomes insufficient, and the application is very limited. On the other hand, when the amount of the hindered amine light stabilizer exceeds 1.0 part by weight, the degree of improvement in the effect is not so large as compared with the amount added. Resin composition containing the propylene-α-olefin copolymer, a benzotriazole-based UV absorber and / or a benzophenone-based UV absorber, a hindered amine-based light stabilizer, and, if necessary, a high melt strength polypropylene. The object can be formed into a sheet using a known method. As such a forming method, for example, specifically, a method of kneading in a molten state using an extruder such as a single-screw extruder or a twin-screw extruder can be mentioned as a preferable method. A propylene-α-olefin copolymer containing no benzotriazole-based ultraviolet absorber and / or benzophenone-based ultraviolet absorber and a hindered amine-based light stabilizer;
Before forming a film, a masterbatch containing a benzotriazole-based UV absorber and / or a benzophenone-based UV absorber and a hindered amine-based light stabilizer using an olefin copolymer and / or another polyolefin-based resin as a carrier resin is dried. By blending or feeding each to the molding machine independently
A film having a predetermined blend ratio can be obtained. Here, as the polyolefin resin, a known resin such as a polypropylene resin or a polyethylene resin can be arbitrarily used as long as the effects of the present invention are not impaired. The higher the concentration of the master batch, the more efficient it is. Usually, a masterbatch having a concentration of 5 to 20 times is used, but the present invention is not limited thereto.

The film of the present invention has a thickness of 5 to 400 μm,
Preferably, it is suitable to use at 20 to 200 μm. If the thickness is less than 5 μm, the shielding of ultraviolet rays tends to be insufficient, and if it exceeds 400 μm, the propylene-based resin film tends to be too hard, which is not preferable. The propylene-based resin film of the present invention includes a T die, a hanger coat die,
It is also possible to manufacture by extrusion using a die such as a circular die. Further, a film may be produced by calender molding using a calender molding machine. Since the film of the present invention has excellent secondary processing properties, a molded article having an excellent appearance can be obtained without causing breakage at the embossed portion during the secondary processing, even when the surface is embossed. be able to. Therefore, processing can be facilitated by heating during the secondary processing. Since the heating temperature depends on the deformation rate of the resin for secondary processing and the content of α-olefin in the propylene-α-olefin copolymer, it cannot be specified unconditionally. In this case, it is possible to obtain a molded article having an excellent appearance by increasing the processing temperature. The heating temperature is specifically 50 to 135 ° C (however, not more than the temperature of the main peak of melting of the propylene-α-olefin copolymer), and preferably 60 to 135 ° C.

Since the propylene-based resin film of the present invention has excellent visible light transmittance, it can be laminated on a film having a printed layer. As a film having such a printing layer, it is appropriate to use a printing film made of a crystalline polyolefin resin. Examples of such a crystalline polyolefin resin include known propylene homopolymers, propylene-α-olefin copolymers, ethylene homopolymers, and ethylene-α-olefin copolymers. These resins may be filled with an inorganic feeler. In this case, as a suitable inorganic filler, for example, talc, calcium carbonate, titanium oxide,
Kaolin clay, aluminum hydroxide, barium sulfate,
Examples include magnesium hydroxide and synthetic silica. These fillers are preferably filled in an amount not exceeding 40% by weight. Furthermore, if necessary, an organic or inorganic pigment may be contained.

The propylene resin film of the present invention can be laminated on a crystalline polyolefin resin film having a print layer by a known method. For example, there are a method of bonding separately manufactured films via an adhesive layer, and a method of coating a resin on a previously manufactured film by melt extrusion.

[0022]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. In addition, the evaluation method of the characteristic in an Example and a comparative example is as follows. Secondary workability: Propylene- in a 100 ° C chamber
A single film consisting of an α-olefin copolymer, a benzotriazole-based UV absorber and a hindered amine-based light stabilizer was subjected to a tensile test at 50 mm / min to determine whether or not there was a yield point. Those having no yield point were judged to have good secondary workability. Weather resistance: The weather resistance of the film laminated at 63 ° C. on the black panel was measured using a carbon arc sunshine weatherometer. The evaluation was made based on the time until the appearance changes. Whitening resistance: Evaluated by bending the film with a finger. Extrusion unevenness: Evaluated by drawdown property. The drawdown is the maximum speed at which the film can be formed without causing thickness unevenness or end-shake of the film.

Example 1 A high-density polyethylene (weight average molecular weight: 128,000) filled with 20% by weight of calcium carbonate was calendered into a film of 80 μm, corona-treated, printed, and printed. Prepared. On the other hand, a propylene-ethylene-butene copolymer (ethylene content: 3.5% by weight, butene content: 6% by weight, propylene content: 9%)
0.5% by weight, melting temperature 131 ° C., secondary peak temperature 97 ° C., weight average molecular weight 390,000 (in terms of homo PP) 100 parts by weight, IRGANO as an antioxidant
X B225 (manufactured by Ciba Specialty Chemicals)
(IRGAFOS 168 (tris (2,4-di-t-butylphenyl) phosphite) and IRGANOX 1010 (pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) ]) And 1:
0.3 part by weight of Tinuvin 622 (manufactured by Ciba Specialty Chemicals) (dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6, succinate) as a hindered amine light stabilizer. 0.2 parts by weight of 6-tetramethylpiperidine polycondensate), Chimassorb 9
44 (manufactured by Ciba Specialty Chemicals) (poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl]
[(2,2,6,6-tetramethyl-4-piperidyl)
Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperazyl) imino]] (molecular weight: 2000
To 3100) as a benzotriazole-based ultraviolet absorber, Tinuvin 328 (manufactured by Ciba Specialty Chemicals) (2- (3,5-di-t-amyl-2).
-Hydroxyphenyl) benzotriazole) and 0.5 parts by weight of calcium stearate were prepared using a co-rotating twin screw extruder at 230 ° C. Was used to prepare an embossed 80 μm film. FIG. 1 shows a DSC thermogram of the propylene-ethylene-butene copolymer used. Finally, the two films were bonded together via an adhesive, and then their properties were evaluated.
The evaluation results are shown in Table 1 below.

Example 2 In Example 1, a propylene-ethylene random copolymer containing 15% by weight of talc (ethylene content: 3.5% by weight, propylene content: 96.5) was used in place of the high-density polyethylene film. Weight%, weight average molecular weight 550,000)
Propylene-ethylene-butene copolymer (ethylene content: 1.5% by weight, butene content: 14% by weight, propylene content: 84.5% by weight, Peak temperature 130
° C, temperature of sub-peak 92 ° C, weight average molecular weight 390,000 (Homo P
Except for using P))), the same procedure as in Example 1 was performed.
A laminate was prepared. In addition, the propylene used here-
FIG. 2 shows a DSC thermogram of the ethylene-butene copolymer.
Shown in Table 1 shows the evaluation results.

Example 3 A propylene-ethylene-butene random copolymer having an MFR of 5.1 g / 10 min (ethylene content: 3.
5% by weight, butene content: 6% by weight, propylene content: 90.5% by weight, temperature of melting main peak 131 ° C, temperature of auxiliary peak 97 ° C, weight average molecular weight 390,000 (homo PP
100 parts by weight) of Montelu's high melt strength polypropylene PF814 (mainly isotactic semi-crystalline polypropylene homopolymer with a branching index of 0.32 and no gel with strain hardening elongational viscosity) 5
Except that it was blended in parts by weight, the T-die
It was laminated on a printed film with a thickness of μm. Table 2 shows the evaluation results. The MFR of the blended resin is 5.
It was 0 g / 10 min and the MT was 1.5 g. In this MFR, 11.32 x MFR ^-0.7854 is 3.19, and 3.
45 × MFR ^{-0 .7749} was 0.99. Therefore, MT =
It turns out that 1.5 is between 0.99 and 3.19.

Example 4 In Example 1, a propylene-ethylene-butene random copolymer having an MFR of 5.1 g / 10 minutes (ethylene content: 3.
5% by weight, butene content: 6% by weight, propylene content: 90.5% by weight, melting main peak temperature 131 ° C., auxiliary peak temperature 97 ° C., weight average molecular weight 390,000 (in terms of homo PP) 100 parts by weight Except for blending 12 parts by weight of Montelu's high melt strength polypropylene PF814 (mainly isotactic semi-crystalline polypropylene homopolymer with a branching index of 0.32 and no gel with strain hardening elongational viscosity) 80μ with T-die at 250 ℃
It was laminated on a printed film with a thickness of m. Table 2 shows the evaluation results. The MFR of the blended resin is 4.9 g
/ 10 minutes and the MT was 2.2 g. In this MFR, 11.32 x MFR ^-0.7854 is 3.24, and 3.45 x MFR
MFR ^{-0.7 749} was 1.00. Therefore, MT = 2.2
Is between 1.00 and 3.24.

Comparative Example 1 A propylene-ethylene-butene copolymer was converted to propylene-
Ethylene-butene random copolymer (ethylene content:
3% by weight, butene content: 5.5% by weight, propylene content: 84.5% by weight, weight average molecular weight: 550,000 (converted to homo PP), temperature of main peak of melting: 147 ° C)
Performed in the same manner as in Example 1. The propylene used was
FIG. 3 shows a DSC thermogram of the ethylene-butene copolymer.
Shown in In addition, Table 1 shows the evaluation results of the obtained laminate. Comparative Example 2 The same procedure was performed as in Example 1 except that no benzotriazole-based ultraviolet absorber was used. Table 1 shows the evaluation results of the obtained laminate.

[0028]

[Table 1] Table 1 Evaluation Example 1 Example 2 Comparative Example 1 Comparative Example 2 Secondary workability Good Good Bad Good Weatherability 2000 or more 2000 or more 2000 or more and 300 or less (time) Whitening resistance Good Good Whitening Good

[0029]

Table 2 Evaluation items Example 3 Example 4 MFR g / 10 min of blend resin 5.0 4.9 Melt tension (MT) g 1.5 2.2 Weather resistance (time) 2000 or more 2000 or more 2000 Whitening resistance Good Good Drawdown property m / Min 60 54

[0030]

According to the present invention, it is possible to obtain a propylene-based resin film which is excellent in weather resistance and whitening resistance, has an improved extrusion unevenness phenomenon by extrusion molding at a high speed, and has excellent secondary workability. Can be

[Brief description of the drawings]

FIG. 1 shows D of a propylene-α-olefin copolymer used in the propylene resin films of Examples 1, 3 and 4.
SC thermogram.

FIG. 2 is a DSC thermogram of a propylene-α-olefin copolymer used in a propylene-based resin film of Example 2.

FIG. 3 is a DSC thermogram of a propylene-α-olefin copolymer used in a propylene-based resin film of Comparative Example 1.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08K 5/3475 C08K 5/3475 C08L 23/16 C08L 23/16 (72) Inventor Yukihiro Kukunaga 2-3-2 Yakko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture. (72) Inventor Yutaka Yokoyama, Oita City, Oita Prefecture, Oita, Japan

Claims (5)

[Claims] 1. A thermogram containing not less than 70% by weight of propylene and measured by a differential scanning calorimeter.
Propylene-α-olefin copolymer 100 in which a peak is observed at ~ 140 ° C and at least one sub-peak and / or inflection point is observed between 30 ° C and said peak.
A propylene-based resin film obtained by adding 0.05 to 1.5 parts by weight of a benzotriazole-based ultraviolet absorber and / or a benzophenone-based ultraviolet absorber and 0.1 to 1.0 part by weight of a hindered amine light stabilizer with respect to parts by weight. . 2. The propylene resin film according to claim 1, further comprising 2 to 25 parts by weight of a high melt strength polypropylene based on 100 parts by weight of the propylene-α-olefin copolymer. 3. The melt tension (MT) at 230 ° C. is 1.0 to 10 g.
And the relationship between MFR and MT is 3.45 × MFR ^−0.7749 ≦
^3. The propylene-based resin film according to claim 1, ^wherein MT ≦ 11.32 × MFR− ^0.7854 . 4. The method according to claim 1, wherein the thickness is 5 to 400 μm.
A propylene-based resin film according to any one of the above. 5. The propylene resin film according to claim 1, wherein the surface of the propylene resin film is embossed.