KR20100085157A - Propylene resin composition for stretched sheet, and stretched sheet and thermally molded article each comprising the composition - Google Patents
Propylene resin composition for stretched sheet, and stretched sheet and thermally molded article each comprising the composition Download PDFInfo
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- KR20100085157A KR20100085157A KR1020107012183A KR20107012183A KR20100085157A KR 20100085157 A KR20100085157 A KR 20100085157A KR 1020107012183 A KR1020107012183 A KR 1020107012183A KR 20107012183 A KR20107012183 A KR 20107012183A KR 20100085157 A KR20100085157 A KR 20100085157A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
Abstract
Description
The present invention relates to a propylene resin composition for a stretched sheet, a stretched sheet and a thermoformed product containing the resin composition.
High-transparent sheets are widely used as packaging materials for food, medical devices, pharmaceuticals, electronic parts, stationery, sundries, and the like. As a raw material, biaxially stretched polystyrene (OPS) sheet, polyvinyl chloride (PVC) sheet, amorphous polyethylene terephthalate (A-PET) sheet, etc. are many because of transparency, rigidity, and secondary moldability (thermoforming).
In recent years, the replacement with polypropylene sheet is advanced from the viewpoint of environmental protection, heat resistance, oil resistance, low specific gravity, and the like.
Since polypropylene is crystalline, it becomes a semitransparent sheet as it is. Therefore, a method of adding a nucleating agent is known as a general technique for improving transparency and rigidity (for example, described in Japanese Patent Laid-Open No. 2002-284942). However, the rigidity (room temperature) and transparency are also insufficient in the above method, so that the replacement of the polypropylene sheet is limited to some applications.
By the way, it is known that polypropylene improves physical properties, such as rigidity and transparency by extending | stretching.
The draw ratio of the biaxially stretched polypropylene film, which is well known as BOPP, is usually performed at a high magnification of about vertical x horizontal = 5 x 10 times. In order to obtain the sheet thickness (0.1-1mm) aimed at by this invention by such high magnification | stretching, it is necessary to make the sheet (disk) thickness before extending | stretching into 5-50 mm (BOPP is usually 1-3 mm). When it becomes such a thick disk, it is difficult to shape a disk and it cannot be extended | stretched with a current installation. And when a disk is made into thickness and low magnification extending | stretching normally, since extending | stretching nonuniformity (thickness nonuniformity) by necking becomes easy to produce, it is difficult to obtain the target sheet thickness.
In the case of uniaxial stretching, even if it is low magnification stretching, the stretching nonuniformity is smaller than the above method, and it is relatively easy to obtain the target sheet thickness, but the stretching ratio needs to be suppressed to 3 times or less due to thermoforming, so that the rigidity is high. And sheet physical properties such as transparency are insufficient (for example, Japanese Patent Application Laid-Open No. 53-94371 and Japanese Patent Application Laid-open No. 53-128673). In addition, a method of uniaxial stretching by combining a special disk quenching method is also known (for example, Japanese Patent Application Laid-Open No. 63-16256, Japanese Patent Application Laid-open No. 63-62377). It is difficult to say, and it is not preferable because equipment cost (manufacturing cost) becomes expensive.
The present invention is to solve the problems according to the prior art as described above, without being limited by stretching methods such as uniaxial stretching, biaxial stretching, disk cooling, and draw ratio, and also excellent stiffness, heat resistance rigidity, transparency, An object of the present invention is to provide a propylene-based resin composition for a stretched sheet having uniform stretchability and thermoformability, and a stretched sheet and a thermoformed body containing the resin composition.
MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the resin composition with a wide composition distribution which combined the propylene-type resin of a specific range of melting | fusing point can be extended | stretched without being restrict | limited by an extending | stretching method, and this resin composition The stretched sheet containing found that the balance of rigidity, heat resistance rigidity, transparency, uniform stretchability, and thermoformability was very good, and came to complete this invention.
That is, this invention is specified by the matter described below.
(1) 10 to 90% by weight of a high melting point propylene resin (A ') having a melting point of 156 to 170 DEG C measured by DSC and at least one low melting point propylene resin having a melting point of 70 to 155 DEG C measured by DSC; (A ") 10-90 weight% (However, the sum total of A 'and A" is 100 weight%), Comprising: The propylene resin for stretched sheet which simultaneously satisfy | fills the requirements of following [1]-[4]. Composition (A).
[1] The MFR (230 ° C., 2.16 kg load) is 0.5 to 10.0 g / 10 min.
[2] The melting point, measured by DSC, is 150 to 170 ° C.
[3] The α-olefin comonomer content is 1 to 11 mol% in the propylene resin composition (A) for the stretched sheet.
[4] Contains nucleated components.
(2) α-olefin comonomer content of the high melting point propylene resin (A ') is 0 to 1.5 mol%, and α-olefin comonomer content of the low melting propylene resin (A ") is 1.6 to 24 mol% ( Propylene-based resin composition (A) for the stretched sheet according to 1).
(3) The single | mono layer sheet (B1) which extended | stretched the propylene resin composition (A) for extending | stretching sheet as described in (1) or (2) at least in 1 axial direction.
(4) The multilayer sheet (B2) using the propylene resin composition (A) for the stretched sheet according to (1) or (2) in at least one of the uppermost layer and the lowermost layer, wherein the multilayer sheet is stretched in at least one axial direction In addition, the melting point (Tm1) of the uppermost layer and the melting point (Tm2) of the lowermost layer of the multilayer sheet
1 ≤ Tm2-Tm1 ≤ 100 (℃)
The multilayer sheet (B2) which satisfies the relationship of.
(5) Resin which comprises the uppermost layer of a multilayer sheet (B2 ') as a multilayer sheet (B2') which used the propylene resin composition (A) for extending | stretching sheet as described in (1) or (2) for both an uppermost layer and a lowermost layer. Α-olefin comonomer content (C1) of the composition and the α-olefin comonomer content (C2) of the resin composition constituting the lowest layer
C1> C2
The multilayer sheet (B2 ') which satisfies the relationship.
(6) A thermoformed product obtained by thermoforming the single layer sheet (B1) according to (3).
(7) A thermoformed product obtained by thermoforming the multilayer sheet (B2) described in (4) or the multilayer sheet (B2 ') described in (5).
(8) A thermoform used as a material for packaging contents of food, medical instruments, medicines, electronic parts, stationery, sundries, etc., wherein the uppermost layer of the multilayer sheet (B2) or (B2 ') is the outer surface side with respect to the contents. The thermoform as described in (7) obtained by thermoforming so that it may become.
The single layer and multilayer stretched sheets containing the propylene resin composition (A) for stretched sheet of the present invention have a very good balance of rigidity, heat resistance rigidity, transparency, uniform stretchability, and thermoforming. And the thermoformed body obtained from this single | mono layer and a multilayer stretched sheet has the characteristic of high rigidity, heat resistance rigidity, transparency, oil resistance, etc., and low specific gravity. Moreover, since the thermoformed body obtained from this multilayer stretched sheet has little post-shrinkage after shaping | molding, and small deformation, it is excellent in shape stability. For this reason, the single layer and multilayer stretched sheets containing the propylene-based resin composition (A) for stretched sheet of the present invention can be widely used as packaging materials for food, medical instruments, pharmaceuticals, electronic parts, stationery, sundries, and the like.
The propylene resin composition (A) for the stretched sheet of the present invention comprises a high melting point propylene resin (A ') and at least one or more low melting point propylene resin (A ").
High melting point propylene resin (A ')
As for the high melting point propylene resin (A '), melting | fusing point (Tm) measured by DSC is 156-170 degreeC, Preferably it is 160-170 degreeC, More preferably, it exists in the range of 163-170 degreeC. When Tm exists in this range, the stretched sheet containing the propylene resin composition (A) of this invention is excellent in rigidity and heat resistance rigidity.
The high melting point propylene resin (A ') is a polymer containing propylene as a structural unit, and is a random copolymer of propylene homopolymer to propylene and ethylene or an alpha -olefin (α-olefin comonomer) having 4 to 20 carbon atoms. . Here, as the alpha olefin having 4 to 20 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetra Decene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. In these, ethylene or the C4-10 alpha-olefin is preferable. The content of the α-olefin comonomer is 0 to 1.5 mol%, preferably 0 to 1.2 mol%, more preferably 0 to 0.6 mol% in the high melting point propylene resin (A ′).
Further, a preferred embodiment of the high melting point propylene resin (A ') has a melt flow rate (MFR) (230 ° C., 2.16 kg load) in the range of 0.3 to 15.0 g / 10 min, more preferably 0.6 to 9.0 g / 10 min. . If MFR exists in this range, the extrusion property of a disk is excellent.
Furthermore, the preferred embodiment of the high melting point propylene-based resin (A ') is 0.960 in which the value of the stereoregularity index [M 5 ] obtained by the following equation (1) from the absorption strength of Pmmmm and Pw in the 13 C-NMR spectrum is 0.960. To 0.990, more preferably 0.970 to 0.990. When the stereoregularity index [M 5 ] is in this range, the rigidity and heat resistance rigidity of the stretched sheet are excellent.
(Wherein, [Pmmmm] represents the absorption strength derived from the methyl group of the 3rd unit in the site | part where the propylene unit is isotactic-bonded continuously 5 units, [Pw] is the absorption derived from the methyl group of a propylene unit) Strength)
The manufacturing method of such a high melting point propylene resin (A ') is the method described in Unexamined-Japanese-Patent No. 2-84404, Unexamined-Japanese-Patent No. 2-229807, Unexamined-Japanese-Patent No. 3-7703, etc., for example. It is available.
Low melting point propylene resin (A ")
The low melting point propylene-based resin (A ″) has a Tm in the range of 70 to 155 ° C., preferably 70 to 150 ° C., more preferably 78 to 148 ° C. If Tm is in this range, the propylene system of the present invention The stretched sheet containing the resin composition (A) is excellent in transparency, uniform stretchability and thermoformability.
The low melting point propylene resin (A ") is a polymer containing propylene as a structural unit, and is a random copolymer of propylene and ethylene or an alpha -olefin (α-olefin comonomer) having 4 to 20 carbon atoms. As alpha-olefin which is 4-20, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1- Hexadecene, 1-octadecene, 1-eicosene, etc. Among these, ethylene or α-olefin having 4 to 10 carbon atoms is preferable.The content of the α-olefin comonomer is a low melting point propylene resin ( A ") in the range 1.6 to 24 mol%, preferably 3.0 to 24 mol%, more preferably 3.7 to 24 mol%.
Further, a preferred embodiment of the low melting point propylene resin (A ″) has a MFR (230 ° C., 2.16 kg load) of 0.3 to 15.0 g / 10 min, more preferably 0.6 to 9.0 g / 10 min. If it exists in the range, the extrusion property of a disk will be excellent.
Such a low melting point propylene-based resin (A ″) can be produced by Tm of 130 ° C. or higher, but can also be produced by the high melting point propylene-based resin (A ′). On the other hand, the method of using a metallocene catalyst is particularly preferable as a method of producing a low melting point propylene-based resin (A ″), since the amount of atactic polypropylene can be suppressed. For example, the methods described in WO 01/027124, Japanese Patent Application Laid-Open No. 2002-275282, Japanese Patent Application Laid-Open No. 2002-275330, Japanese Patent Application Laid-Open No. 2002-275331, Japanese Patent Application Laid-Open No. 2002-275332, etc. can be used. Can be.
Propylene-based resin composition (A) for stretched sheet
The propylene resin composition (A) for stretched sheet of this invention is a resin composition which combined the high melting point propylene resin (A ') and at least 1 type or more low melting point propylene resin (A "). The composition ratio is 10 to 90% by weight of the high melting point propylene resin (A ') in the resin composition (A), preferably 20 to 80% by weight, and at least one or more low melting point propylene resins (A ") (When it is 2 or more types, it is 10 to 90 weight%, Preferably it is 20 to 80 weight% as total amount of resin (A ").
The propylene resin composition (A) for the stretched sheet of the present invention has an MFR (230 ° C., 2.16 kg load) of 0.5 to 10.0 g / 10 min, preferably 1.0 to 5.0 g / 10 min, and a Tm of 150 to 170. C, preferably in the range of 155 to 170 ° C, more preferably 158 to 170 ° C, and the α-olefin comonomer content is in the range of 1.0 to 11 mol%, preferably 1.5 to 8 mol% in the resin composition (A). And also contains nucleating components.
The propylene resin composition (A) for stretched sheet of this invention can be manufactured by multistage superposition | polymerization. For example, in two or more stages of polymerization tanks connected in series, it is preferable to produce a high melting point propylene resin (A ') at the front end and to continuously produce a low melting point propylene resin (A ") at the rear end. It is possible.
In addition, in addition to the above, the high melting point propylene resin (A ') and the low melting point propylene resin (A ") prepared separately are melt-kneaded using a single screw extruder, a multi-screw extruder, a kneader, or a Banbury mixer, etc. It is also possible to obtain a composition (A), and also to provide the resin directly to a sheet molding machine.
Nucleus
As a nucleation component contained in the propylene resin composition (A) for stretched sheets of this invention, a well-known nucleating agent can be used without a restriction. Examples thereof include sorbitol compounds, phosphate compounds, aliphatic dicarboxylic acids having 4 to 12 carbon atoms and metal salts thereof, aromatic carboxylic acids and metal salts thereof, rosin acid metal salt compounds, magnesium silicate (talc), and the like. Moreover, the polypropylene (polymer nucleating agent) obtained by prepolymerizing the reactive monomer used as a nucleus component in a polypropylene polymerization catalyst, and then superposing | polymerizing propylene is also contained in a nucleus component. Of these nucleating components, the polymer nucleating agent is preferable because of its high compatibility and nucleating effect and very little contamination with the sheet molding machine or the thermoforming machine.
As a reactive monomer used in the prepolymerization of the said polymer nucleating agent, 3-methyl-1- butene, 3-methyl-1- pentene, 4-methyl-1- pentene, 4-methyl-1- hexene, 4, 4- di Methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, allyl naphthalene, allyl norbornene, styrene, dimethyl styrene, vinyl Naphthalene, allyl toluene, allyl benzene, vinyl cyclohexane, vinyl cyclopentane, vinyl cycloheptane, allyl trialkylsilane, etc. are mentioned.
As the method for producing the polymer nucleating agent, the method described in JP-A 4-202505, JP-A 4-202506, JP-A 4-202510 and the like can be used.
These nucleating components are 0.001 to 0.5 parts by weight, preferably 0.0018 to 0.3 parts by weight with respect to 100 parts by weight of the propylene resin composition (A) for the stretched sheet.
additive
When forming a stretched sheet using the propylene resin composition (A) for stretched sheet of this invention as a raw material, it is an antioxidant, a light stabilizer, a ultraviolet absorber, a metal soap, a hydrochloric acid absorber, and a lubricating agent in the range which does not deviate from the objective of this invention. Additives, such as an antistatic agent, an antifogging agent, and an antiblocking agent, may be added.
Although the addition amount of these additives changes with kinds, what is necessary is just a range which does not impair the objective of this invention, and it is 3 weight part or less with respect to 100 weight part of propylene resin compositions (A) for stretched sheets normally.
Stretched Sheets and Thermoforms
The sheet containing the propylene resin composition (A) for the stretched sheet of the present invention and drawn in at least one axial direction has a very good balance between rigidity, heat resistance rigidity, transparency, uniform stretchability, and thermoformability.
The stretched sheet of this invention is obtained by a well-known manufacturing method, For example, the said propylene resin composition (A) for stretched sheets is supplied to an extruder (in the case of multiple layers, it uses several extruders), and resin temperature is 190- Adjusted to 280 ° C., extruded from the T die attached to the extruder tip (in the case of multiple layers just before or after joining in the T die), withdrawn by a chill roll adjusted to a temperature of 20 to 80 ° C. Mold. Further, reheated with a preheat roll adjusted to a temperature of 130 to 160 ° C, roll drawn at a draw ratio of 2 to 5 times in the longitudinal direction, and 0 to 10% relaxation with an annealing roll adjusted to a temperature of 100 to 160 ° C. It can be obtained by winding up while.
The stretching method is not limited, and in addition to the longitudinal uniaxial stretching, the uniaxial stretching may be performed in the transverse direction with a tenter, or the sequential biaxial stretching in the transverse direction with a tenter after the longitudinal uniaxial stretching. Stretching or simultaneous biaxial stretching may be performed simultaneously in the longitudinal and horizontal directions only with the tenter.
The preferable draw ratio at the time of manufacturing the extending | stretching sheet of this invention is 2 to 6 times, more preferably 3 to 5 times in the case of uniaxial stretching, and 2 to 6 times each in length / width in the case of biaxial stretching. More preferably, it is 3 to 5 times of range.
The stretched sheet of the present invention is a single layer sheet (B1) made of a propylene resin composition (A) for a stretched sheet, or a multilayer sheet (B2) of two or more layers containing the resin composition (A).
Usually, a polypropylene stretched sheet is characterized by shrinkage because molecular chains strained by stretching are alleviated by heat. Since the glass transition temperature (Tg) of polypropylene is 0 degrees C or less, it shrinks gradually even at normal temperature (post-shrinkage). The thermoformed product, which is secondary processed by thermoforming such as hot plate molding or vacuum press molding, may be post-shrunk and deformed by storage in summer (high temperature) or long term storage (containers, etc.). In the case of a shape having a rectangular shape, deformation of the edge of the thermoformed body is likely to be reversed to the outer side with respect to the original state). Since it is the same also in the thermoformed body which consists of the single | mono layer sheet B1 of this invention, the shape, storage method, etc. of a thermoformed body are restrict | limited to some extent.
On the other hand, since the said deformation | transformation is very small in the thermoformed body which consists of the multilayer sheet (B2) of this invention, restrictions, such as a shape and a storage method, can be eliminated or alleviated.
The multilayer sheet (B2) of this invention uses the propylene resin composition (A) for extending | stretching sheet of this invention at least in any one of an uppermost layer or a lowermost layer, The polypropylene which has a melting | fusing point lower than a lowermost layer in the uppermost layer, Preferably the stretched sheet Propylene-based resin composition (A) is used. At this time, melting | fusing point difference ((DELTA) Tm) of lowermost layer (both outermost layer) is 1-100 degreeC, Preferably it is 3-30 degreeC, More preferably, it is 3-15 degreeC. That is, the melting point Tm1 of the uppermost layer of the multilayer sheet and the melting point Tm2 of the lowermost layer satisfy the relationship of (I), preferably the relationship of (II), and more preferably the relationship of (III). It is important to design the layer configuration to meet the requirements.
(I) 1 ≤ Tm2-Tm1 ≤ 100 (° C)
(II) 3 ≤ Tm2-Tm1 ≤ 30 (℃)
(III) 3 ≤ Tm2-Tm1 ≤ 15 (° C)
In addition, the multi-layered sheet (B2 ') of this invention uses the propylene resin composition (A) for extending | stretching sheet of this invention for both the uppermost layer and the lowermost layer, and (alpha) -olefin comonomer content (C1) of the resin composition which comprises an uppermost layer. ) And the α-olefin comonomer content (C2) of the resin composition constituting the lowest layer
It is important to satisfy the relationship C1> C2.
Further, when thermoforming the multilayer sheet, deformation is caused by post-shrinkage by molding the sheet so that the top layer (low Tm) is on the outer surface side of the thermoformed body and the bottom layer (high Tm) on the inner surface side. It becomes possible.
That is, when thermoforming the multilayer sheet of this invention which has the above structure, the uppermost layer (low Tm side) of the multilayer sheet B2 or (B2 ') becomes an outer surface side with respect to a content, and the lowest layer (high Tm side). ), And according to another expression, the uppermost layer (lower Tm side) of the multilayer sheet (B2) or (B2 ') is the lowermost layer (higher Tm side) outside the convex surface of the shape of the thermoformed body. By shaping the sheet in a direction adjacent to the inside of the concave surface, it becomes possible to suppress deformation due to post-shrinkage.
In addition, when thermoforming the multilayer sheet B2 'of this invention which has the above structure, the uppermost layer (C1 side) of the multilayer sheet B2' becomes an outer surface side with respect to a content, and the lowermost layer (C2 side) According to another expression, the sheet is such that the uppermost layer (C1 side) of the multilayer sheet B2 'is adjacent to the convex surface outside of the shape of the thermoformed body and the lowermost layer (C2 side) is adjacent to the inside of the concave surface. Also by molding in the direction of, it is possible to suppress deformation caused by post-shrinkage.
Usually, extending | stretching of polypropylene is performed in the temperature range of crystallization temperature (Tc) or more and Tm or less. The amount of post-shrinkage of the stretched sheet depends on the stretching temperature, and the lower the stretching temperature (near Tc) is, the larger the post-shrinkage amount is, and the higher the stretching temperature (near Tm) tends to be smaller. Therefore, the thermoformed body made of the multilayer sheet B2 has the uppermost layer (low Tm) on the outer surface side of the thermoformed body and the lowermost layer (high Tm) on the inner surface side, so that the outer surface side is closer to Tm than the inner surface side. By stretching at, the deformation is very small since the amount of post-shrinkage on the outer surface side of the thermoformed body becomes smaller than the inner surface side. In addition, since the post-shrinkage amount of the inner and outer surfaces can be arbitrarily controlled by adjusting the melting point difference ΔTm, the layer thickness ratio, the stretching temperature and the like of the multilayer sheet, it is possible to cope with various shapes.
The multilayer sheet (B2) of this invention can add further value by combining another resin with an intermediate | middle layer in the range which does not deviate from the objective of this invention. For example, when an ethylene vinyl alcohol copolymer is used for an intermediate | middle layer, the improvement of oxygen and a carbon dioxide barrier property, and the use of the polypropylene resin composition containing hydrogenated petroleum resin for an intermediate | middle layer, etc. can be mentioned. In addition, as another resin used for an intermediate | middle layer, For example, polyvinyl alcohol resin, polyvinylidene chloride resin, polyacrylonitrile resin, polyamide-type resins, such as metaxylenediamine 6 and nylon 6, polyethylene terephthalate And polyester-based resins such as polybutylene terephthalate.
In addition, since the thermoformed body obtained from the stretched sheet of the present invention has high rigidity, heat resistance rigidity, transparency, oil resistance, and low specific gravity, it is widely used as a packaging material for foods, medical instruments, pharmaceuticals, electronic parts, stationery, sundries, and the like. Can be.
[Examples]
Next, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.
The measuring method of the physical property in an Example is as follows.
1) Melt Flow Rate (MFR [g / 10min])
It measured at the temperature of 230 degreeC, and 2.16 kg of loads based on ASTMD-1238. The pellet was directly injected into the cylinder and melted without introducing nitrogen in particular.
2) Melting Point (Tm [℃])
Endothermic peak which appears when DSC heated up at 10 degree-C / min from 30 degreeC to 230 degreeC, hold | maintained at 230 degreeC for 10 minutes, cooled to 10 degreeC / min to 30 degreeC, and heated up at 10 degree-C / min again The temperature was taken as melting point.
3) Isotactic pentad fraction (mmmm: [M 5 ])
The absorption intensity of Pmmmm and Pw in the 13 C-NMR spectrum was determined by Equation 1 above. However, peak attribution was performed according to the document [Polymer, 1993, Vol 34, No 14, 3129-3131].
4) Uniform elongation (thickness non-uniformity [-])
The thickness of the stretched sheet was measured at a total of 30 places at predetermined intervals, and the value obtained by dividing the standard deviation by the average thickness was used as an index of uniform stretchability (the smaller the value, the better the uniform stretchability).
5) Tensile Modulus (MPa)
Test pieces of ASTM D-638 type 4 were punched out of the sheets, and were determined from the initial gradient of the stress-strain curve when pulled out at 46 mm between the chucks, speed 50 mm / min, temperature 23 ° C. or 110 ° C.
6) Blur (HAZE [%])
It measured by TURBIDIMETER made from Nippon Denshoku Industries Co., Ltd. using the integral sphere 150φ based on JISK7361.
7) Heating Shrinkage (SH [%])
The test piece of width 10mm and length 100mm (L0) was punched from the sheet | seat, it heated for 15 minutes with the 130 degreeC air oven, the length L1 after heating was measured, and it calculated from the following formula (2).
8) Thermoforming (shaping rating [point])
Using a container model mold (dimensions: □ 90 mm, depth: 20 mm) with a hot plate molding machine, thermoforming was performed under predetermined molding conditions, and the shape (model mold shaping) of the obtained thermoform was visually evaluated at 5 out of 5 points ( The larger the value, the better the thermoformability, and a rating of 3 or more is preferable).
9) Deformation amount of thermoform (bending deformation amount [mm])
The thermoformed body was aged in a 50 ° C. air oven for 1 day to measure the warp amount of the thermoformed edge.
10) Specific gravity
It measured by the underwater substitution method based on JIS7112.
Example 1
After prepolymerization of 3-methyl-1-butene (3MB-1) as the nucleus component, high melting point propylene resin (A'-) having Tm = 167 ° C, MFR = 2g / 10min, mmmm = 0.972 To 100 parts by weight of a resin composition obtained by combining 25% by weight of a low melting propylene resin (A ″ -1) having Tm = 135 ° C. and MFR = 2 g / 10min in which 1% of 75% copolymerized propylene and 6 mol% of ethylene. 0.1 parts by weight of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane (IRGANOX 1010, manufactured by Chiba Specialty Chemicals, Inc.) as an antioxidant; 0.1 parts by weight of tris (2,4-di-t-butylphenol) phosphate (IRGAFOS 168, manufactured by Chiba Specialty Chemicals, Inc.) and 0.1 parts by weight of calcium stearate (manufactured by Nippon Yushi) as a neutralizer, It was melt-kneaded at a resin temperature of 230 ° C. and granulated into pellets by using a pellet, wherein the proportion of the nucleus component 3MB-1 polymer was It is 0.027 weight% in the paper composition The physical properties of the obtained resin composition (pellet) are shown in Tables 1 and 2.
The pellets were fed to a longitudinal uniaxially stretched sheet molding machine, extruded from a T die at a resin temperature of 250 ° C, shaped into a 1.2 mm thick disk while being taken up with a cooling roll at a temperature of 30 ° C, and reheated with a preheating roll at a temperature of 150 ° C. The film was stretched at a draw ratio of 4 times to perform roll stretching, and was annealed at a temperature of 110 ° C to obtain a longitudinal monoaxially oriented sheet having a thickness of 0.3 mm. The physical properties of the obtained sheet are shown in Tables 1 and 2.
The stretched sheet was thermoformed in a hot plate temperature range of 100 to 160 ° C by using the container model mold with a hot plate forming machine, setting a pressure of air pressure of 0.64 MPa, a vacuum degree of 0.09 MPa, a sheet heating time of 3s, and a shaping time of 3s. Among the thermoforms obtained, there was no cloudiness and the best rating was shown in Tables 1 and 2.
[Example 2]
Resin composition (3MB-1 polymer) which combined 50 weight% of high-melting-point propylene resins (A'-1) used by Example 1, and 50 weight% of low-melting-point propylene resins (A "-1) used by Example 1 The ratio of was carried out similarly to Example 1 except having used 0.018 weight%) in the resin composition, and the result is shown in Table 1.
Example 3
After prepolymerizing 3-methyl-1-butene as the nucleus component, 50 weights of high-melting-point propylene resin (A'-2) of Tm = 166 占 폚, MFR = 11 g / 10min, and mmmm = 0.972 obtained by homopolymerizing propylene. % And the low melting point propylene-based resin (A "-1) used in Example 1 50% by weight of the resin composition (The ratio of 3MB-1 polymer is 0.017 weight% in a resin composition) except having used and It carried out similarly and the result is shown in Table 1.
Example 4
50 wt% of the high melting point propylene resin (A'-2) used in Example 3, a low melting point propylene resin (A "-2 of Mm = 10 g / 10min, Tm = 135 degreeC which copolymerized propylene and 6 mol% of ethylene ) Was carried out in the same manner as in Example 1 except that the resin composition (combination of 3MB-1 polymer was 0.017% by weight in the resin composition) in which 50% by weight was combined, and the results are shown in Table 1.
Example 5
50 wt% of the high melting point propylene resin (A'-1) used in Example 1, a low melting point propylene resin (A "of Tm = 140 占 폚, MFR = 0.5 g / 10min, in which propylene and ethylene 5.4 mol% were copolymerized. -3) was carried out similarly to Example 1 except having used the resin composition which combined 50 weight% (the ratio of 3MB-1 polymer is 0.018 weight% in a resin composition), and the result is shown in Table 1.
Example 6
Low-melting-point propylene-based resin (A "used 40% by weight of the high-melting-point propylene-based resin (A'-3) of Tm = 165 degreeC, MFR = 0.5g / 10min, mmmm = 0.979 which homopolymerized propylene. -3) and 50% by weight of the resin composition (10% by weight of the propylene-based resin (A'-1) used in Example 1 as the nucleation component (combination of 3MB-1 polymer is 0.0036% by weight in the resin composition)) Except having used, it carried out similarly to Example 1 and shows the result in Table 1.
Example 7
25 wt% of the high melting point propylene resin (A'-1) used in Example 1, a low melting point propylene resin (A " Resin composition 100 consisting of 25% by weight of ultra-low melting point propylene-based resin (A "-5) having Tm = 78 ° C and MFR = 7 g / 10min in which 50% by weight of 4) and 23.5 mol% of propylene and 1-butene were copolymerized. Per parts by weight, further, as a nucleating agent, bis [2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxafoss Fossin-6-oxide] It was melt kneaded in the same manner as in Example 1 except that a resin composition obtained by combining 0.13 parts by weight of aluminum hydroxide salt (NA-21, manufactured by ADEKA Corporation) was assembled into pellets (3MB-1). The proportion of the polymer is 0.009% by weight in the resin composition). In addition, except that the pellet was supplied to a sheet molding machine and the preheat roll temperature was changed to 130 ° C., the stretched sheet was molded in the same manner as in Example 1, and the results are shown in Table 1.
Comparative Example 1
From the resin composition used in Example 1, except for the low melting point propylene resin (A ''-1), only the high melting point propylene resin (A'-1) was 100% by weight (the ratio of the 3MB-1 polymer was 0.036% in the resin). Except having made into%), it carried out similarly to Example 1, and shows the result in Table 1.
Comparative Example 2
The high melting point propylene resin (A'-3) was 50% by weight, except for the nucleation component (A'-1) from the resin composition used in Example 6, and the low melting point propylene resin (A "-3) was obtained. Except having set it as the resin composition which combined 50 weight%, it carried out similarly to Example 1, and shows the result in Table 1.
Comparative Example 3
100% by weight of the low melting point propylene resin (A ″ -4) except for the high melting point propylene resin (A′-1) and the ultra low melting point propylene resin (A ″ -5) from the resin composition used in Example 7. It carried out similarly to Example 7 except having set it as the resin composition which combined only 0.13 weight part of nucleating agents (NA-21), and the result is shown in Table 1.
[Comparative Example 4]
50% by weight of the propylene-based resin (A'-1) used in Example 1 and 50% by weight of the ultra-low melting propylene-based resin (A "-5) used in Example 7 (ratio of 3MB-1 polymer) Except having used 0.018 weight% in silver resin compositions, it carried out similarly to Example 7 and showed the result in Table 1.
Example 8
The pellets obtained in Example 1 were fed to a sequential biaxially stretched sheet molding machine, extruded from a T die at a resin temperature of 250 ° C., and a disk of 1.8 mm in thickness was formed while being taken out with a cooling roll at a temperature of 30 ° C., and preheated at a temperature of 150 ° C. After reheating with a roll, stretching is performed at a draw ratio of 3 times, followed by feeding to a tenter, stretching to a stretching temperature of 155 ° C., and stretching at 3 times, and stretching at a transverse ratio. A sequential biaxially oriented sheet of mm was obtained. The physical properties of the obtained sheet are shown in Table 2.
Example 9
In Example 8, the raw material of 3.0 mm thick was shape | molded, and it carried out similarly to Example 8 except having changed the lateral stretch to 5 times, and the result is shown in Table 2.
Example 10
The disc of 1.8 mm in thickness obtained in Example 8 was cut into a size of □ 85 mm, and simultaneous biaxial stretching was performed using a table-type biaxial stretching machine with a stretching temperature of 155 占 폚 and a stretching ratio of vertical x horizontal = 3 x 3 times. And annealing while relaxing 5% in width at a temperature of 160 ° C to obtain a simultaneous biaxially stretched sheet having a thickness of 0.2 mm. The physical properties of the obtained sheet are shown in Table 2.
[Comparative Example 5]
The pellet obtained in Example 1 was supplied to the sheet molding machine, and it was extruded from the T die at resin temperature of 250 degreeC, and was taken out by the cooling roll of temperature 30 degreeC, and obtained the unstretched sheet of thickness 0.3mm. The physical properties of the obtained sheet are shown in Table 2.
Example 11
In the upper layer (low melting point layer), 20 weight% of high-melting-point propylene resin (A'-1) used by Example 1 was copolymerized with 6 mol% of propylene and ethylene, and the talc was used for the multilayer sheet molding machine which has two series of extruders. Using a resin composition (assembly was carried out in the same manner as in Example 1) in which 0.03 parts by weight of Tm = 139 ° C. and 80% by weight of low melting point propylene resin (A ″ -6) having a MFR of 3 g / 10 min. 50% by weight of the high melting point propylene resin (A′-1) and 50% by weight of the low melting point propylene resin (A ″ -6) in the lower layer. It became 0.0072 weight% in the composition, and granulation was carried out using the disk of two kinds of two layers (layer thickness ratio upper layer: lower layer = 1: 2) of 1.2 mm in total thickness using the same thickness as Example 1. Furthermore, similarly to Example 1, the longitudinal uniaxial stretched sheet having a thickness of 0.3 mm was molded by roll stretching to obtain a thermoform of this sheet. The physical properties measured about the obtained sheet and the thermoformed body are shown in Table 3.
Example 12
In Example 11, it carried out similarly to Example 11 except having changed the layer thickness ratio into upper layer: lower layer = 1: 4, and the result is shown in Table 3.
Example 13
In Example 11, 5 weight% of the high melting point propylene resin (A'-1) used in Example 1 and 95 weight% of the low melting point propylene resin (A "-6) were used for the upper layer (low melting point layer). Using the combined resin composition (the ratio of the 3MB-1 polymer was 0.0018% by weight in the resin composition, the granulation was carried out in the same manner as in Example 1), the layer thickness ratio was the upper layer: lower layer = 1: 1, preheat roll temperature Except having changed into 130 degreeC, it carried out similarly to Example 11, and shows the result in Table 3.
Example 14
Longitudinal uniaxial stretching (single layer sheet) was performed similarly to Example 1 with the resin composition used for the lower layer in Example 11, and the result is shown in Table 3.
[Comparative Example 6]
At present, the physical properties of the non-stretched polypropylene (PP) sheet (thickness 0.3 mm) used in the cover material of a food container etc. are shown in Table 3.
Comparative Example 7
At present, the physical properties of the biaxially stretched polystyrene sheet (OPS sheet) (thickness of 0.25 mm) used in the cover material of a lunch box container, etc. are shown in Table 3.
Industrial Applicability
The stretched sheet containing the propylene-based resin composition (A) for the stretched sheet of the present invention has a very good balance of rigidity, heat resistance rigidity, transparency, uniform stretchability, and thermoformability, and the thermoformed body obtained from the stretched sheet is rigid. Since it has high heat resistance, transparency, oil resistance, and low specific gravity, it can be widely used as a packaging material for food, medical equipment, pharmaceuticals, electronic parts, stationery, sundries, and the like.
Claims (8)
10 to 90% by weight of at least one or more low melting point propylene-based resin (A ″) having a melting point of 70 to 155 ° C. as measured by DSC, provided that the sum of A ′ and A ″ is 100% by weight;
The propylene resin composition (A) for stretched sheet | seat which satisfy | fills the requirements of following [1]-[4].
[1] The melt flow rate (230 ° C., 2.16 kg load) is 0.5 to 10.0 g / 10 min.
[2] The melting point, measured by DSC, is 150 to 170 ° C.
[3] The α-olefin comonomer content is 1 to 11 mol% in the propylene resin composition (A) for the stretched sheet.
[4] Contains nucleated components.
The α-olefin comonomer content of the high melting point propylene resin (A ′) is 0 to 1.5 mol%, and the α-olefin comonomer content of the low melting propylene resin (A ″) is 1.6 to 24 mol%. Propylene-based resin composition (A) for drawn sheet.
The multilayer sheet is stretched in at least one axial direction, and
The melting point (Tm1) of the uppermost layer and the melting point (Tm2) of the lowermost layer of the multilayer sheet
1 ≤ Tm2-Tm1 ≤ 100 (℃)
The multilayer sheet (B2) characterized by satisfying the relationship of.
C1> C2
The multilayer sheet (B2 ') characterized by satisfying the relationship of.
A thermoform used as a material for packaging contents of foods, medical instruments, medicines, electronic parts, stationery, sundries, etc., wherein the uppermost layer of the multilayer sheet (B2) or (B2 ') is heated to the outer surface side with respect to the contents. A thermoformed product obtained by molding.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007294625 | 2007-11-13 | ||
| JPJP-P-2007-294625 | 2007-11-13 |
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| KR1020107012183A KR20100085157A (en) | 2007-11-13 | 2008-11-10 | Propylene resin composition for stretched sheet, and stretched sheet and thermally molded article each comprising the composition |
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| Country | Link |
|---|---|
| JP (2) | JPWO2009063819A1 (en) |
| KR (1) | KR20100085157A (en) |
| CN (1) | CN101855289A (en) |
| TW (1) | TW200932803A (en) |
| WO (1) | WO2009063819A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPWO2009063819A1 (en) * | 2007-11-13 | 2011-03-31 | 株式会社プライムポリマー | Propylene-based resin composition for stretched sheet, stretched sheet and thermoformed body containing the composition |
| TWI621630B (en) * | 2013-02-28 | 2018-04-21 | Sumitomo Chemical Co | Polypropylene resin composition, and sheet and film thereof |
| KR101820613B1 (en) | 2013-08-14 | 2018-01-19 | 보레알리스 아게 | Propylene composition with improved impact resistance at low temperature |
| JP2016528368A (en) | 2013-08-21 | 2016-09-15 | ボレアリス・アクチェンゲゼルシャフトＢｏｒｅａｌｉｓ Ａｇ | High flow polyolefin composition having high rigidity and toughness |
| KR20160043014A (en) | 2013-08-21 | 2016-04-20 | 보레알리스 아게 | High flow polyolefin composition with high stiffness and toughness |
| PL2853563T3 (en) | 2013-09-27 | 2016-12-30 | Films suitable for BOPP processing from polymers with high XS and high Tm | |
| ES2568615T3 (en) | 2013-10-11 | 2016-05-03 | Borealis Ag | Label film oriented in the machine direction |
| EP2865713B1 (en) | 2013-10-24 | 2016-04-20 | Borealis AG | Blow molded article based on bimodal random copolymer |
| ES2661108T3 (en) | 2013-10-24 | 2018-03-27 | Borealis Ag | Low melting polypropylene homopolymer with high regioerror content and high molecular weight |
| EP3063185B9 (en) | 2013-10-29 | 2017-11-15 | Borealis AG | Solid single site catalysts with high polymerisation activity |
| EP3071606B1 (en) | 2013-11-22 | 2017-08-16 | Borealis AG | Low emission propylene homopolymer with high melt flow |
| EP3077426B1 (en) | 2013-12-04 | 2022-10-05 | Borealis AG | Phthalate-free pp homopolymers for meltblown fibers |
| WO2015091839A1 (en) | 2013-12-18 | 2015-06-25 | Borealis Ag | Bopp film with improved stiffness/toughness balance |
| WO2015107020A1 (en) | 2014-01-17 | 2015-07-23 | Borealis Ag | Process for preparing propylene/1-butene copolymers |
| JP6474417B2 (en) | 2014-02-06 | 2019-02-27 | ボレアリス エージー | Soft and transparent impact copolymers |
| JP2017508032A (en) | 2014-02-06 | 2017-03-23 | ボレアリス エージー | Soft copolymer with high impact strength |
| EP2907841A1 (en) | 2014-02-14 | 2015-08-19 | Borealis AG | Polypropylene composite |
| EP2947118B1 (en) | 2014-05-20 | 2017-11-29 | Borealis AG | Polypropylene composition for automotive interior applications |
| JP6365084B2 (en) * | 2014-08-04 | 2018-08-01 | 日本ポリプロ株式会社 | Propylene polymer composition and thermoformed article using the same |
| JP6386874B2 (en) * | 2014-10-24 | 2018-09-05 | 出光興産株式会社 | Polyolefin composition, polyolefin stretched film, and method for producing stretched film |
| JP6845001B2 (en) * | 2016-12-09 | 2021-03-17 | 株式会社エフピコ | Polypropylene sheet, polypropylene sheet manufacturing method, and secondary molded product |
| JP6980588B2 (en) * | 2018-03-28 | 2021-12-15 | 株式会社エフピコ | Biaxially stretched polypropylene laminated sheet and molded body |
| JP7301504B2 (en) * | 2018-07-06 | 2023-07-03 | 三井化学東セロ株式会社 | Food packaging film and food package |
| JP7321682B2 (en) * | 2018-07-06 | 2023-08-07 | 三井化学東セロ株式会社 | Food packaging film and food package |
| JP7355591B2 (en) * | 2019-10-11 | 2023-10-03 | 三井化学株式会社 | Stretched film and its uses |
| JP7470502B2 (en) * | 2019-10-23 | 2024-04-18 | 三井化学東セロ株式会社 | Food packaging film and food packaging body |
| JP7377060B2 (en) * | 2019-10-23 | 2023-11-09 | 三井化学東セロ株式会社 | Food packaging film and food packaging |
| JP7470503B2 (en) * | 2019-10-23 | 2024-04-18 | 三井化学東セロ株式会社 | Food packaging film and food packaging body |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS58973B2 (en) * | 1978-08-17 | 1983-01-08 | 東洋製罐株式会社 | Biaxially stretched molded container with excellent shape appearance |
| JP3462303B2 (en) * | 1995-06-19 | 2003-11-05 | 花王株式会社 | Porous sheet and absorbent article using the same |
| JP3836202B2 (en) * | 1996-12-12 | 2006-10-25 | 株式会社プライムポリマー | Propylene polymer composition and molded article thereof |
| JPH11254522A (en) * | 1998-03-11 | 1999-09-21 | Tokuyama Corp | Polypropylene film |
| JP3832129B2 (en) * | 1999-02-05 | 2006-10-11 | 株式会社プライムポリマー | Polypropylene resin composition and injection molded product |
| JP2005154476A (en) * | 2003-11-20 | 2005-06-16 | Mitsui Chemicals Inc | Polypropylene resin composition and molded product therefrom |
| JP2006328300A (en) * | 2005-05-30 | 2006-12-07 | Mitsui Chemicals Inc | Polypropylene resin and its application for high transparent sheet |
| JPWO2009063819A1 (en) * | 2007-11-13 | 2011-03-31 | 株式会社プライムポリマー | Propylene-based resin composition for stretched sheet, stretched sheet and thermoformed body containing the composition |
-
2008
- 2008-11-10 JP JP2009541120A patent/JPWO2009063819A1/en active Pending
- 2008-11-10 CN CN200880115937.6A patent/CN101855289A/en active Pending
- 2008-11-10 WO PCT/JP2008/070392 patent/WO2009063819A1/en active Application Filing
- 2008-11-10 KR KR1020107012183A patent/KR20100085157A/en not_active Application Discontinuation
- 2008-11-13 TW TW97143804A patent/TW200932803A/en unknown
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Also Published As
| Publication number | Publication date |
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| TW200932803A (en) | 2009-08-01 |
| JPWO2009063819A1 (en) | 2011-03-31 |
| JP5931950B2 (en) | 2016-06-08 |
| WO2009063819A1 (en) | 2009-05-22 |
| JP2014169446A (en) | 2014-09-18 |
| CN101855289A (en) | 2010-10-06 |
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