CN101855289A - 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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- CN101855289A CN101855289A CN200880115937.6A CN200880115937A CN101855289A CN 101855289 A CN101855289 A CN 101855289A CN 200880115937 A CN200880115937 A CN 200880115937A CN 101855289 A CN101855289 A CN 101855289A
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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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
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- Containers Having Bodies Formed In One Piece (AREA)
Abstract
Disclosed are: a propylene resin composition for a stretched sheet having excellent stiffness, heat resistant stiffness, transparency, uniform stretchability and thermal moldability; and a stretched sheet and a thermally molded article, each of which comprises the resin composition. The propylene resin composition for a stretched sheet comprises 10 to 90 wt% of a high-melting-point propylene resin (A') having a melting point of 156 to 170 DEG C as measured by DSC and 10 to 90 wt% of at least one low-melting-point propylene resin (A'') having a melting point of 70 to 155 DEG C as measured by DSC (provided that the total amount of the components (A') and (A'') is defined as 100 wt%), and fulfils the following requirements [1] to [4]: [1] the propylene resin composition has a melt flow rate (230 DEG C, 2.16 kg load) of 0.5 to 10.0 g/10 min; [2] the propylene resin composition has a melting point of 150 to 170 DEG C as measured by DSC; [3] the propylene resin composition (A) contains an a-olefin comonomer at a content of 1 to 11 mol%; and [4] the propylene resin composition contains a nucleating agent.
Description
Technical field
The present invention relates to propylene resin composition for stretched sheet and the stretched sheet and the thermally molded article each that contain this resin combination.
Background technology
High clear sheet is widely used as the wrapping material of food, medicine equipment, pharmaceuticals, electronic unit, stationery, groceries etc.As raw material,, use biaxial stretch-formed polystyrene (OPS) sheet material, polyvinyl chloride (PVC) sheet material or amorphous polyethylene terephthalate (A-PET) sheet material etc. mostly from the transparency, rigidity and post forming (hot formability).
In recent years, from viewpoints such as environment protection, heat-resisting rigidity, oil-proofness and low-gravities, carrying out replacement to crystalline p p sheet.
Because polypropylene has crystallinity, so former state becomes translucent sheet material.Therefore, as the general method that the transparency and rigidity are improved, the known method (for example putting down in writing in the TOHKEMY 2002-284942 communique) that the interpolation nucleator is arranged.But even because in aforesaid method, the rigidity (normal temperature) and the transparency are also insufficient, therefore, also are defined in a part of purposes to the replacement of crystalline p p sheet.
But known polypropylene makes rerum naturas such as rigidity, the transparency improve by stretching.
The stretching ratio of the biaxial-stretched polypropylene films that is known as BOPP carries out with the high magnification about length * wide=5 * 10 times usually.In order to obtain sheet thickness (0.1～1mm) by such high magnification stretching as the object of the invention, must make sheet material (reel film) thickness before stretching is that (BOPP normally 1～3mm) for 5～50mm, if form the reel film of such thickness, then be difficult to the reel film is carried out moulding, in existing installation, can not stretch.Like this, the reel film is made common thickness, when carrying out the low range stretching, because therefore generation, is difficult to obtain the purpose sheet thickness by the stretching irregular (gage distortion) that the remnants (constriction) that stretch produce easily.
During uniaxial extension, can low range stretch even carry out, stretch and irregularly also lack than aforesaid method, and become more readily available the purpose sheet thickness, but from hot formability, because stretching ratio must be controlled at below 3 times, therefore, sheet material such as rigidity, transparency rerum natura becomes insufficient (for example, Japanese kokai publication sho 53-94371 communique, Japanese kokai publication sho 53-128673 communique).In addition, also known have method that the special reel film cooling mode of combination carries out uniaxial extension (for example, Japanese Patent Publication 63-16256 communique, Japanese Patent Publication 63-62377 communique), though but the sheet material rerum natura is improved a little, but be difficult to say so fully, in addition, undesirable because cost of equipment (manufacturing cost) becomes at high price.
Patent documentation 1: TOHKEMY 2002-284942 communique
Patent documentation 2: Japanese kokai publication sho 53-94371 communique
Patent documentation 3: Japanese kokai publication sho 53-128673 communique
Patent documentation 4: Japanese Patent Publication 63-16256 communique
Patent documentation 5: Japanese Patent Publication 63-62377 communique
Summary of the invention
The present invention makes in order to solve the problem of following prior art as described above to produce, provide a kind of drawing process such as uniaxial extension, the cooling of biaxial stretch-formed, reel film and stretching ratio that are not subjected to restrict, and have superior stiffness, heat-resisting rigidity, the transparency, even Propenes resin composition and stretched sheet that contains this resin combination and the thermally molded article each used of the stretched sheet of stretchiness and hot formability.
The present inventor furthers investigate in order to address the above problem, found that, made up the widely distributed resin combination of propylene resin composition each other of specified range fusing point, can not be subjected to the restriction of drawing process and stretch, and, the stretched sheet that contains this resin combination, the balance of its rigidity, heat-resisting rigidity, the transparency, even stretchiness and hot formability is extremely good, thereby has finished the present invention.
That is, the present invention is specific by the item institute of following record.
(1) a kind of propylene resin composition for stretched sheet (A), contain: the fusing point of measuring with DSC is 156～170 ℃ high-melting-point propylene resin (A ') 10～90 weight %; With at least a above fusing point of measuring with DSC be 70～155 ℃ the lower melting propylene resinoid (A ") 10～90 weight %, wherein, A ' and A " total be 100 weight %,
And this propylene resin composition for stretched sheet (A) satisfies following condition [1]～[4]:
[1] MFR (230 ℃, the 2.16kg load) is 0.5～10.0g/10min;
[2] fusing point of measuring with DSC is 150～170 ℃;
[3] in propylene resin composition for stretched sheet (A), alpha-olefin comonomer content is 1～11mol%;
[4] contain into nuclear composition.
(2) as (1) described propylene resin composition for stretched sheet (A), the alpha-olefin comonomer content of high-melting-point propylene resin (A ') is 0～1.5mol%, and (the alpha-olefin comonomer content of A ") is 1.6～24mol% to the lower melting propylene resinoid.
(3) a kind of single sheet (B1) is at least at single shaft direction stretching (1) or (2) described propylene resin composition for stretched sheet (A).
(4) a kind of multi-layer sheet (B2), at least at the superiors or undermost arbitrary layer of use (1) or (2) described propylene resin composition for stretched sheet (A), this multi-layer sheet stretches in the single shaft direction at least, and, fusing point of the superiors of this multi-layer sheet (Tm1) and undermost fusing point (Tm2) satisfy 1≤Tm2-Tm1≤100 (℃) relation.
(5) a kind of multi-layer sheet (B2 '), at the superiors and undermost two-layer use (1) or (2) described propylene resin composition for stretched sheet (A), the alpha-olefin comonomer content (C1) of the resin combination of formation multi-layer sheet (B2 ') the superiors and the alpha-olefin comonomer content (C2) of the undermost resin combination of formation satisfy the relation of C1＞C2.
(6) a kind of thermally molded article each that (B1) thermoforming of (3) described single sheet is obtained.
(7) a kind of with (4) described multi-layer sheet (B2) or (B2 ') thermoforming of (5) described multi-layer sheet and the thermally molded article each that obtains.
(8) as (7) described thermally molded article each, use as the material of contents such as wrap food, medicine equipment, pharmaceuticals, electronic unit, stationery, groceries, this thermally molded article each becomes the mode thermoforming of outside one side with the superiors of above-mentioned multi-layer sheet (B2) or (B2 ') with respect to the foregoing thing and obtains.
The invention effect
The individual layer and the multilayer stretched sheet material that contain propylene resin composition for stretched sheet of the present invention (A), the balance of its rigidity, heat-resisting rigidity, the transparency, even stretchiness and hot formability is extremely good.And from the thermally molded article each that this individual layer and multilayer stretched sheet material obtain, rigidity, heat-resisting rigidity, the transparency, oil-proofness are contour, and have low-gravity feature.In addition, the thermally molded article each that is obtained by this multilayer stretched sheet material is because the post shrinkage after the moulding is few, distortion is little, so the shape stability excellence.Therefore, contain the individual layer and the multilayer stretched sheet material of propylene resin composition for stretched sheet of the present invention (A), can be extensive use of as the wrapping material of food, medicine equipment, pharmaceuticals, electronic unit, stationery, groceries etc.
Embodiment
Propylene resin composition for stretched sheet of the present invention (A) contains high-melting-point propylene resin (A ') and at least a above lower melting propylene resinoid (A ").
High-melting-point propylene resin (A ')
The fusing point (Tm) that high-melting-point propylene resin (A ') is measured with DSC is in 156～170 ℃ scope, preferably in 160～170 ℃ scope, more preferably in 163～170 ℃ scope.Tm contains the rigidity and the heat-resisting excellent rigidity of the stretched sheet of Propenes resin composition of the present invention (A) when this scope.
High-melting-point propylene resin (A ') is to contain the polymkeric substance of propylene as structural unit, is the homopolymer of propylene, and perhaps propylene and ethene or carbonatoms are the random copolymers of 4～20 alpha-olefin (alpha-olefin comonomer).Here, as carbonatoms is 4～20 alpha-olefin, for example can enumerate 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Wherein, optimal ethylene or carbonatoms are 4～10 alpha-olefin.The content of alpha-olefin comonomer is 0～1.5mol% in high-melting-point propylene resin (A '), is preferably 0～1.2mol%, more preferably 0～0.6mol%.
In addition, the optimal way of high-melting-point propylene resin (A ') is that melt flow rate (MFR) (MFR) (230 ℃, the 2.16kg load) is in the scope of 0.3～15.0g/10min, more preferably in the scope of 0.6～9.0g/10min.If MFR in this scope, the extrudability excellence of reel film then.
In addition, the optimal way of high-melting-point propylene resin (A ') is, by
13Pmmmm in the C-NMR spectrum and the absorption intensity of Pw, the stereoregularity index [M that utilizes following formula (Eq-1) to obtain
5] value in 0.960～0.990 scope, more preferably in 0.970～0.990 scope.If stereoregularity index [M
5] in this scope, the then rigidity of stretched sheet and heat-resisting excellent rigidity.
(in the formula, [Pmmmm] expression from 5 unit of propylene units continuously, the absorption intensity of the 3rd unitary methyl in the isotactic bonded position, [Pw] expression is from the absorption intensity of the methyl of propylene units.)
The manufacture method of such high-melting-point propylene resin (A ') for example can be used the method for putting down in writing in Japanese kokai publication hei 2-84404 communique, Japanese kokai publication hei 2-229807 communique, Japanese kokai publication hei 3-7703 communique etc.
Lower melting propylene resinoid (A ")
(Tm of A ") is in 70～155 ℃ scope, preferably in 70～150 ℃ scope, more preferably in 78～148 ℃ scope for the lower melting propylene resinoid.If Tm in this scope, then contains the transparency of the stretched sheet of Propenes resin composition of the present invention (A), even stretchiness, hot formability excellence.
(A ") contains the polymkeric substance of propylene as structural unit to the lower melting propylene resinoid, is that propylene and ethene or carbonatoms are the random copolymers of 4～20 alpha-olefin (alpha-olefin comonomer).Here, as carbonatoms is 4～20 alpha-olefin, for example can enumerate 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Wherein, optimal ethylene or carbonatoms are 4～10 alpha-olefin.The content of alpha-olefin comonomer, (among the A ") is 1.6～24mol%, is preferably 3.0～24mol%, more preferably 3.7～24mol% at the lower melting propylene resinoid.
In addition, (optimal way of A ") is that MFR (230 ℃, the 2.16kg load) is preferably in the scope of 0.3～15.0g/10min, more preferably in the scope of 0.6～9.0g/10min to the lower melting propylene resinoid.If MFR in this scope, the extrudability excellence of reel film then.
As such lower melting propylene resinoid (manufacture method of A "); if Tm more than 130 ℃, then can use the manufacture method of above-mentioned high-melting-point propylene resin (A '), but when Tm is lower than 130 ℃;, thereby can not use because the isotatic polypropylene growing amount increases.With respect to this, use the method for metallocene catalyst, owing to can suppress the isotatic polypropylene growing amount, therefore especially as the lower melting propylene resinoid (manufacture method of A ") and preferred; for example, can use the method for in WO01/027124 communique, TOHKEMY 2002-275282 communique, TOHKEMY 2002-275330 communique, TOHKEMY 2002-275331 communique, TOHKEMY 2002-275332 communique etc., putting down in writing.
Propylene resin composition for stretched sheet (A)
Propylene resin composition for stretched sheet of the present invention (A) be combination high-melting-point propylene resin (A ') and at least a more than lower melting propylene resinoid (A ") and the resin combination that obtains.The composition of resin combination (A), in resin combination (A), high-melting-point propylene resin (A ') is 10～90 weight %, is preferably 20～80 weight %; (A ") (more than two kinds the time, for resin (the total amount of A ")) is 10～90 weight %, is preferably 20～80 weight % at least a above lower melting propylene resinoid.
Propylene resin composition for stretched sheet of the present invention (A), MFR (230 ℃, 2.16kg load) is in the scope of 0.5～10.0g/10min, preferably in the scope of 1.0～5.0g/10min, Tm is in 150～170 ℃ scope, preferably in 155～170 ℃ scope, more preferably in 158～170 ℃ scope, in resin combination (A), the content of alpha-olefin comonomer is in the scope of 1.0～11mol%, preferably in the scope of 1.5～8mol%, and contain into nuclear composition.
Propylene resin composition for stretched sheet of the present invention (A) can be by the multi-stage polymeric manufacturing.For example, in the polymerization tank more than two sections that is connected in series, can make high-melting-point propylene resin (A '), make lower melting propylene resinoid (A ") continuously at leading portion at back segment.
In addition, in addition, (A "); also can access Propenes resin composition (A); in addition also can directly supply with the sheet forming machine with above-mentioned resin for high-melting-point propylene resin (A ') that melting mixings such as use single shaft forcing machine, multiple screw extruder, kneader or Banbury are made respectively and lower melting propylene resinoid.
Become nuclear composition
As the one-tenth nuclear composition that is contained in the propylene resin composition for stretched sheet of the present invention (A), can use known nucleator ad lib.For example, can enumerate Sorbitol Powder compounds, phosphate compounds, carbonatoms is 4～12 aliphatic dicarboxylic acid and metal-salt, aromatic carboxylic acid and metal-salt thereof, metallic rosinate compounds and Magnesium Silicate q-agent (talcum) etc.In addition, prepolymerization is as after the reactive monomer that becomes nuclear composition in the polypropylene polymerizing catalyst, and with propylene polymerization, the polypropylene that obtains (polymkeric substance nucleator) is also included within the nuclear composition.Become in the nuclear composition at these, because the intermiscibility and the nucleating effect height of above-mentioned polymkeric substance nucleator, and few to the pollution of sheet forming machine and thermoforming machine, so preferred.
Employed reactive monomer in the prepolymerization as above-mentioned polymkeric substance nucleator, can enumerate 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, allyl group naphthalene, allyl group norbornylene, vinylbenzene, dimethyl styrene class, vinyl naphthalene class, allyl group toluene class, allyl benzene, vinyl cyclohexane, vinyl pentamethylene, vinyl suberane, allyl group trialkyl silica alkanes etc.
The manufacture method of above-mentioned polymkeric substance nucleator can be used the method for putting down in writing in Japanese kokai publication hei 4-202505 communique, Japanese kokai publication hei 4-202506 communique, Japanese kokai publication hei 4-202510 communique etc.
With respect to propylene resin composition for stretched sheet (A) 100 weight parts, these become nuclear composition is 0.001～0.5 weight part, is preferably 0.0018～0.3 weight part.
Additive
When being shaped to stretched sheet as raw material with propylene resin composition for stretched sheet of the present invention (A), in the scope that does not exceed the object of the invention, can add additives such as antioxidant, fast light stablizer, UV light absorber, metallic soap, hydrochloric acid absorbent, lubricant, antistatic agent, antifogging agent and anti.
The addition of these additives according to kind and difference, but so long as do not damage the scope of the object of the invention and get final product, usually, with respect to 100 weight part propylene resin composition for stretched sheet (A), is below 3 weight parts.
Stretched sheet and thermally molded article each
Contain propylene resin composition for stretched sheet of the present invention (A), and at least at single shaft direction tensile sheet material, the balance of its rigidity, heat-resisting rigidity, the transparency, even stretchiness and hot formability is extremely good.
Stretched sheet of the present invention can obtain by known manufacture method, for example, supply with above-mentioned propylene resin composition for stretched sheet (A) (using many forcing machines during multilayer) to forcing machine, resin temperature is adjusted into 190～280 ℃, extrude (during multilayer from the T pattern tool that is installed in the forcing machine front end, make it the back, interflow before being about to arrive T pattern tool or in the T pattern tool), utilize the cooling roller that is adjusted into 20～80 ℃ of temperature to stretch and batch, form the reel film.Reheat in the preheat roll that is adjusted into 130～160 ℃ of temperature carries out roller at vertical stretching ratio with 2～5 times and stretches, and utilizes the lehr rollers limit that is adjusted into 100～160 ℃ of temperature to make it lax 0～10% limit and batches and obtain.
In addition, drawing process is not defined, except that above-mentioned vertical uniaxial extension, also can be to the horizontal uniaxial extension of horizontal tensile with the tentering device, also can be biaxial stretch-formed one by one with the tentering device behind above-mentioned vertical uniaxial extension, or tensile be simultaneously biaxial stretch-formed simultaneously at vertical and horizontal only to use the tentering device to horizontal tensile.
Preferred stretching ratio when making stretched sheet of the present invention is 2～6 times scope during uniaxial extension, 3～5 times scope more preferably, in addition, when biaxial stretch-formed, vertically/laterally be respectively 2～6 times scope, more preferably 3～5 times scope.
Stretched sheet of the present invention is single sheet (B1) that is formed by propylene resin composition for stretched sheet (A) or the multi-layer sheet more than two layers (B2) that contains this resin combination (A).
Usually, the polypropylene stretched sheet has by stretching and causes the molecular chain strained because the feature that thermogenesis relaxes thereby shrinks.Because polyacrylic second-order transition temperature (Tg) is below 0 ℃, therefore, even also slowly shrink (post shrinkage) at normal temperatures.The thermally molded article each of pressing thermoformings such as empty moulding that polypropylene stretched sheet secondary processing is obtained by hot plate moulding, vacuum, exist preservation in summer (high temperature) and prolonged preservation etc. to produce the situation (under the situation of the quadrangular shapes of tool such as container, turn on one's side to the outside with respect to original state easily and roll up and the generation distortion in the edge of thermally molded article each) of post shrinkage, distortion.Owing in the thermally molded article each that forms by single sheet of the present invention (B1), also have kindred circumstances, therefore, in the shape of thermally molded article each, store method etc., be subjected to restriction to a certain degree.
With respect to this,,, therefore, can eliminate or relax the restriction of shape, store method etc. because above-mentioned distortion is minimum by the thermally molded article each that multi-layer sheet of the present invention (B2) forms.
Multi-layer sheet of the present invention (B2), at least in the superiors or undermost arbitrary layer, use propylene resin composition for stretched sheet of the present invention (A), in the superiors, use fusing point to be lower than undermost polypropylene, preferably use propylene resin composition for stretched sheet (A).At this moment, the fusing point poor (Δ Tm) of the superiors and orlop (two outermost layers) is 1～100 ℃, is preferably 3～30 ℃, more preferably 3～15 ℃.That is, design level structure importantly makes the fusing point (Tm1) of these multi-layer sheet the superiors and the relation that undermost fusing point (Tm2) satisfies (I), and the preferred relation that satisfies (II) more preferably satisfies the relation of (III).
(I)1≤Tm2-Tm1≤100(℃)
(II)3≤Tm2-Tm1≤30(℃)
(III)3≤Tm2-Tm1≤15(℃)
In addition, multi-layer sheet of the present invention (B2 '), at the superiors and undermost two-layer use propylene resin composition for stretched sheet of the present invention (A), importantly, the alpha-olefin comonomer content (C2) of the alpha-olefin comonomer content (C1) of the resin combination of the formation the superiors and the undermost resin combination of formation satisfies the relation of C1＞C2.
In addition, during this multi-layer sheet of thermoforming, make that the direction of sheet material is consistent carries out moulding, make the above-mentioned the superiors (low Tm) be inner face side, thereby can suppress distortion by the post shrinkage generation for the exterior side of thermally molded article each, above-mentioned orlop (high Tm).
Promptly, when thermoforming has the multi-layer sheet of the present invention of aforesaid structure, make that the direction of sheet material is consistent carries out moulding, make that the superiors' (low Tm side) of multi-layer sheet (B2) or (B2 ') are that the orlop (high Tm side) of exterior side, multi-layer sheet (B2) or (B2 ') is an inner face side with respect to content with respect to content, in addition, according to other performance, the superiors of multi-layer sheet (B2) or (B2 ') (low Tm side) at the shape convex side of thermally molded article each, orlop (high Tm side) in the concave surface inboard, thereby can suppress the distortion that produces by post shrinkage.
In addition, when thermoforming has the multi-layer sheet of the present invention (B2 ') of aforesaid structure, make that the direction of sheet material is consistent carries out moulding, make that the superiors' (C1 side) of multi-layer sheet (B2 ') are that exterior side, orlop (C2 side) are inner face side with respect to content with respect to content, in addition, according to other performance, the superiors of multi-layer sheet (B2 ') (C1 side) at the shape convex side of thermally molded article each, orlop (C2 side) in the concave surface inboard, thereby also can suppress the distortion that produces by post shrinkage.
Usually, polyacrylic being stretching in the temperature range that crystallized temperature (Tc) is above, Tm is following carried out.The post shrinkage amount of stretched sheet depends on its draft temperature, expresses that then post shrinkage amount of draft temperature low more (the closer to Tc) is more big, the more little tendency of draft temperature high more (the closer to Tm) then post shrinkage amount.Therefore, the thermally molded article each that forms by above-mentioned multi-layer sheet (B2), because the exterior side at this thermally molded article each has the above-mentioned the superiors (low Tm), has above-mentioned orlop (high Tm) in inner face side, therefore, exterior side stretches with the temperature than the more close Tm of inner face side, the post shrinkage amount of thermally molded article each exterior side is less than the post shrinkage amount of inner face side, and therefore, it is minimum to become.In addition, by the fusing point of regulating this multi-layer sheet poor (Δ Tm), layer thickness ratio and draft temperature etc., the post shrinkage amount of outside in can controlling arbitrarily, therefore, can be corresponding to multiple shape.
Multi-layer sheet of the present invention (B2) in the scope that does not exceed the object of the invention, can obtain more value added by make up other resin in the middle layer.For example, can enumerate by in the middle layer, using the vinyl-vinyl alcohol copolymer to improve the oxygen and carbon dioxide block, if in the middle layer, use the polypropylene resin composite that contains hydrogenated petroleum resin then water vapor block raising etc.In addition, as other resin that can in the middle layer, use, for example, can enumerate polyester resins such as polyamide-based resin, polyethylene terephthalate and polybutylene terephthalate such as polyvinyl alcohol resin, polyvinylidene chloride resin, polyacrylonitrile resin, m-xylene diamine 6 and nylon 6.
In addition, the thermally molded article each that obtains by stretched sheet of the present invention, because rigidity, heat-resisting rigidity, the transparency, oil-proofness are contour, and proportion is low, therefore, the wrapping material that can be used as food, medicine equipment, pharmaceuticals, electronic unit, stationery, groceries etc. are extensive use of.
[embodiment]
Then, describe the present invention in detail, but the present invention is not limited by these embodiment based on embodiment.
Physical property measurement method among the embodiment is as follows.
1) melt flow rate (MFR) (MFR[g/10min])
According to ASTM D-1238, measure with 230 ℃ of temperature, load 2.16kg.In barrel, do not import nitrogen especially, directly in barrel, drop into particle, make it fusion.
2) fusing point (Tm[℃])
In DSC, be warmed up to 230 ℃ with 10 ℃/min from 30 ℃, 230 ℃ keep 10 minutes after, be cooled to 30 ℃ with 10 ℃/min, heat up with 10 ℃/min again, with the endotherm peak temperature that occurs this moment as fusing point.
3) isotactic five unit number of components (mmmm:[M
5])
By
13Pmmmm in the C-NMR spectrum and the absorption intensity of Pw are utilized following formula (Eq-1) decision.Wherein, the peak belongs to according to Polymer, and 1993, Vol34, No14,3129-3131 carries out.
4) even stretchiness (gage distortion [-])
The thickness of measuring space stretched sheet with regulation adds up to 30 places, and the value that its standard deviation is obtained divided by mean thickness is as the even index of stretchiness (value is more little, and even stretchiness is good more).
5) modulus in tension (MPa)
Obtain the test film of ASTM D-638 type 4 types from the sheet material stamping-out, making the chuck spacing is that 46mm, speed are that 50mm/min, temperature are 23 ℃ or 110 ℃, utilizes the initial stage gradient of the stress-distortion line when stretching to obtain.
6) mist degree (HAZE[%])
Utilization is measured according to the Japanese electric look industrial TURBIDIMETER of use integrating sphere 150 Φ of JIS K7361.
7) heat shrink rate (SH[%])
Obtain the test film of wide 10mm, long 100mm (L0) from the sheet material stamping-out, heating is 15 minutes in 130 ℃ air oven, measures the length (L1) after the heating, utilizes following formula (Eq-2) to calculate.
8) hot formability (excipient scoring [branch])
In the hot plate shaper, use container model mould (size: 90mm, the degree of depth: 20mm) carry out thermoforming, the thermally molded article each shape that range estimation obtains with the condition of molding of stipulating, estimated (the big more hot formability of value is good more, and scoring is preferred more than 3 minutes) in 5 minutes with full marks.
9) thermally molded article each deflection (buckling deformation amount [mm])
Thermally molded article each was worn out 1 in 50 ℃ air oven, measure the edge warping amount of thermally molded article each.
10) proportion
According to JIS K7112, the mid-method of changing of water is measured.
[embodiment 1]
Prepolymerization as the 3-methyl-1-butene (3MB-1) that becomes nuclear composition afterwards, with respect to resin combination 100 weight parts, as antioxidant, cooperate 0.1 weight part four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane (IRGANOX1010, Ciba Specialty Chemicals society produces, trade mark) and three (2, the 4-DI-tert-butylphenol compounds) phosphoric acid ester of 0.1 weight part (IRGAFOS168, Ciba Specialty Chemicals society produces, trade mark), as neutralizing agent, cooperate the calcium stearate (Japanese grease society produce) of 0.1 weight part, use single screw extrusion machine, with 230 ℃ of melting mixings of resin temperature, granulation becomes particulate state.Wherein, the lower melting propylene resinoid of Tm=135 ℃ of obtaining of high-melting-point propylene resin (A '-1) the 75 weight % of Tm=167 ℃ of being obtained by the propylene homopolymerization of this resin combination, MFR=2g/10min, mmmm=0.972 and propylene and ethene 6mol% copolymerization, MFR=2g/10min (A " 1) 25 weight % combine.At this moment, as the ratio of the 3MB-1 polymkeric substance that becomes nuclear composition, in above-mentioned resin combination 0.027 weight %.The rerum natura of the resin combination (particle) that expression obtains in table 1,2.
Supply with above-mentioned particle to vertical uniaxial extension sheet forming machine, extrude from T pattern tool with 250 ℃ of resin temperatures, the reel film that edge forming is thickness 1.2mm is batched with the cooling roller stretching of 30 ℃ of temperature in the limit, behind the preheat roll reheat with 150 ℃ of temperature, carrying out roller with 4 times of stretching ratios stretches, with 110 ℃ of annealing of temperature, obtain vertical uniaxial extension sheet material of thickness 0.3mm.The rerum natura of the sheet material that expression obtains in table 1,2.
In the hot plate shaper, use the said vesse mould, set pressing absolutely empty atmospheric pressure is that 0.64MPa, vacuum tightness are that 0.09MPa, sheet material heat-up time is that 3s, excipient time are 3s, above-mentioned stretched sheet is carried out thermoforming with the scope of 100～160 ℃ of hot plate temperatures, do not have gonorrhoea, the best excipient to mark in the thermally molded article each that expression obtains in table 1,2.
[embodiment 2]
Except use the resin combination (ratio of 3MB-1 polymkeric substance is 0.018 weight %) that combines by lower melting propylene resinoid used among high-melting-point propylene resin used among the embodiment 1 (A '-1) 50 weight %, the embodiment 1 (A " 1) 50 weight % in resin combination; carry out its result of expression in table 1 similarly to Example 1.
[embodiment 3]
After the 3-methyl-1-butene of prepolymerization as the one-tenth nuclear composition, the resin combination (ratio of 3MB-1 polymkeric substance is 0.017 weight % in resin combination) that used lower melting propylene resinoid among high-melting-point propylene resin (A '-2) 50 weight %, the embodiment 1 of Tm=166 ℃ of being obtained by the propylene homopolymerization of use, MFR=11g/10min, mmmm=0.972 (A " 1) 50 weight % combine in addition; carry out its result of expression in table 1 similarly to Example 1.
[embodiment 4]
Except the resin combination (ratio of 3MB-1 polymkeric substance is 0.017 weight % in resin combination) that the lower melting propylene resinoid that uses Tm=135 ℃ of being obtained by embodiment 3 used high-melting-point propylene resin (A '-2) 50 weight %, propylene and ethene 6mol% copolymerization, MFR=10g/10min (A " 2) 50 weight % combine; carry out similarly to Example 1, in table 1, represent its result.
[embodiment 5]
Except the resin combination (ratio of 3MB-1 polymkeric substance is 0.018 weight % in resin combination) that the lower melting propylene resinoid that uses Tm=140 ℃ of being obtained by high-melting-point propylene resin used among the embodiment 1 (A '-1) 50 weight %, propylene and ethene 5.4mol% copolymerization, MFR=0.5g/10min (A " 3) 50 weight % combine; carry out similarly to Example 1, in table 1, represent its result.
[embodiment 6]
Used lower melting propylene resinoid in high-melting-point propylene resin (A '-3) the 40 weight %, the embodiment 5 that use Tm=165 ℃ of obtaining, MFR=0.5g/10min, mmmm=0.979 (A " 3) 50 weight % by the propylene homopolymerization with as the resin combination (ratio of 3MB-1 polymkeric substance is 0.0036 weight % in resin combination) that becomes propylene resin (A '-1) 10 weight % used among the embodiment 1 of nuclear composition to combine; carry out similarly to Example 1, in table 1, represent its result.
[embodiment 7]
With respect to containing high-melting-point propylene resin used among the embodiment 1 (A '-1) 25 weight %, Tm=138 ℃ of obtaining of propylene and ethene 4mol% copolymerization, the lower melting propylene resinoid of MFR=1.3g/10min (A " 4) 50 weight %; and Tm=78 ℃ of obtaining of propylene and the copolymerization of 23.5mol%1-butylene; resin combination 100 weight parts of the ultralow fusing point propylene resin of MFR=7g/10min (A " 5) 25 weight %, recombinant is as two [2 of nucleator, 4,8,10-tetra-tert-6-hydroxyl-12H-dibenzo [d, g] [1,3,2] dioxy phospha eight ring-6-oxide compounds] aluminium hydroxide salt (NA-21, ADEKA society produces, trade mark) 0.13 weight part obtains resin combination.Except using this resin combination, melting mixing similarly to Example 1, granulation becomes particulate state (ratio of 3MB-1 polymkeric substance is 0.009 weight %) in resin combination.In addition, supply with above-mentioned particle, change to 130 ℃, be shaped to stretched sheet similarly to Example 1, its result of expression in table 1 except making the preheat roll temperature to the sheet forming machine.
[comparative example 1]
Remove lower melting propylene resinoid (A " 1) in the resin combination used from embodiment 1 except using; only with high-melting-point propylene resin (A '-1) be 100 weight % (ratio of 3MB-1 polymkeric substance is 0.036 weight % in resin) in addition; carry out its result of expression in table 1 similarly to Example 1.
[comparative example 2]
Remove into nuclear composition (A '-1) except using in the resin combination used from embodiment 6, beyond the resin combination that formation is combined by high-melting-point propylene resin (A '-3) 50 weight %, lower melting propylene resinoid (A " 3) 50 weight %; carry out its result of expression in table 1 similarly to Example 1.
[comparative example 3]
Remove high-melting-point propylene resin (A '-1) and ultralow fusing point propylene resin (A " 5) in the resin combination used from embodiment 7 except using; beyond the resin combination that formation is only combined by lower melting propylene resinoid (A " 4) 100 weight % and nucleator (NA-21) 0.13 weight part, carry out its result of expression in table 1 similarly to Example 7.
[comparative example 4]
Except use the resin combination (ratio of 3MB-1 polymkeric substance is 0.018 weight %) that combines by ultralow fusing point propylene resin used among propylene resin used among the embodiment 1 (A '-1) 50 weight % and the embodiment 7 (A " 5) 50 weight % in resin combination; carry out its result of expression in table 1 similarly to Example 7.
[embodiment 8]
Supply with the particle that embodiment 1 obtains to biaxial stretch-formed sheet forming machine one by one, extrude from T pattern tool with 250 ℃ of resin temperatures, the reel film that edge forming is thickness 1.8mm is batched with the cooling roller stretching of 30 ℃ of temperature in the limit, preheat roll with 150 ℃ of temperature carries out reheat, stretch for 3 times with stretching ratio, afterwards, supply with to the tentering device, carry out cross directional stretch for 3 times with 155 ℃ of draft temperatures, stretching ratio, annealing with 160 ℃ of lax 5% width edge of temperature in the limit, obtains the biaxial stretch-formed one by one sheet material of thickness 0.2mm.The rerum natura of the sheet material that expression obtains in table 2.
[embodiment 9]
Change to 5 times except the reel film that in embodiment 8, is shaped to thickness 3.0mm and with cross directional stretch, carry out similarly to Example 8, its result of expression in table 2.
[embodiment 10]
The reel film of the thickness 1.8mm that obtains among the embodiment 8 is cut into the size of 85mm, on the biaxial stretch-formed machine of bench-type, with draft temperature be 155 ℃, stretching ratio serve as vertically * laterally=3 * 3 times carry out the while biaxial stretch-formed after, biaxial stretch-formed sheet material when obtaining thickness 0.2mm is annealed with 160 ℃ of lax 5% width edge of temperature in the limit.The rerum natura of the sheet material that expression obtains in table 2.
[comparative example 5]
The particle that obtains in the sheet forming machine is supplied with embodiment 1 is extruded from T pattern tool with 250 ℃ of resin temperatures, and the limit stretches with the cooling roller of 30 ℃ of temperature and batches the no stretched sheet that the limit obtains thickness 0.3mm.The rerum natura of the sheet material that expression obtains in table 2.
[table 2]
[embodiment 11]
Use has the multi-layer sheet shaper of the forcing machine of two series, used high-melting-point propylene resin (A '-1) 20 weight % in upper strata (low melting point layer) uses by embodiment 1, with propylene and ethene 6mol% copolymerization, and be combined with Tm=139 ℃ of 0.03 weight part steatitic, the resin combination (granulation is carried out similarly to Example 1) that the lower melting propylene resinoid of MFR=3g/10min (A '-6) 80 weight % combine, use by above-mentioned high-melting-point propylene resin (A '-1) 50 weight % in lower floor, the resin combination (ratio of 3MB-1 polymkeric substance is 0.0072 weight % in resin combination; granulation is carried out similarly to Example 1) that above-mentioned lower melting propylene resinoid (A " 6) 50 weight % combine, (bed thickness is than being the upper strata: reel film lower floor=1: 2) to be shaped to two kinds two layers of total thickness 1.2mm.Be vertical uniaxial extension sheet material of thickness 0.3mm with the roller drawing and forming similarly to Example 1 again, obtain the thermally molded article each of this sheet material.The rerum natura that expression is measured the sheet material that obtains and thermally molded article each in table 3.
[embodiment 12]
Except in embodiment 11, the bed thickness ratio being changed to the upper strata: the lower floor=1: 4, carry out its result of expression in table 3 similarly to Example 11.
[embodiment 13]
Except the resin combination (ratio of 3MB-1 polymkeric substance is 0.0018 weight % in resin combination; granulation is carried out similarly to Example 1) that used high-melting-point propylene resin (A '-1) 5 weight % and lower melting propylene resinoid (A " 6) 95 weight % combine in upper strata (low melting point layer) uses by embodiment 1 in embodiment 11; the bed thickness ratio is changed to the upper strata: lower floor=1: 1; the preheat roll temperature is beyond 130 ℃; carry out similarly to Example 11, its result of expression in table 3.
[embodiment 14]
Resin combination with using in lower floor among the embodiment 11 carries out vertical uniaxial extension (single sheet) similarly to Example 1, its result of expression in table 3.
[comparative example 6]
The rerum natura of middle no oriented polypropylene (PP) sheet materials (thickness 0.3mm) that use such as lid stock of the present food product containers of expression in table 3.
[comparative example 7]
The rerum natura of the middle biaxial stretch-formed polystyrene sheet materials (OPS sheet material) (thickness 0.25mm) that use such as lid stock of the present packed meal container of expression in table 3.
[table 3]
Utilizability on the industry
The stretched sheet that contains propylene resin composition for stretched sheet of the present invention (A), the balance of rigidity, heat-resisting rigidity, the transparency, Uniform Tension and hot formability is extremely good, and the thermally molded article each that is obtained by this stretched sheet, rigidity, heat-resisting rigidity, the transparency, oil resistivity is contour and proportion is low, therefore, can be extensive use of as the packaging material of food, medicine equipment, pharmaceuticals, electronic unit, stationery, groceries etc.
Claims (8)
1. a propylene resin composition for stretched sheet (A) is characterized in that,
Contain: the fusing point of measuring with DSC is 156～170 ℃ high-melting-point propylene resin (A ') 10～90 weight %; With
At least a above fusing point of measuring with DSC be 70～155 ℃ the lower melting propylene resinoid (A ") 10～90 weight %,
Wherein, A ' and A " total be 100 weight %,
This propylene resin composition for stretched sheet (A) satisfies following condition [1]～[4]:
[1] melt flow rate (MFR) (230 ℃, the 2.16kg load) is 0.5～10.0g/10min;
[2] fusing point of measuring with DSC is 150～170 ℃;
[3] in propylene resin composition for stretched sheet (A), alpha-olefin comonomer content is 1～11mol%;
[4] contain into nuclear composition.
2. propylene resin composition for stretched sheet as claimed in claim 1 (A) is characterized in that:
The alpha-olefin comonomer content of described high-melting-point propylene resin (A ') is 0～1.5mol%, and (the alpha-olefin comonomer content of A ") is 1.6～24mol% to described lower melting propylene resinoid.
3. a single sheet (B1) is characterized in that:
At least at single shaft direction stretching claim 1 or 2 described propylene resin composition for stretched sheet (A).
4. a multi-layer sheet (B2) is characterized in that:
At least use claim 1 or 2 described propylene resin composition for stretched sheet (A) the superiors or undermost arbitrary layer,
This multi-layer sheet stretches in the single shaft direction at least, and,
Fusing point of the superiors of this multi-layer sheet (Tm1) and undermost fusing point (Tm2) satisfy 1≤Tm2-Tm1≤100 (℃) relation.
5. a multi-layer sheet (B2 ') is characterized in that:
At the superiors and undermost two-layer use claim 1 or 2 described propylene resin composition for stretched sheet (A), and
Constitute the alpha-olefin comonomer content (C1) of resin combination of described multi-layer sheet (B2 ') the superiors and the relation that the alpha-olefin comonomer content (C2) that constitutes undermost resin combination satisfies C1＞C2.
6. thermally molded article each is characterized in that:
By the described single sheet of claim 3 (B1) thermoforming is obtained.
7. thermally molded article each is characterized in that:
By described multi-layer sheet of claim 4 (B2) or the described multi-layer sheet of claim 5 (B2 ') thermoforming are obtained.
8. thermally molded article each as claimed in claim 7 is characterized in that:
Material as contents such as wrap food, medicine equipment, pharmaceuticals, electronic unit, stationery, groceries uses, and
By the superiors of this thermally molded article each with described multi-layer sheet (B2) or (B2 ') are obtained with respect to the mode thermoforming that described content becomes outside one side.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007294625 | 2007-11-13 | ||
| JP2007-294625 | 2007-11-13 | ||
| PCT/JP2008/070392 WO2009063819A1 (en) | 2007-11-13 | 2008-11-10 | Propylene resin composition for stretched sheet, and stretched sheet and thermally molded article each comprising the composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101855289A true CN101855289A (en) | 2010-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880115937.6A Pending CN101855289A (en) | 2007-11-13 | 2008-11-10 | Propylene resin composition for stretched sheet, and stretched sheet and thermally molded article each comprising the composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JPWO2009063819A1 (en) |
| KR (1) | KR20100085157A (en) |
| CN (1) | CN101855289A (en) |
| TW (1) | TW200932803A (en) |
| WO (1) | WO2009063819A1 (en) |
Families Citing this family (28)
| 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 |
| WO2015022127A1 (en) | 2013-08-14 | 2015-02-19 | Borealis Ag | Propylene composition with improved impact resistance at low temperature |
| MX2016001930A (en) | 2013-08-21 | 2016-05-26 | Borealis Ag | High flow polyolefin composition with high stiffness and toughness. |
| US9890275B2 (en) | 2013-08-21 | 2018-02-13 | Borealis Ag | High flow polyolefin composition with high stiffness and toughness |
| PT2853563T (en) | 2013-09-27 | 2016-07-14 | Borealis Ag | Films suitable for bopp processing from polymers with high xs and high tm |
| EP2860031B1 (en) | 2013-10-11 | 2016-03-30 | Borealis AG | Machine direction oriented film for labels |
| EP3060589B9 (en) | 2013-10-24 | 2018-04-18 | Borealis AG | Low melting pp homopolymer with high content of regioerrors and high molecular weight |
| EP2865713B1 (en) | 2013-10-24 | 2016-04-20 | Borealis AG | Blow molded article based on bimodal random copolymer |
| US9670293B2 (en) | 2013-10-29 | 2017-06-06 | Borealis Ag | Solid single site catalysts with high polymerisation activity |
| US9751962B2 (en) | 2013-11-22 | 2017-09-05 | Borealis Ag | Low emission propylene homopolymer with high melt flow |
| CN105793298B (en) | 2013-12-04 | 2019-06-28 | 博里利斯股份公司 | The PP homopolymer without phthalic acid ester for meltblown fibers |
| KR101873134B1 (en) | 2013-12-18 | 2018-06-29 | 보레알리스 아게 | Bopp film with improved stiffness/toughness balance |
| US10227427B2 (en) | 2014-01-17 | 2019-03-12 | Borealis Ag | Process for preparing propylene/1-butene copolymers |
| ES2827285T3 (en) | 2014-02-06 | 2021-05-20 | Borealis Ag | Soft copolymers with high impact resistance |
| ES2767498T3 (en) | 2014-02-06 | 2020-06-17 | Borealis Ag | Transparent and smooth impact copolymers |
| EP2907841A1 (en) | 2014-02-14 | 2015-08-19 | Borealis AG | Polypropylene composite |
| ES2659731T3 (en) | 2014-05-20 | 2018-03-19 | 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 |
| 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 |
| 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 |
| JP7355591B2 (en) * | 2019-10-11 | 2023-10-03 | 三井化学株式会社 | Stretched film and its uses |
| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|---|
| JPWO2009063819A1 (en) | 2011-03-31 |
| JP5931950B2 (en) | 2016-06-08 |
| WO2009063819A1 (en) | 2009-05-22 |
| JP2014169446A (en) | 2014-09-18 |
| KR20100085157A (en) | 2010-07-28 |
| TW200932803A (en) | 2009-08-01 |
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