0001]The present invention relates to a thermoplastic elastomer composition, to a process for their preparation, and moldings.
BACKGROUND
[0002]Olefinic thermoplastic elastomer composition, as a material having a suitable flexibility and rubber elasticity and excellent formability, convenience goods, kitchenware, home appliances, machine parts, electrical parts, automobile parts, various are used in the fields, is performed raw material composition, the adjustment of such blending ratio used depending on required performance.
[0003]
　With the recent expanding applications, even in the olefinic thermoplastic elastomer composition, under a wide temperature environment, it is required to exhibit high properties as an elastomer. In particular applications where security of operating in a low-temperature environment is strictly required, it is increasing its social demands.
[0004]
　For example, an automobile interior material made of a cover of the air bag system, while being easily broken by the pressure of the airbag, without being scattered debris like hurt occupant, yet if not expandable material airbag reliably not not. Therefore The elastomer composition used in the airbag cover, even at a low temperature, the composition properties of the elastomer such as impact resistance and elongation is increased further is required.
[0005]
　Etc. Patent Document 1 and 2, an air bag cover made olefinic and / or styrene-based thermoplastic elastomer is described.
　In Patent Documents 3 to 5, olefin thermoplastic elastomer for an air bag cover having a low-temperature impact resistance have been proposed.
CITATION
Patent Document
[0006]
Patent Document 1: JP-A-4-314648 JP
Patent Document 2: JP-A 6-156178 Patent Publication
Patent Document 3: JP-A 10-279745 JP
Patent Document 4: JP 2004-285237 Patent Publication
Patent Document 5: International Publication No. 2014/46139
Summary of the Invention
Problems that the Invention is to Solve
[0007]
　However, the airbag cover according to Patent Document 1 and 2, if the formulation to ensure a necessary rigidity for practical use, because the impact strength at low temperatures is low, possible debris scattered when the airbag is activated There is sex, it was found that safety problems. Also, if you lower the rigidity for the feel and low-temperature impact resistance improvement, wear easily, due to the poor scratch resistance, the practical use has been found that it is necessary to apply a coating or the like on the surface .
[0008]
　Olefinic thermoplastic elastomer described in Patent Documents 3 to 5 also has the disadvantage of elongation and impact resistance at low temperatures is inferior, the air bag cover with the elastomer, in a wide temperature range from low to high temperature , cover is found that can not be completely prevented from scattering by an abnormal destruction.
[0009]
　Airbag cover, when the cover of the deployment, are designed to cleave fractured from tear line (groove-like thin wall portion). If, in particular, low-temperature environment, the elongation of the airbag cover is reduced, it fragments the airbag cover is likely to scatter away from the body, as a result, there is a possibility of damaging an occupant. Therefore, the thermoplastic elastomer used in the airbag cover, it is desirable to have excellent elongation and impact resistance at low temperatures.
[0010]
　In one embodiment of the present invention is excellent in the elongation and impact resistance, particularly a thermoplastic elastomer composition and molded article excellent in elongation and impact resistance at low temperatures. In one embodiment of the present invention, by using a thermoplastic elastomer composition in a wide temperature range from low to high temperatures, provide an air bag cover which can be to prevent the cover from scattering by an abnormal destruction to.
Means for Solving the Problems
[0011]
　The present inventor has conducted extensive studies to solve the above problems, according to the following configuration examples, it can solve the above problems, and have completed the present invention.
　Configuration Example of the present invention is as follows.
[0012]
　[1] (A) a melting point above 100 ° C. crystalline olefin
　resin, an olefin resin that satisfies (B) following requirement (B-1) ~
　(B-3), (C) an ethylene · alpha-olefin a copolymer
comprising a proportion of the resin (B) / co a polymer weight ratio of (C) 100/0 ~ 1 /99, and
　the resin (a) / (the resin (B) + a proportion of the copolymer (C)) in a weight ratio of 70 / 30-30 / 70,
　the thermoplastic elastomer composition.
　(B-1) has a backbone that is the ethylene copolymer (MC) and a side chain of an olefin polymer (SC), graft satisfying the following requirements (i) and (ii) containing a polymer [GP]
　ethylene copolymer constituting the (i) main chain (MC) is a repeating unit derived from ethylene, at least one selected from α- olefins having a carbon number of 3 ~ 20 alpha - and a repeating unit derived from an olefin, the α- repeating units derived from an olefin in the range of 10 ~ 50 mol% based on all repeating units are contained in the main chain (MC)
　(ii) side chain (SC ) is an ethylene polymer is at least one selected from the consisting side chains (SP) from consisting side chains (SE) and propylene polymer
　(B-2) is measured by differential scanning calorimetry That the melting point is in the range of ~ 170 ° C. 60
　(B-3) a glass transition temperature measured by differential scanning calorimetry is in the range of -80 ~ -30 ° C.
[0013]
　[2] ASTM D790 measured flexural modulus in conformity with is less than 650 MPa, the thermoplastic elastomer composition according to [1].
[0014]
　[3] The crystalline olefin resin (A), the 100 parts by weight of the total amount of the olefin resin (B) and the ethylene · alpha-olefin copolymer (C), filler (E) 5 parts comprising less, [1] or a thermoplastic elastomer composition according to [2].
[0015]
　[4] The crystalline olefin resin (A), the compliant with ISO 1133, 230 ° C., the melt flow rate measured at 2.16kg load is 0.1 ~ 500g / 10min, [1] ~ thermoplastic elastomer composition according to any one of [3].
[0016]
　[5] the side chain in the graft type copolymer [GP] (SC) is a composed side chains of ethylene polymer (SE),
　the side chain (SE) is a repeating unit derived from ethylene, and includes repeating units derived from at least one selected from α- olefin having 3 to 20 carbon atoms optionally on all the repeating units of the content of units derived from the ethylene is contained in the side chain (SE) in the range of 95 ~ 100
　mol%, [1] ~ thermoplastic elastomer composition according to any one of [4].
[0017]
　[6] The olefin resin (B), in differential scanning calorimetry showed a melting peak in the range of 60 ~ 130 ° C., a heat of fusion ΔH of the melting peak in the range of 5 ~ 100J / g, [1 thermoplastic elastomer composition according to any one of to [5].
[0018]
　[7] The E value is the percentage of 20 ° C. below the orthodichlorobenzene-soluble content as measured by cross fractionation chromatograph olefin resin (B) is not more than 45 wt%, [1] ~ [6] thermoplastic elastomer composition according to any one of.
[0019]
　[8] The intrinsic viscosity measured in decalin of 135 ° C. of the olefin resin (B) is in the range of 0.1 ~ 12 dl / g, the thermoplastic according to any one of [1] to [7] elastomer composition.
[0020]
　[9] The weight-average molecular weight of the ethylene polymer constituting the side chains (SE) is in the range of 500 to 30,000, [1] Thermoplastic elastomer composition according to any one of to [8].
[0021]
　[10] the side chain of the graft type polymer [GP] is 1000 per backbone polymer carbon atoms in the molecular chain, are present at 0.5 to 20 average frequency, [1] to [9] thermoplastic elastomer composition according to any one of.
[0022]
　[11] The olefin resin (B) satisfy the following requirements (B-7), [1 ] Thermoplastic elastomer composition according to any one of - [10].
　(B-7) in compliance with the ASTM D1238E olefin-based resin (B), 190 ℃, the melt flow rate measured at 2.16kg load and M (g / 10min), measured in the 135 ° C. decalin when the intrinsic viscosity of the olefin resin (B) which is an H (dl / g), the value a represented by the following equation (Eq-1) is in the range of 30 ~ 280
　a = M / exp (-3.3H) ··· (Eq- 1)
[0023]
　[12] The ethylene · alpha-olefin copolymer (C), in compliance with ASTM D1238E, 190 ℃, melt flow rate measured at 2.16kg load is 0.01 ~ 50 g / 10min, [ 1] the thermoplastic elastomer composition according to any one of - [11].
[0024]
　[13] in the absence of a crosslinking agent, the resin (A), the said resin (B) and the copolymer (C), the resin (A) / (the resin (B) + copolymer ( the weight ratio of C)) comprises a step of dynamic heat treatment of the mixture in a proportion to be 70/30 ~ 30/70, method for producing a thermoplastic elastomer composition according to any one of [1] to [12] .
[0025]
　[14] [1] ~ comprises a thermoplastic elastomer composition according to any one of [12], the molded body.
　[15] [1] ~ comprises a thermoplastic elastomer composition according to any one of [12], automobile parts.
　[16] [1] ~ comprises a thermoplastic elastomer composition according to any one of [12], automotive interior skin material.
　[17] [1] in any one of - [12] comprises a thermoplastic elastomer composition according automotive airbag cover.
[0026]
　[18] (A) and the melting point is above 100 ° C. crystalline olefin resin,
　(B) and structural units derived from ethylene, structural units derived from at least one selected from α- olefin having 3 to 20 carbon atoms wherein the door,
　the glass transition temperature is at -110 ~ -20 °
　C., in compliance with ASTM D1238E, 190 ℃, melt flow rate measured at 2.16kg load is 0.1 ~ 10 g / 10 min olefin and system
　resin, and (C) an ethylene · alpha-olefin copolymer,
　wherein a ratio of 100 / 0-1 / 99 in weight ratio of the resin (B) / the copolymer (C), and
　the in a weight ratio of the resin (a) / (the resin (B) + the copolymer (C)) comprises at a rate of 70 / 30-30 / 70,
further
　flexural modulus was measured according to ASTM D790 200 ~ 1000MPa der And
　elongation at break of -40 ℃ measured in accordance with JIS K6251 is 50 to 600%,
the thermoplastic elastomer composition.
[0027]
　[19] [18] comprises a thermoplastic elastomer composition according to, automobile interior skin materials or automotive airbag cover.
Effect of the invention
[0028]
　According to the thermoplastic elastomer composition according to one embodiment of the present invention is excellent in mechanical properties such as stiffness, molded articles excellent in impact resistance and elongation at break at low temperature is obtained. The molded body, from the viewpoint of such as the effect is more alive, automotive parts used in the interior or exterior of automobiles, for example, as automobile interior parts, automobile interior skin material, the air bag cover is for automobiles, automobile exterior the parts, mudguards and spoiler lip, fender liner is preferably exemplified.
DESCRIPTION OF THE INVENTION
[0029]
　«Thermoplastic elastomer composition»
　(hereinafter also referred to as "the present composition 1".) The thermoplastic elastomer composition according to an embodiment of the present invention 1,
　(A) a melting point above 100 ° C. Crystalline olefinic resin ( hereinafter referred to as "resin (a)".)
　and, (B) and the following requirements (B1) an olefin-based resin satisfying ~ a (B-3) (hereinafter "resin (B1)" also referred
　to.), (C ) ethylene · alpha-olefin also called (3 or more carbon atoms) copolymer (hereinafter "copolymer (C)".) and the,
　at a weight ratio of the resin (B1) / copolymer (C) 100 / includes 0 in a ratio of ~ 1/99, and,
　a proportion of the resin (a) / (the resin (B1) + copolymer (C)) in a weight ratio of 70/30 ~ 30/70.
[0030]
　Further, (hereinafter also referred to as "the present composition 2".) The thermoplastic elastomer composition 2 according to an embodiment of the present invention,
　the the resin (A), the
　structural unit derived from (B) ethylene, carbon atoms 3 - and a structural unit derived from at least one selected from 20 α- olefin,
　the glass transition temperature is at -110 ~ -20 ° C.,
　a melt flow rate (ASTM D1238E, 190 ℃, 2.16kg load ) is also referred to as 0.1 ~ 10 g / 10 min at which olefin resin (hereinafter "resin (B2)".), and
　the copolymer and (C),
the resin (B2) / the copolymer ( wherein a rate of 100 / 0-1 / 99 in a weight ratio of C), and
　the resin (a) / (the resin (B2) + copolymer 70 / 30-30 weight ratio of (C)) / 70 is a composition in a proportion of,
the composition,
　the bending bullet Is 200 ~ 1000 MPa sex ratio (ASTM D790), and
　elongation at break of -40 ℃ (JIS K6251) is 50 to 600%.
[0031]
　Hereinafter, in conjunction the composition 1 and the composition 2, also referred to as the present composition, together with the resin (B1) and the resin (B2), referred to as resin (B).
[0032]
　In the present composition, said the resin (A), the weight ratio of the total amount of the resin (B) and copolymer (C) ((A) / [(B) + (C)]) is 70 / 30 to 30/70, preferably 65 / 35-35 / 65, more preferably 60 / 40-40 / 60. By the weight ratio is in the range, the composition is excellent in balance between strength and flexibility, in particular exhibits a suitable performance as various products such as automobile interior materials.
[0033]
　In the present composition, the resin (B) and copolymer (C) and the weight ratio of ((B) / (C)) is 100 / 0-1 / 99, preferably 100 / 0-10 / 90 , more preferably 90 / 10-30 / 70. By the weight ratio is in the range, the composition is considered a low-temperature characteristics and mechanical properties derived from the resin (B) is desirably developing, the composition, elongation and impact resistance at low temperatures excellent, particularly excellent in impact resistance at low temperatures.
[0034]
　Flexural modulus was measured according to ASTM D790 of the composition 2 is not particularly limited as long as the effect of the present invention, in terms of equal is suitable to the airbag cover is 200 ~ 1000 MPa, the composition flexural modulus of things, more preferably not more than 650 MPa, more preferably less than than 100 MPa 600 MPa, particularly preferably not more than 500MPa or more 300 MPa. By flexural modulus is in the above range, preferred compositions having flexibility are obtained, which composition can be used particularly suitably for various products such as automobile interior materials.
　Flexural elastic modulus can be specifically measured by the method described in the following Examples.
[0035]
　Elongation at break at -40 ℃ was measured according to JIS K6251 of the composition 2 is 50 to 600%, elongation at break at -40 ℃ of the composition, more preferably from 50 to 550 %, more preferably 50 to 500%.
　Composition is elongation at break at -40 ℃ in said range, said to be a composition particularly excellent in elongation at low temperatures, and in a wide temperature range from low to high temperatures, the cover is abnormal destruction scattering it can be suitably used for an air bag cover which can be prevented from.
　Elongation at break of at the -40 ℃ can be specifically measured by the method described in the following Examples.
[0036]
　[Crystalline olefin resin (A)]
　The present composition contains a resin (A). By including the resin (A), the it is possible to obtain a composition excellent in fluidity and heat resistance.
[0037]
　Resin (A) is not particularly limited as long as it is a crystalline polymer obtained by using an olefin, one or more mono-olefins, crystalline obtained by polymerizing by either high-pressure or low-pressure process it is preferably a high molecular weight solid product. Examples of such polymers, isotactic monoolefin polymers, syndiotactic monoolefin polymers, and the like.
[0038]
　Resin (A) may be obtained by synthesis by a conventional method, it may be a commercially available product. Resin (A) may be used alone, or two or more may be used.
[0039]
　The monoolefin as a raw material for resin (A), the ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1 - pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and the like. These olefins may be used alone, or two or more may be used. Further, polymerization mode is also a block type in a random type, no problem be adopted any polymerization mode as long resulting crystalline resin like material.
[0040]
　The resin (A), melting point (Tm) measured by differential scanning calorimetry (DSC) is not less 100 ° C. or higher, preferably 105 ° C. or higher. By melting point of the resin (A) (Tm) is 100 ° C. or more, the resulting composition has excellent mechanical properties and heat resistance.
[0041]
　Differential scanning calorimetry is performed, for example, in the following manner.
　Packed about specimen 5mg dedicated aluminum pan, Inc. Perkin Elmer of DSCPyris1, using DiamonsDSC or DSC7, heated at 320 ° C. / min from 30 ° C. to 230 ° C., then held at 230 ° C. 10 minutes, 230 ° C. up to 30 ° C. and cooled at 10 ° C. / min from and held for a further 5 minutes at 30 ° C., then determine the melting endothermic curve at the time of raising the temperature at 10 ° C. / min. At the time of DSC measurement, if multiple peaks are detected, to define the peak temperature detected by the highest temperature side as the melting point (Tm).
[0042]
　The melt flow rate of the resin (A) (MFR, ISO1133,230 ℃, 2.16kg load) lower limit, it is preferably a 0.1 g / 10min, more preferably 1 g / 10min, more preferably 5 g / 10min, the upper limit it is 500 g / 10min, more preferably 100 g / 10min, still more preferably 80 g / 10min.
[0043]
　The resin (A), the following propylene resin (A-1) are particularly preferred from the viewpoint of the composition can be easily obtained superior mechanical properties and economical efficiency such as stiffness and hardness.
[0044]
　Propylene resin (A-1) is either a homopolymer of propylene or a copolymer of propylene and at least one selected from α- olefins ethylene and 4 to 20 carbon atoms.
　For propylene copolymers, the content of structural units derived from propylene in the copolymer relative to the total constituent units 100 mol%, preferably 40 mol% or more, more preferably 50 mol% or more. As the copolymer, a random copolymer, may be a block copolymer. Propylene resin (A-1) is polymerized in a conventional Ziegler-Natta catalyst.
[0045]
　Specific examples of the α- olefin having 4 to 20 carbon atoms described above, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2 - ethyl-1-butene, 2,3-dimethyl-1-butene, 1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl 1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-dec , 1-undecene, and 1-dodecene.
　The α- olefin of the ethylene and 4 to 20 carbon atoms, ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene are preferably used. These may be used alone, or two or more may be used.
[0046]
　Examples of the propylene-based resin (A-1), can be used from commercially available propylene-based resin is not particularly limited. Examples of commercially available propylene-based resin, a so-called homo-polypropylene resin, random polypropylene resins, block polypropylene resins.
[0047]
　The following describes preferred embodiments of the propylene-based resin (A-1).
　Propylene resin (A-1) has a melt flow rate (MFR, ISO 1133 ° C., 2.16 kg load), preferably 0.1 ~ 500 g / 10 min. The lower limit is preferably 0.2 g / 10 min, more preferably from 0.3 g / 10 min, the upper limit is preferably 300 g / 10 min, more preferably 100 g / 10 min, particularly preferably 70 g / 10 a minute. Dispersion of MFR of the propylene-based resin (A-1) is, if 0.1 g / 10 min is less than a propylene-based resin of the composition (A-1) and resin (B) and the copolymer (C) may sex is deteriorated, the mechanical strength of the composition may be reduced. If MFR of the propylene-based resin (A-1) is greater than 500 g / 10 min, the propylene-based resin (A-1) intensity of itself is lowered, the mechanical strength of the composition may become low.
[0048]
　MFR is the molecular weight of the index of the propylene-based resin (A-1), propylene resin (A-1) had a weight average molecular weight of the polypropylene in terms determined by gel permeation chromatography (GPC) (Mw) is, preferably 80,000 to 900,000, more preferably 100,000 to 700,000, particularly preferably from 150,000 to 700,000.
[0049]
　Tensile modulus of the propylene-based resin (A-1) is not particularly limited as long as the effect of the present invention is preferably 500 ~ 3000 MPa, more preferably 600 ~ 2500 MPa, more preferably 650 ~ 2200 MPa. Tensile modulus, in compliance with JIS K7113-2, is a value obtained by measuring the pressed sheet 2mm thick at 23 ° C.. The compositions tensile modulus comprising propylene-based resin (A-1) in the above range has a higher rigidity and high hardness.
[0050]
　[Olefin resin (B)]
　The resin (B), satisfies the following requirements (B-1) ~ (B -3).
　By including the resin (B), excellent in elongation at low temperatures, it is possible to further obtain a composition having excellent impact resistance at low temperatures (especially -45 ° C.).
　Resin (B) may be used alone, or two or more may be used.
[0051]
　
　resin (B) comprises a graft polymer [GP]. Graft polymer [GP] has a backbone that is the ethylene copolymer (MC) and a side chain of an olefin polymer (SC), the requirements (i) and (ii) Fulfill.
　Incidentally, the term "graft polymer" in the present invention means that the T-type polymers or comb polymers having one or more side chains to the main chain of the polymer.
[0052]
　
　ethylene polymer constituting the main chain (MC) is a repeating unit derived from ethylene, derived from at least one α- olefin selected from α- olefin having 3 to 20 carbon atoms including a repeating unit. Repeating units derived from the α- olefin, based on the total repeating units contained in the main chain (MC), preferably in the range of 10 ~ 50 mol%.
　When graft polymer [GP] has such a main chain (MC), to obtain the present composition having excellent mechanical properties such as flexibility and impact resistance at low temperatures is required easily.
[0053]
　Examples of α- olefins having 3 to 20 carbon atoms include propylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3 dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, ethyl-1-hexene , dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene 1-decene, 1-undecene, 1-dodecene, and the like. These olefins may be used alone, or two or more may be used.
[0054]
　Preferably, an α- olefin having 3 to 10 carbon atoms, more preferably a α- olefins having 3 to 8 carbon atoms. Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, linear olefins such as 1-decene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3 - it includes branched olefins methyl-1-butene and the like. Of these, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene are preferred, 1-butene, 1-pentene, 1-hexene, 1-octene are more preferable.
　Ethylene copolymerized with 1-butene as α- olefin having 3 to 20 carbon atoms, 1-pentene, 1-hexene or 1-octene by using, most excellent in low temperature characteristics, at low temperatures elongation and impact resistance the compositions can be obtained more excellent balance of physical properties.
[0055]
　The proportion of the repeating units derived from ethylene in the backbone of the graft type polymer [GP], based on all repeating units contained in the main chain, preferably 50 ~ 90 mol%, more preferably 60 ~ 85 mol%, further preferably 65 ~ 78 mol%. The proportion of repeating units derived from α- olefin, based on all repeating units contained in the main chain, preferably 10 ~ 50 mol%, more preferably 15 ~ 40 mol%, more preferably 22 ~ 35 mol% .
　Note that "the main chain" means the percentage of time that a 100 mole% of all repeating units contained in the main chain.
[0056]
　By molar ratio of repeating units derived from ethylene and α- olefin in the main chain is in the above range, the resin (B) is flexible, because it has a property of excellent low-temperature characteristics, the resin (B) the composition comprising the more excellent low-temperature impact resistance. On the other hand, when the repeating units derived from α- olefin is below the range, there may be obtained a resin (B) is a resin inferior in flexibility and low temperature properties, the composition comprising the resin is low-temperature impact resistance It tends to be inferior to. Further, if the molar ratio of repeating units derived from α- olefin exceeds the above range, since adversely act upon the copolymerization of macromonomers to form a later-described side chain, by graft type polymer described below [GP] effect is hardly exhibited, they tend to be compositions having poor balance between the impact resistance and other mechanical properties.
[0057]
　Molar ratio of repeating units derived from ethylene and α- olefin in the main chain, by controlling the ratio of the concentration of α- olefin concentration of ethylene is present in the polymerization reaction system in the process of manufacturing the main chain It can be adjusted.
[0058]
　The molar ratio of repeating units derived from α- olefin contained in the main chain (mol%), i.e. α- olefin composition in the main chain, for example, do not contain terminal unsaturation polypropylene or terminal unsaturation polyethylene described later or be obtained by a conventional method alpha-olefin composition of the ethylene · alpha-olefin copolymer obtained under the condition, the side chain of the alpha-olefin composition of the resin (B), terminal unsaturated polypropylene and terminally unsaturated polyethylene ( obtained from subtracting the influence derived from the SC).
[0059]
　
　side chain (SC) is at least one selected from consisting side chains (SP) from consisting side chains (SE) and propylene polymer from ethylene polymer, preferably ethylene it is composed sidechain (SE) from the polymer. Side chain (SC) is a resin the side chain (SE) and / or side chain (SP) (B), in order to have a suitable mechanical strength, the composition comprising the resin (B) is better with a balance of physical properties such. Further, the side chain (SC) is a resin the side chain (SE) and / or side chain (SP) (B), because the stickiness is reduced, by using the resin (B), the pellet handling properties excellent, excellent in economical efficiency in the formulation process. In particular side chain (SC) if a side chain (SE), the characteristic is expressed significantly.
[0060]
- side chains (SC) if a side chain (SE)
　side chain (SC) is the case of the side chain (SE), satisfies any one or more of the following requirements (iii) ~ requirement (v) it is preferable to have, it is more preferable to satisfy all the requirements of the requirements (iii) ~ requirement (v).
[0061]
　
　side chain (SC) is a side chain (SE), the repeating units derived from ethylene, and if necessary to guide the at least one selected from α- olefin having 3 to 20 carbon atoms includes repeating units wither, content of units derived from the ethylene is based on all the repeating units 100 mol% contained in the side chain (SE), preferably in the range of 95 ~ 100 mol%. Content of units derived from said ethylene, more preferably 98 ~ 100 mol%, more preferably from 99.5 ~ 100 mol%.
[0062]
　The α- olefin having 3 to 20 carbon atoms, is the same as the olefin mentioned in the section of the requirements (i). By the content of units derived from ethylene is in the range, the side chain (SE) is the crystalline ethylene polymer chains. By the side chain (SE) is crystalline, distinguished by the resin (B) is sticky reduced handling, excellent in heat resistance as an adhesive resin, and a suitable elasticity modulus. Further, the resin (B) is mixed with resin (A), the it is possible to obtain a composition excellent in balance between rigidity and low-temperature impact resistance.
[0063]
　
　The weight average molecular weight of the ethylene polymer constituting the side chains (SE) (Mw) is preferably 500 to 30,000, more preferably 1,000 to 10,000.
　If the Mw is below 500, reduces the melting point derived from the side chain (SE), the resin tends to physical crosslinking points weakening crystal components form of (B), of the composition comprising the resin (B) there is a possibility that mechanical properties is reduced. On the other hand, if the Mw exceeds 30,000, the relative amounts of amorphous or low crystalline component comprising an ethylene copolymer portion in the backbone (MC) tends to decrease, has sufficient flexibility and impact resistance it may not be possible to obtain a composition.
[0064]
　Incidentally, Mw ethylene polymer constituting the side chains (SE) is an ethylene polymer which corresponds to the separated side chain as the eluting components of the low quantity side (SE) in GPC (macromonomers), or are previously synthesized It was, by performing the GPC analysis of the ethylene polymer which corresponds to the side chain (SE) (macromonomers), that is, obtains a weight average molecular weight of terminally unsaturated polyethylene produced in the following step (B) by GPC measurement.
[0065]
　As a method for adjusting the Mw of the ethylene polymer constituting the side chains (SE), a method of changing the type of transition metal compound used for the later-described terminal unsaturation polyethylene generating catalyst, and a method of adjusting the polymerization conditions and the like.
[0066]
　
　the side chain of the graft type polymer [GP], the carbon atom per 1000 backbone polymer molecular chain, preferably present at 0.5 to 20 average frequency, more preferably 0.5-15 amino average frequency, more preferably is present from 0.5 to 10 average frequency.
[0067]
　By using a resin in which the side chain is introduced into the main chain at an average frequency of the range (B), it is possible to surface hardness is high and obtain the present composition excellent in high impact while maintaining rigidity.
　On the other hand, if it is introduced into the main chain at an average frequency of side chains falls below the above range, there is a tendency that the effect of physical cross-linking points due to the side chains is reduced, the composition containing the resin, the rigidity and hardness there is a case to be lowered. Also, if the side chain is introduced into the main chain at an average frequency of more than the above range, since there is a tendency that the relative amounts of crystalline component comprising an ethylene polymer portion increases, the composition containing the resin, resistant in some cases the impact resistance is lowered.
[0068]
　Method for calculating the average frequency of the side chains, for example, below, [a] carbon isotope nuclear magnetic resonance spectra ( 13 process according to a method using a C-NMR) or,, [b] Gel permeation chromatography (GPC) it can be used.
[0069]
　[A] graft polymer [GP] may include a repeating unit backbone derived from ethylene, a repeating unit derived from at least one α- olefin selected from α- olefin having 3 to 20 carbon atoms isotope carbon nuclear magnetic resonance spectra ( 13 joint portion as measured by C-NMR), apart from the methine carbon derived from the α- olefin in the range of 37.8 ~ 38.1ppm, a side chain and the main chain it is preferred that the signal which can be attributed to the methine carbon is observed.
　If the signal is observed, it is possible to obtain a side chain average frequency by the following expression.
　[Side chain average frequency] = 1000 × [I PE-Methine ] / {[I all-C ] × (100- [R2 '] - [M]) /
　100}; [I PE-Methine ]: and a side chain integral value of the methine carbons of the joint portion of the main chain
　[I all-C ]: total carbon the integral value
　[R2 ']: graft polymer [GP] other than the polymer by-produced during the production of [R2] resin (B weight ratio)
　(wt%) [M]: weight ratio of graft polymer [GP] macromonomers added or generated during the production resin (B) (wt%)
　Incidentally, the graft polymer [GP] other than the polymer by-produced during production [R2], is added as the time of polymerization refers to a component such as from a scavenger-catalyst species. Because usually, component [R2] In contrast, graft polymer produced [GP] amount overwhelmingly large, the amount of [R2] can be regarded as zero.
[0070]
　[B] As described above, the resin peak on the low molecular weight side obtained when analyzed by (B) a gel permeation chromatography (GPC), a copolymer remained without copolymerization during the reaction the ethylene polymer (macro derived from a monomer). Therefore, the area ratio of the remained without copolymerized with the resin (B) ethylene polymer, can be determined the weight ratio of the remaining macromonomer contained in the resin (B). Graft polymer [GP] If the addition or composition by weight of the macromonomer produced during manufacture is evident, it is possible to determine the side chain average frequency from the difference between the weight ratio of the macromonomer remaining with its composition by weight. Specifically, it can be determined by the following equation.
　[Side chain average frequency] = {([M] - [M ']) / (100- [M'])} × (1 / [Mn -M ]) × [14 / {1 - ([M] - [M ']) / (100- [M'])}] ×
　(1/1000); [M]: graft polymer [GP] graft-type polymer of the macromonomer to be added or generated during the production [GP] resin obtained at the time of manufacture (B) weight ratio of the total amount (wt%) [M
　']: graft polymer remaining macromonomer obtained from GPC [GP] resin obtained at the time of manufacture (B) weight ratio of the total amount (
　% wt) [Mn -M ]: number average molecular weight of the macromonomer (Mn)
[0071]
　Incidentally, the method [a], the average frequency which is determined by [b], if by-produced resin (B) other than the ethylene · alpha-olefin copolymer are present, the copolymer side chains number 0 present is the value when the counted as.
[0072]
　The number of side chains can be adjusted by controlling the molar concentration of the macromonomer in the polymerization system. For example, in certain polymerization conditions, when a predetermined side chain molecular weight, allowing a larger charge weight or product weight of the macromonomer, the molar concentration of the macromonomer is increased, the side of the graft polymer [GP] to produce chain number is increased. Furthermore, when the charged weight or product weight of the macromonomer is constant, by decreasing the side chain molecular weight, the molar concentration of the macromonomer is increased, increasing the side chain number in graft polymer [GP] to produce be able to.
　Further, by selecting the type described transition metal compound (A), it is possible to adjust the side chains number of graft polymer [GP], for example, shows a high copolymerization at high temperatures, high molecular weight by selecting the olefin polymerization catalyst comprising a transition metal compound capable of generating a polymer may increase the side chain number.
[0073]
• If the side-chain (SC) is a side chain (SP)
　side chain (SC) is, when the propylene polymer consists side chains (SP), one of the following requirements (vi) and requirements (vii) it is preferable to satisfy one or more or, more preferably satisfies the requirements (vi) and requirements (vii).
[0074]
　
　side chain (SC) is a propylene composed side chains of the polymer (SP), a repeating unit derived from propylene, optionally ethylene and carbon atoms 4 ~ 20 alpha- and a repeating unit derived from at least one selected from olefins, based on all repeating units 100 mol% of the content of recurring units derived from the propylene contained in the side chain (SP), preferably 95 ~ 100 mol is the percent of the range. The content of the repeating units derived from the propylene, more preferably 99.5 ~ 100 mol%.
　By content of repeating units derived from propylene is in the range, the side chain (SP) is a crystalline propylene polymer chains. Resin (B) by the side chain (SP) is crystalline excellent handling, by using the resin (B), to obtain the present composition more excellent balance between rigidity and low-temperature impact resistance.
[0075]
　In the side chain (SP), ethylene and propylene than the α- olefins within a range not to impair the role and characteristics may be small amounts copolymerized. The α- olefin having 3 to 20 carbon atoms, is the same as the olefin mentioned in the section of the requirements (i).
[0076]
　
　The weight average molecular weight of the propylene polymer constituting the side chains (SP) (Mw) is preferably 5,000 to 100,000, more preferably 5,000 to 60,000, more preferably 5,000 to 25,000.
　The present composition Mw of the propylene polymer constituting a side chain (SP) is blended with the resin (B) in the above range, while retaining the hardness and rigidity, excellent in impact resistance at low temperatures. And Mw of the propylene polymer is less than 5,000 which constitutes a side chain (SP), the hardness and rigidity of the resulting composition is a risk decreases. And Mw of the propylene polymer is greater than 100,000 which constitutes a side chain (SP), may cause the fluidity and workability deterioration during molding of the resulting composition, also amorphous or low crystalline component because of the relative decreases, there is a possibility that flexibility of the resulting composition, elongation and impact resistance is lowered.
[0077]
　Mw of the propylene polymer constituting a side chain (SP) is the weight average molecular weight of terminally unsaturated polypropylene produced in the following step (A) can be obtained by measuring at an ordinary method. For example, a weight average molecular weight of the polypropylene in terms of the terminally unsaturated polypropylene obtained by GPC, can be used as a weight-average molecular weight of the propylene polymer constituting the side chains.
　The method of adjusting the weight average molecular weight of the propylene polymer constituting the side chains (SP), in the process described below (A), a method, and the like to adjust the polymerization temperature and polymerization pressure.
[0078]
　
　The resin (B), in differential scanning calorimetry (DSC), preferably there is a melting point (Tm) in the range of 60 ~ 170 ° C.. That is, the resin (B) has a melting peak measured by DSC in the range of 60 ~ 170 ° C..
　The melting peak appears temperature, i.e. the melting point (Tm), after sample was melted by a single heating step by DSC, is crystallized by cooling step to 30 ° C., the second time heating process (heating rate 10 ° C. / min) is obtained by analyzing the endothermic peak observed during. Specific differential scanning calorimetry may see the method described in Example.
[0079]
　In a preferred embodiment described above, the side chain (SC) if a side chain (SE), the melting point due to the side chain (SE) is observed usually in the range of 60 ~ 130 ° C.. Resin having a melting point attributable to the side chain (SE) is in the range (B), while retaining the hardness and rigidity by a physical crosslinking point to which the crystalline component is formed, also has high impact resistance at low temperatures. Also, by melting due to the side chain (SE) is in the range, has heat resistance, and, since the resin stickiness is reduced (B) is obtained, by using the resin (B) , in the preparation of this composition, excellent pellet handling properties, excellent in economical efficiency in the formulation process.
　As a method of adjusting the melting point due to the side chain (SE) to the range, in a step described later (B), a method, and the like to adjust the polymerization temperature and polymerization pressure.
[0080]
　Side chain (SC) is, if a side chain (SP), the melting point due to the side chain (SP) is observed usually in the range of 100 ~ 170 ° C.. Resin having a melting point attributable to the side chain (SP) is in the range (B), as in the case of the side chain (SE), while retaining the hardness and rigidity, also have high impact resistance at low temperatures, heat also excellent in sex.
　As a method of adjusting the melting point due to the side chain (SP) in the range, in a step described later (A), a method, and the like to adjust the polymerization temperature and polymerization pressure.
[0081]
　
　resin (B1) is in the observed range of the glass transition temperature (Tg) of -80 ~ -30 ° C. in the DSC, the resin (B2), it Tg observed in DSC It is in the range of -110 ~ -20 ℃. Tg is primarily due to the nature of the ethylene-based polymer constituting the main chain of the graft type polymer [GP] (MC). Tg is, the composition containing a resin (B) in the above range, expresses good impact resistance at low temperatures.
[0082]
　Tg of the above range can be obtained by controlling the type and composition of which is α- olefin constituent unit contained in the ethylene-based polymer constituting the main chain (MC). Specific determination method can be referred to examples.
　The resin (B) preferably satisfy further the following requirements (B-4).
[0083]
　
　The resin (B), the intrinsic viscosity [eta] measured in a 135 ° C. decalin, preferably in the range of 0.1 ~ 12 dl / g, more preferably 0.2 to 10 dl / g, more preferably from 0.5 ~ 5dl / g. [Eta] is the composition comprising the resin (B) in the above range exhibits good rigidity and mechanical strength, also compatible better moldability.
[0084]
　In a preferred embodiment described above, when the side chain (SC) is a side chain (SE), resin (B), it is preferable to satisfy any of the following requirements (B-5) and (B-6), further following requirement (B-5) and it is more preferable to satisfy (B-6) at the same time, it is particularly preferred that meets further requirements (B-7).
[0085]
　
　melting point as measured by DSC of the resin (B) (Tm) is preferably 80 ~ 130 ° C., more preferably 80 ~ 125 ° C., more preferably 90 ~ 120 ° C..
　Also, the heat of fusion ΔH calculated from a melting peak area, preferably 5 ~ 100 J / g, more preferably 5 ~ 80 J / g, more preferably 5 ~ 70 J / g, particularly more preferably at 8 ~ 60 J / g is there.
[0086]
　Tm and ΔH observed in the range is mainly derived from the ethylene polymer is a side chain (SC) of the graft polymer constituting the resin (B) [GP], Tm and ΔH is the range there by using the resin (B), the composition can be easily obtained which is excellent by the balance between rigidity and low-temperature impact resistance. On the other hand, if the Tm or ΔH is below the range, there is a tendency that the rigidity of the resulting composition is lowered. Also, if the ΔH exceeds the range, there is a tendency that the impact resistance of the resulting composition is lowered.
[0087]
　
　ratio (E value) of the measured 20 ° C. less orthodichlorobenzene-soluble content by cross fractionation chromatography (CFC) of the resin (B) is preferably not more than 45 wt%, more preferably not more than 35 wt%, more preferably not more than 30 wt%. The lower limit is not particularly limited, but is usually 5 wt%. Specific determination method can be referred to examples.
[0088]
　Usually, a commercially available ethylene · alpha-olefin copolymer, such as ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-octene copolymers, propylene, 1-butene or 1-octene a polymer composition of the α- olefin is adjusted to be about 10 ~ 50 mol% of an equal, it shows an amorphous or low crystalline, readily soluble to a specific organic solvent in a temperature below room temperature. For example, a commercially available ethylene / 1-butene copolymer, for example, TAFMER A-5055S (manufactured by Mitsui Chemicals Co., Ltd.) is the most relative to the 20 ° C. or less ortho-dichlorobenzene soluble, E value is typically 93 or more percent.
[0089]
　On the other hand, the main chain while an ethylene copolymer as described above (ethylene · alpha-olefin copolymer), graft polymer side chain is a crystalline ethylene polymer [GP] is lower at room temperature the poorly soluble in o-dichlorobenzene. Therefore polymer [GP] is characterized in that E value is small.
[0090]
　That E values ​​of the resin (B) is small, an indirect evidence that the backbone structure and side chain structure of the graft polymer [GP] is chemically bonded, further resin (B graft polymer [GP] indicates that it contains significant amounts). The content of the graft polymer contained in the resin (B) [GP] is not particularly limited as long as the effect of the present invention, preferably 10 ~ 100 wt%, more preferably 20 ~ 90 wt%.
[0091]
　In this composition, the resin (B) is generally similar to the commercially available ethylene · alpha-olefin copolymer used as a modifier, dispersed in the resin (A), the grant to improve impact resistance It is thought to play a role in. Here a case of using only commercially available ethylene · alpha-olefin copolymer, although the impact resistance is improved depending on the amount, the original rigidity and mechanical strength resin (A) is lowered. On the other hand, in the case of using the resin (B1), the side chain of the graft type polymer in domain ethylene · alpha-olefin copolymer to form [GP] forms a physical crosslinking point, a high stiffness to the domain itself , hardness, born mechanical strength, as a result, the composition not only excellent remarkably in impact resistance at low temperature, is presumably excellent in the balance between rigidity. Thus, the graft polymer [GP] is included considerable amount in the resin (B1) is preferred for demonstrating a good balance of physical properties in the present compositions.
[0092]
　In view of such a composition is excellent due to a balance between the impact resistance and rigidity can be easily obtained, the resin ΔH and E value and is less than the (B) (a), (b), (c it is preferable to satisfy one of relations).
[0093]
　(A) [Delta] H is 5 J / g or more, of less than 15 J / g, E value is less 45 wt%, preferably less 40 wt%, more preferably 10 ~ 35 wt%.
　(B) [Delta] H is 15 J / g or more, of less than 30 J / g, E value is less 40 wt%, preferably less 35 wt%, more preferably 5 ~ 30 wt%.
　(C) If ΔH is more than 30 J / g, E value is less 33 wt%, preferably not more than 31 wt%.
[0094]
　Said relationship is satisfied, because the content of graft polymer contained in the resin (B) [GP] indicates that sufficiently large, by using the resin (B), rigidity and low-temperature impact resistance it can be obtained of more excellent the composition balance easily.
[0095]
　If the relationship is not satisfied, that is, the E value increases, the content of graft polymer contained in the resin (B) [GP] is not sufficient, the ethylene · alpha-olefin copolymer and ethylene polymer or propylene heavy It becomes properties such as a polymer blend of coalesced, the sometimes becomes difficult to exhibit a good balance of physical properties described.
　For example, [Delta] H is 5 J / g or more, as in the case of less than 15 J / g, a side chain component amount, especially when the ethylene polymer component amount is small, the E value exceeds the 45 wt%, the existing ethylene · alpha - closer to the performance in the case of using the olefin copolymer, the case of using the resin, the impact resistance is likely to is improved it becomes compositions not excellent rigidity. Also, as in the case ΔH is 30 J / g or more, the side chain component amount, especially when the ethylene polymer component amount is relatively large, E value exceeds the 33 wt%, was not incorporated into the main chain side chain component, the number of especially ethylene polymer component, the case of using the resin, the resulting composition is not only inferior in impact resistance, rigidity may be reduced significantly.
[0096]
　As already explained, the ethylene · alpha-olefin copolymer crystalline ethylene polymer site resins containing significant amount of components that are chemically bound (B) is the aforementioned requirements (B-5) requirements and (B-6) can be satisfied simultaneously. To obtain such a resin, a catalyst can be obtained by selecting appropriately used in the step of copolymerizing ethylene and α- olefin and terminal vinyl ethylene polymer, examples of the catalyst, the transition metal compound described later even bridged metallocene compound in the (C) [C] is preferred.
[0097]
　
　in conformity with ASTM D1238E resin (B), 190 ℃, melt flow rate as measured at 2.16kg load the (MFR) and M (g / 10min), of 135 ° C. decalin the measured intrinsic viscosity [eta] when the H (dl / g) in the middle, the value a represented by the following equation (Eq-1), preferably 30 to 280 and more preferably 60-250 range, more preferably from 70-200.
　A = M / exp (-3.3H) ··· (Eq-1)
[0098]
　That the resin (B) has an A value of this range indicates that high side chain (macromonomer) introduction rate, requirement (B-7) Resin (B) satisfying the resin ( even when incorporated into a), preferable since it is difficult to cause the deterioration of physical properties such as rigidity of the macromonomer and the non-grafted polymer remaining will cause.
[0099]
　
　in conformity with ASTM D1238E resin (B), 190 ℃, MFR measured at 2.16kg load, preferably 0.1 ~ 10 g / 10min, more preferably 0.1 ~ 8.0g / 10min, more preferably 0.1 ~ 6.0g / 10min, particularly preferably 0.2 ~ 4.0g / 10min.
　If MFR of the resin (B) is in the range, tensile tend expressing elongation and impact resistance excellent effect, by using the resin (B), excellent in mechanical properties and moldability such as rigidity it is possible to obtain a composition.
[0100]
　[Olefin other properties of the resin (B)]
　- modulus
　elasticity of the resin (B) is not particularly limited as long as the effect of the present invention, preferably 2 ~ 120 MPa, more preferably 3 ~ 100 MPa, more preferably is 5 ~ 90MPa. The composition comprising the resin (B) elastic modulus is in the above range, more excellent balance between rigidity and impact resistance.
　Resin (B) is rich in flexibility since the main chain structure of the graft-type polymer [GP] is composed of the ethylene · alpha-olefin copolymer. That is, the composition comprising a resin (B) is favorably expressing the impact resistance.
　The elastic modulus in the present invention is a tensile elastic modulus conforming to ASTM D638.
[0101]
　- phase separation structure
　resin (B) is preferably a phase showing a crystalline component observed by a transmission electron microscope (TEM) is a non-continuous phase order of micrometers. Incidentally, observation whether it has a phase structure described above, for example, carried out as follows.
[0102]
　First, the resin (B), using a hydraulic hot press molding machine preset at 170 ° C., after heating for five minutes, after molding by pressurizing one minute at 10MPa, 3 minutes under a pressure of 10MPa at 20 ° C. obtaining a specimen by making a pressed sheet having a predetermined thickness by cooling. The test piece was a small piece of 0.5mm square, ruthenate (RuO 4 stained with). Further ultramicrotome equipped with a diamond knife, and the thickness of ultrathin sections of about 100nm and the resulting pieces. The ultra-thin section by depositing carbon and observed with a transmission electron microscope (accelerating voltage 100 kV).
[0103]
　According to the observation method, the side-chain ethylene polymer component graft polymer [GP] Since intercrystalline amorphous region of lamellar structures formed by the said components is dyed selectively ruthenate, higher contrast It is observed as.
[0104]
　Resin (B) is preferably a phase showing a crystalline component consisting of the side chain ethylene polymer of the thus graft-type polymer to be observed [GP] is a non-continuous phase of the order of micrometers.
　Resin graft polymer non-crystalline or low-crystalline main-chain crystalline side chain linked covalently to [GP] mainly (B) is compatible effect of an amorphous component and a crystalline component is large, believed to microphase separation structure as described above for this is formed.
[0105]
　The discontinuous phase observed in the resin (B) is a physical crosslinking points consisting of the side chain ethylene polymer, also the physical crosslinking in ethylene · alpha-olefin copolymer domains which are formed in the composition considered point is formed. Therefore, the by using the resin (B) having a non-continuous phase, it is contemplated that the composition excellent in balance between rigidity and low-temperature impact resistance can be easily obtained.
　On the other hand, when using the polymer blends of ethylene · alpha-olefin copolymer and ethylene polymer, microphase separation structure as described above is not formed, coarse crystal phase is observed. Therefore, in the composition using the polymer blend, physical crosslinking points in the olefin copolymer domains are not formed, tend to not be able to obtain a composition exhibiting excellent property balance.
[0106]
　
　The resin (B), for example, the following steps (A) and / or step (B), followed by a step (C), optionally steps (D) produced by the process comprising the steps.
[0107]
　Step (A): (. Hereinafter also referred to as "transition metal compound [A]") dimethylsilyl bis-indenyl Group 4 of the periodic table compounds of transition metals containing a ligand having a skeleton [A] for olefin polymerization comprising polymerizing propylene in the presence of a catalyst, a process for producing a terminally unsaturated polypropylene
　step (B): phenoxyimine group 4 of the periodic table having an amine ligand or a group V compound of a transition metal of [B] (hereinafter " . also referred to as a transition metal compound [B] ") polymerizing ethylene in the presence of an olefin polymerization catalyst comprising the steps of producing a terminally unsaturated polyethylene
　step (C): group 4 of the periodic table transition metal compound [C (hereinafter referred to as "transition metal compound [C]".) in the presence of an olefin polymerization catalyst comprising, prepared in step (a) produced in the terminally unsaturated polypropylene and / or step (B) An end unsaturated polyethylene, and ethylene copolymerized with at least one α- olefin selected from α- olefin having 3 to 20 carbon atoms, an olefinic resin (B) comprising a graft-type polymer [GP] production to process
　step (D): step (a), (B) or (C) after each step of optionally recovering the polymer produced in each process
[0108]
　Incidentally, when the side chain (SC) to produce a graft-type polymer is a side chain (SE) [GP] may be carried out the step (B) and the step (C) at the same time. The enabling said step (B) and the step (C) and at the same time, an olefin polymerization catalyst comprising a transition metal compound [B], even in conditions where the comonomer such as ethylene and α- olefin coexist, ethylene selectively polymerizing is because it generates a terminal unsaturation polyethylene. It is carried out the step (B) and the step (C) and at the same time, preferably also on the simplification of the manufacturing process.
[0109]

　Step (A) is a process for manufacturing the raw material to become terminally unsaturated polypropylene graft polymer composed side chains of propylene polymer in the [GP] (SP).
　The A terminal unsaturation polypropylene means a polypropylene having unsaturated end represented by the following terminal structure (I) ~ (IV). "Poly" in the terminal structure (I) ~ (IV) shows the terminal structure, the coupling position of the propylene polymer molecule chains other than said distal end structure.
[0110]
[Formula 1]

[0111]
　Proportion of unsaturated terminal in the terminal unsaturated polypropylene, total carbon atoms per 1000 of the propylene polymer, but is usually from 0.1 to 10, more preferably from 0.4 to 5.0 units. Furthermore, the proportion of unsaturated terminal represented by general end structure called terminal vinyl (I), so-called terminal vinyl amount, total carbon atoms per 1000 of the propylene polymer, usually 0.1-2.0 units although, preferably, 0.2-2.0, more preferably 0.4-2.0 units. When a terminal vinyl amount is small, the amount of introduced into the backbone of the terminally unsaturated polypropylene is reduced in step (C), since the amount of graft polymer [GP] is reduced, no desired effect can be obtained If there is a.
[0112]
　The unsaturated terminal of quantification the terminal structure of terminally unsaturated polypropylene 1 is determined by determining by H-NMR. 1 H-NMR can be measured according to a conventional method. Assignment of the terminal structure may be carried out according to the method described in Macromolecular Rapid Communications 2000, 1103, and the like.
[0113]
　For example, derived from the end structure (I) δ4.9 ~ 5.1 the integral value of the (2H) A, when the total integrated value derived from a propylene polymer including a terminal structure that is B, per 1000 carbon atoms the proportion of the terminal structure (I) is obtained by the formula of 1000 × [(a / 2) / (B / 2)]. May determine the proportion of other terminal structure, it may be replaced with the integral value of the peak attributable to the structure while paying attention to the ratio of the hydrogen. The proportion of the terminal structure (I) of the unsaturated end is generally 30% or more, preferably 50% or more, more preferably 60% or more. Incidentally, the proportion of the terminal structure (I) of the unsaturated terminal described above, the terminal structure (I) ~ described above present in 1000 per carbon atoms contained in the terminally unsaturated polypropylene respective numbers of (IV) to the sum illustrates a ratio of the number of terminal structures present in 1000 per carbon atom (I) in percentage.
[0114]
　The transition metal compound [A] is to function as a polymerization catalyst for producing the terminally unsaturated polypropylene, the olefin polymerization catalyst used in step (A), the transition metal compound [A] and, later-described compound [D] it is preferably used in combination with.
　As the olefin polymerization catalyst, Resconi, L. JACS 1992, 114, has been known for a long time, etc. 1025-1032.
[0115]
　The side chain of the graft type polymer [GP], isotactic or syndiotactic terminally unsaturated polypropylene, more preferably a suitable isotactic terminally unsaturated polypropylene.
　Such highly stereoregular and is used to produce polypropylene having high terminal unsaturation polypropylene content having a terminal structure (I), the transition metal compound as a [A] is, JP-A 6-100579, JP- Kohyo 2001-525461, JP 2005-336091, JP 2009-299046, JP-a No. 11-130807, JP-preferably used compounds disclosed by JP 2008-285443 Laid be able to.
[0116]
　The More specifically the transition metal compound [A], mention may be made of bridged bis (indenyl) zirconocene compounds and bridged bis (indenyl) hafnocene is selected from the group consisting of class compounds Preferred examples. More preferably, a dimethylsilyl bridged bis (indenyl) zirconocene or hafnocene. More specifically, it can be used as dimethylsilyl bis (2-methyl-4-phenyl indenyl) zirconium dichloride or dimethylsilyl bis (2-methyl-4-phenyl indenyl) zirconium dimethyl suitable compounds.
　Transition metal compound used in step (A) [A] may be one kind, or two or more kinds.
[0117]
　Step (A), gas phase polymerization, slurry polymerization, bulk polymerization, solution (dissolution) is also feasible in any of the methods of polymerization, particularly the polymerization form is not limited.
[0118]
　Step (A) is, if carried out in solution polymerization, as the polymerization solvent, for example, aliphatic hydrocarbons, and aromatic hydrocarbons. Specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosine, cyclopentane, cyclohexane, alicyclic hydrocarbons such as cyclopentane, benzene, toluene, xylene aromatic hydrocarbons such as ethylene chloride, chlorobenzene, and halogenated hydrocarbons such as dichloromethane. These polymerization solvents may be used also well or two or more used alone. Among them, from the viewpoint of the load reduction of post-treatment steps such as step (D), hexane is preferred.
[0119]
　The polymerization temperature in step (A) is usually 50 ~ 200 ° C., preferably 80 ~ 0.99 ° C., more preferably 80 ~ 130 ° C., the polymerization temperature is appropriately controlled, the desired molecular weight and stereoregularity it is possible to obtain a sexual terminally unsaturated polypropylene.
[0120]
　Polymerization pressure of step (A) is generally atmospheric pressure ~ 10 MPa gauge pressure, preferably normal pressure ~ 5 MPa gauge pressure, the polymerization reaction is a batch, semi-continuous, also be carried out in any of the methods of continuous can. Among these, it is preferable to employ a method of performing polymerization by supplying to the reactor a monomer continuously.
[0121]
　The reaction time (average residence time when the copolymerization is carried out by a continuous method), catalyst concentration, varies depending on the conditions such as polymerization temperature, usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours it is.
[0122]
　Polymer concentration in the reaction system of step (A), steady-state operation is 5 ~ 50 wt%, preferably, 10 ~ 40 wt%. Viscosity limit in the polymerization ability, from the viewpoint of load and productivity of the process (D) post-treatment step (desolvation), such as, is preferably 15 ~ 50 wt%.
[0123]
　The weight average molecular weight of terminally unsaturated polypropylene produced in step (A) (Mw) is preferably 5,000 to 100,000, more preferably 5,000 to 60,000, more preferably from 5000 to 25,000. The use of terminally unsaturated polypropylene having a Mw within the above range, it is possible to increase relatively in later-described step (C), the molar concentration of terminally unsaturated polypropylene of the ethylene or α- olefins, terminally unsaturated introduction efficiency into the main chain of the polypropylene increases. On the other hand, if the Mw exceeds the above range, in a step described later (C), the molar concentration of terminal unsaturation polypropylene is relatively low, the introduction efficiency into the main chain of the terminally unsaturated polypropylene tends to be low. Also, if the Mw is below the range, there is a tendency that the melting point of the resulting resin (B) is lowered.
[0124]
　The molecular weight distribution of terminally unsaturated polypropylene produced in step (A) (Mw / Mn) is usually 1.5-3.0, typically about 1.7-2.5.
　As the terminally unsaturated polypropylene used in the later-described step (C), in some cases, it may be a mixture of different molecular weight.
[0125]
　
　Step (B) is a step of producing a raw material comprising terminally unsaturated polyethylene graft polymer composed side chains of ethylene polymer in the [GP] (SE).
　Here, the terminally unsaturated polyethylene, which comprises polyethylene having a vinyl group at one end of the polymer chain, the terminally unsaturated polyethylene, polyethylene with a vinyl group at one end, usually 60% or more, preferably from 70% or more, more preferably 80% or more, particularly preferably 90% or more. Terminally unsaturated polyethylene, besides polyethylene having a vinyl group at one terminal of the polymer chain, unsaturated carbon atoms such as a vinylene group or a vinylidene group - which may include polyethylene or both ends unsaturated polyethylene having a carbon bond.
　Terminal vinyl Motoritsu (all unsaturated carbon - to carbon bond, the ratio of terminal vinyl groups) is usually 60% or more, preferably 70% or more, more preferably 80% or more, even more preferably 90% or more .
[0126]
　Ratio of terminal vinyl groups in the terminal unsaturated polyethylene, the total carbon atoms per 1000 ethylene polymer is generally 0.1 to 30, preferably from 0.5 to 20, more preferably from 1.0 to 10 in is there.
　Ratio of terminal vinyl groups in the terminal vinyl group ratio and terminal unsaturated polyethylene, 1 can be calculated by a conventional method by polymer structure analysis by H-NMR measurement.
[0127]
　Transition metal compound [B]]
　The transition metal compound (B) is preferably a specific compound having a structure represented by the following formula [B], as an olefin polymerization catalyst used in step (B) is , the transition metal compound [B], it is preferable to use a later-described compound [D].
[0128]
[Formula 2]

[0129]
　Wherein [B], M represents a Group 4 of the periodic table or Group 5 transition metal atoms.
　m is an integer of 1-4. when m is 2 or greater, R among the structural units mutually formula [B] 2 ~ R 8 may be linked the two groups among the groups represented by.
[0130]
　R 1 has the formula C n ' H 2n' + 1 represents a hydrocarbon group (n 'is 1 is an integer of 1-8) 1 carbon atoms represented by 1-8.
[0131]
　R 2 ~ R 5 , which may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, part of which is substituted with a substituent group of the hydrocarbon group, heterocyclic compound residue, oxygen containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, to form a ring more than is bonded to each other of these it may be.
[0132]
　R 6 ~ R 8 , which may be the same or different from each other, a part of which is substituted with a halogen atom of the hydrocarbon group or a hydrocarbon group, of which at least one aromatic hydrocarbon radical or some of the aromatic hydrocarbon group is a group substituted by a halogen atom.
　R 6 ~ R 8 may be the same or different from each other.
[0133]
　n is a number satisfying a valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, part of which is substituted with a substituent group of the hydrocarbon group, an oxygen-containing group, a sulfur-containing group, nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is an integer of 2 or more the even multiple X are identical to each other or different, and plural groups may be bonded to each other to form a ring represented by X.
[0134]
　Olefin polymerization catalyst comprising a transition metal compound [B] is mainly polymerized ethylene and has a feature of generating ethylene polymer comprising a single terminal vinyl group with high selectivity. Further, the olefin polymerization catalyst comprising a transition metal compound [B] has a characteristic that can produce a relatively low molecular weight ethylene polymer (the range of 500 to 10000 Mw). Olefin polymerization catalyst comprising a transition metal compound [B] is, by having the characteristic, the resulting ethylene polymer graft-type polymer using [GP] side chain is introduced efficiently, the by using a graft polymer [GP], it is possible to obtain a composition having excellent physical property balance between impact resistance and stiffness at low temperatures easily.

claims

(A) and the melting point is above 100 ° C. crystalline olefin
　resin, (B) an olefin-based resin satisfying the following requirements (B-1) ~
　(B-3), (C) an ethylene · alpha-olefin copolymer preparative,
wherein a ratio of the resin (B) / the copolymer in a weight ratio of (C) 100/0 ~ 1 /99, and
　the resin (a) / (the resin (B) + co weight polymer (C)) in a proportion of a weight ratio of 70 / 30-30 / 70,
　the thermoplastic elastomer composition.
　(B-1) has a backbone that is the ethylene copolymer (MC) and a side chain of an olefin polymer (SC), graft satisfying the following requirements (i) and (ii) containing a polymer [GP]
　ethylene copolymer constituting the (i) main chain (MC) is a repeating unit derived from ethylene, at least one selected from α- olefins having a carbon number of 3 ~ 20 alpha - and a repeating unit derived from an olefin, the α- repeating units derived from an olefin in the range of 10 ~ 50 mol% based on all repeating units are contained in the main chain (MC)
　(ii) side chain (SC ) is an ethylene polymer is at least one selected from the consisting side chains (SP) from consisting side chains (SE) and propylene polymer
　(B-2) is measured by differential scanning calorimetry That the melting point is in the range of ~ 170 ° C. 60
　(B-3) a glass transition temperature measured by differential scanning calorimetry is in the range of -80 ~ -30 ° C.
[Requested item 2]
　ASTM D790 measured flexural modulus in conformity with is less than 650 MPa, the thermoplastic elastomer composition of claim 1.
[Requested item 3]
　The crystalline olefin resin (A), the 100 parts by weight of the total amount of the olefin resin (B) and the ethylene · alpha-olefin copolymer (C), filler (E) 5 parts by weight or less including, according to claim 1 or a thermoplastic elastomer composition according to 2.
[Requested item 4]
　Wherein the crystalline olefin resin (A), the compliant with ISO 1133, 230 ° C., a melt flow rate measured at 2.16kg load is 0.1 ~ 500 g / 10min, more of claims 1 to 3, thermoplastic elastomer composition according to one or.
[Requested item 5]
　Side chain (SC) in the graft type polymer [GP] is a composed side chains of ethylene polymer (SE),
　the side chain (SE) is a repeating unit derived from ethylene, and optionally includes repeating units derived from at least one selected from α- olefin having 3 to 20 carbon atoms Te, content of units derived from the ethylene is based on all the repeating units contained in the side chain (SE), 95 ~ in the range of 100 mol%,
　the thermoplastic elastomer composition according to any one of claims 1 to 4.
[Requested item 6]
　The olefin resin (B) is, in differential scanning calorimetry showed a melting peak in the range of 60 ~ 130 ° C., a heat of fusion ΔH of the melting peak in the range of 5 ~ 100 J / g, according to claim 1 to 5, the thermoplastic elastomer composition according to any one of.
[Requested item 7]
　E value The is the percentage of 20 ° C. below the orthodichlorobenzene-soluble content as measured by cross fractionation chromatograph olefin resin (B) is not more than 45 wt%, any one of claims 1 to 6, thermoplastic elastomer composition according to.
[Requested item 8]
　Intrinsic viscosity measured at 135 ° C. in decalin of the olefin resin (B) is in the range of 0.1 ~ 12 dl / g, the thermoplastic elastomer composition according to any one of claims 1 to 7 .
[Requested item 9]
　The weight average molecular weight of the ethylene polymer constituting the side chains (SE) is in the range of 500 to 30,000, the thermoplastic elastomer composition according to any one of claims 1-8.
[Requested item 10]
　Side chain of the graft type polymer [GP] is, the main chain polymer molecules 1000 carbon atoms per chain, is present at 0.5 to 20 average frequency, any one of claims 1 to 9, thermoplastic elastomer composition according to.
[Requested item 11]
　The olefin resin (B) satisfy the following requirements (B-7), the thermoplastic elastomer composition according to any one of claims 1 to 10.
　(B-7) in compliance with the ASTM D1238E olefin-based resin (B), 190 ℃, the melt flow rate measured at 2.16kg load and M (g / 10min), measured in the 135 ° C. decalin when the intrinsic viscosity of the olefin resin (B) which is an H (dl / g), the value a represented by the following equation (Eq-1) is in the range of 30 ~ 280
　a = M / exp (-3.3H) ··· (Eq- 1)
[Requested item 12]
　The ethylene · alpha-olefin copolymer (C), in compliance with ASTM D1238E, 190 ℃, melt flow rate measured at 2.16kg load is 0.01 ~ 50 g / 10min, claim 1 the thermoplastic elastomer composition according to any one of 11.
[Requested item 13]
　In the absence of a crosslinking agent, the resin (A), the said resin (B) and the copolymer (C), the resin (A) / (the resin (B) + the copolymer (C)) method of manufacturing a weight ratio comprising the step of dynamic heat treatment of the mixture in a proportion to be 70 / 30-30 / 70, the thermoplastic elastomer composition according to any one of claims 1 to 12.
[Requested item 14]
　To any one of claims 1 to 12 comprising the thermoplastic elastomer composition according molded article.
[Requested item 15]
　To any one of claims 1 to 12 comprising the thermoplastic elastomer composition according automobile parts.
[Requested item 16]
　To any one of claims 1 to 12 comprising the thermoplastic elastomer composition according, automotive interior skin material.
[Requested item 17]
　To any one of claims 1 to 12 comprising the thermoplastic elastomer composition according automotive airbag cover.
[Requested item 18]
　(A) and the melting point is above 100 ° C. crystalline olefin resin,
　and a (B) and structural units derived from ethylene, structural units derived from at least one selected from α- olefin having 3 to 20 carbon atoms ,
　the glass transition temperature is at -110 ~ -20 °
　C., in compliance with ASTM D1238E, and 190 ° C., olefin resin melt flow rate as measured at 2.16kg load is 0.1 ~ 10 g / 10 min ,
　(C) and the ethylene · alpha-olefin copolymer,
　wherein a ratio of the resin (B) / the copolymer in a weight ratio of (C) 100/0 ~ 1 /99, and
　the resin (a ) / the weight ratio of (the resin (B) + the copolymer (C)) comprises at a rate of 70 / 30-30 / 70,
further
　flexural modulus 200 ~ 1000 MPa was measured according to ASTM D790 , and the and,
　Elongation at break of -40 ℃ measured in accordance with JIS K6251 is 50 to 600%,
the thermoplastic elastomer composition.
[Requested item 19]
　To claim 18 comprising a thermoplastic elastomer composition according automotive interior skin material or automotive airbag cover.