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JP-7854841-B2 - Resin compositions and their uses

JP7854841B2JP 7854841 B2JP7854841 B2JP 7854841B2JP-7854841-B2

Inventors

  • 田中 正和
  • 佐々木 豊明

Assignees

  • 三井化学株式会社

Dates

Publication Date
20260507
Application Date
20220421
Priority Date
20210430

Claims (16)

  1. A 4-methyl-1-pentene polymer (X) that satisfies all of the following requirements (a) to (f) , Phosphate ester salt-based nuclear agents and Includes, A resin composition comprising 0.1 to 1 part by mass of the phosphate ester salt nucleating agent per 100 parts by mass of the 4-methyl-1-pentene polymer (X) . (a) The content of constituent units derived from 4-methyl-1-pentene is greater than 99.4 mol% and less than or equal to 100 mol%, and the content of constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 mol% or more and less than 0.6 mol%. (b) The mesodiad fraction (m) measured by 13¹C -NMR is between 98.5% and 100%. (c) The intrinsic viscosity [η] measured in decalin solvent at 135°C is 0.1 to 6.0 dl/g. (d) The decane-soluble portion at 23°C is 5.0% by mass or less. (e) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 200 to 260°C. (f) The heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) is 45 J/g or more.
  2. The resin composition according to claim 1, wherein the phosphate ester salt nucleating agent comprises sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate.
  3. The resin composition according to claim 1, comprising 0.1 parts by mass of the phosphate ester salt nucleating agent per 100 parts by mass of the 4-methyl-1-pentene polymer (X).
  4. The resin composition according to claim 1 , wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (g). (g) The density measured in accordance with the density gradient pipe method of JIS K7112 is 815 to 850 kg/ m³ .
  5. The resin composition according to claim 1 , wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (h). (h) The melt flow rate (MFR), measured at 260°C and under a 5 kg load in accordance with ASTM D1238, is 0.1 to 500 g/10 min.
  6. A molded article comprising the resin composition described in claim 1.
  7. The molded article according to claim 6 , wherein the maximum wall thickness is 100 mm or less and the minimum wall thickness is 0.001 mm or more.
  8. The molded article according to claim 6 , which is an injection-molded article or an extruded article.
  9. The molded article according to claim 6 , which is in the form of a film or a sheet.
  10. A food packaging material or food storage container comprising a molded body according to any one of claims 6 to 9 .
  11. A laminate in which at least one layer comprises the resin composition described in any one of claims 1 to 5 .
  12. The process includes a step of forming a film made of a resin composition containing a 4-methyl-1-pentene polymer (X) and a phosphate ester salt nucleating agent under film forming conditions of a die temperature of 200 to 320°C and a chill-roll temperature of 70 to 120°C. The resin composition contains 0.1 to 1 part by mass of the phosphate ester salt nucleating agent per 100 parts by mass of the 4-methyl-1-pentene polymer (X), A method for producing a film, wherein the 4-methyl-1-pentene polymer (X) satisfies all of the following requirements (a) to (f). (a) The content of constituent units derived from 4-methyl-1-pentene is greater than 99.4 mol% and less than or equal to 100 mol%, and the content of constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 mol% or more and less than 0.6 mol%. (b) The mesodiad fraction (m) measured by 13¹C -NMR is between 98.5% and 100%. (c) The intrinsic viscosity [η] measured in decalin solvent at 135°C is 0.1 to 6.0 dl/g. (d) The decane-soluble portion at 23°C is 5.0% by mass or less. (e) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 200 to 260°C. (f) The heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) is 45 J/g or more.
  13. The method for producing a film according to claim 12, wherein the phosphate ester salt nucleating agent comprises sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate.
  14. The method for producing a film according to claim 12, wherein the resin composition contains 0.1 parts by mass of the phosphate ester salt nucleating agent per 100 parts by mass of the 4-methyl-1-pentene polymer (X).
  15. The method for producing a film according to claim 12 , wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (g). (g) The density measured in accordance with the density gradient pipe method of JIS K7112 is 815 to 850 kg/ m³ .
  16. A method for producing a film according to any one of claims 12 to 15 , wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (h). (h) The melt flow rate (MFR), measured at 260°C and under a 5 kg load in accordance with ASTM D1238, is 0.1 to 500 g/10 min.

Description

This invention relates to a 4-methyl-1-pentene polymer, molded articles such as films using the same, their applications, and a method for producing the film. 4-methyl-1-pentene polymers, whose main constituent monomer is 4-methyl-1-pentene, are widely used in various applications because they have superior properties such as heat resistance, transparency, and electrical properties compared to polyethylene and polypropylene, as well as superior release properties and solvent resistance (see, for example, Patent Document 1). For example, films are used as FPC release films and release films for composite material molding, taking advantage of their good release properties, while molded articles are used in laboratory equipment and mandrels for rubber hose manufacturing, taking advantage of their chemical resistance, water resistance, and transparency. On the other hand, molded articles made from resin compositions containing known 4-methyl-1-pentene polymers may require further improvement in terms of heat resistance (see, for example, Patent Document 2). International Publication No. 2013/099876 BrochureJapanese Patent Publication No. 2013-122061International Publication No. 2014/050817 Brochure The present invention will be described below. In this specification, the numerical range A to B means A or greater and B or less, unless otherwise specified. Furthermore, unless otherwise specified, the terms "polymerization" and "(co)polymerization" are used to encompass both homopolymerization and copolymerization. <4-methyl-1-pentene polymer (X)> The 4-methyl-1-pentene polymer (X) of the present invention satisfies all of the following requirements (a) to (f). 《Requirement (a)》 (a) The content of constituent units derived from 4-methyl-1-pentene is greater than 99.4 mol% and less than or equal to 100 mol%, and the content of constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (content of constituent units derived from α-olefins) is 0 mol% or more and less than 0.6 mol%. The 4-methyl-1-pentene polymer (X) of the present invention preferably has a content of 99.5 to 100 mol% of constituent units derived from 4-methyl-1-pentene and a content of 0 to 0.5 mol% of constituent units derived from α-olefin, more preferably has a content of more than 99.5 mol% and 100 mol% or less of constituent units derived from 4-methyl-1-pentene and a content of 0 mol% or more and less than 0.5 mol%, even more preferably has a content of 99.6 to 100 mol% of constituent units derived from 4-methyl-1-pentene and a content of 0 to 0.4 mol% of constituent units derived from α-olefin, and particularly preferably has a content of more than 99.6 mol% and 100 mol% or less of constituent units derived from 4-methyl-1-pentene and a content of 0 mol% or more and less than 0.4 mol% of constituent units derived from α-olefin. The 4-methyl-1-pentene polymer (X) of the present invention is preferable from the viewpoint of heat resistance and light weight when it satisfies the above-mentioned content of constituent units. Furthermore, it is preferable that the content of α-olefin-derived constituent units is low and the degree of crystallinity is high, thereby suppressing gas permeation in molded articles such as films containing the 4-methyl-1-pentene polymer (X). Examples of ethylene and α-olefins having 3 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. In this specification, ethylene is included in α-olefins. Among these, linear α-olefins having 5 to 20 carbon atoms are preferred from the viewpoint of imparting flexibility to molded articles obtained from 4-methyl-1-pentene polymers (X), linear α-olefins having 6 to 20 carbon atoms are more preferred, linear α-olefins having 8 to 20 carbon atoms are even more preferred, and linear α-olefins having 10 to 20 carbon atoms are particularly preferred. Specifically, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred, and 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are particularly preferred. When the 4-methyl-1-pentene polymer (X) has structural units derived from α-olefins, the structural units derived from α-olefins may be a single type or two or more types. The 4-methyl-1-pentene polymer (X) may further have constituent units derived from other polymerizable compounds other than 4-methyl-1-pentene and α-olefins having 2 to 20 carbon atoms, to the extent that it does not impair the objectives of the present invention. Examples of other polymerizable compounds include: vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or their derivatives such as maleic anhydride; conjugated dienes such as butadiene, isopr