JP5489729B2 - Resin composition and film containing the same - Google Patents

Description

  The present invention relates to a resin composition containing a polyethylene resin and / or a polypropylene resin, a 4-methyl-1-pentene polymer, and a compatibilizing agent, and a film containing the resin composition.

  Additives are often added to polyethylene resins and polypropylene resins in order to obtain physical properties required for the molded products. For example, a saturated or unsaturated higher fatty acid amide, a saturated or unsaturated alkylene bisamide, or a fatty acid monoglyceride is added to obtain surface smoothness when formed into a film or the like. Furthermore, an inorganic fine powder (for example, a fine powder of silica, zeolite, talc, calcium carbonate, diatomaceous earth, etc.) that is an antiblocking agent (hereinafter referred to as “AB agent”) may be added.

  In recent years, propylene-based elastomers containing propylene as a main component have been known as soft materials made of polyolefins having excellent flexibility, heat resistance, and transparency, as well as environmental suitability and hygiene (Patent Documents 1, 1). 2). Unlike conventional olefin-based elastomers, such propylene-based elastomers exhibit excellent transparency, heat resistance (high softening temperature), and scratch resistance, so electrical / electronic equipment parts, industrial materials, furniture, stationery, Expansion to a wide range of applications such as general goods, miscellaneous goods, containers / packaging goods, toys, leisure goods, and medical goods has been attempted. However, there are cases where the feeling of stickiness of the material becomes a problem, and the application application may be limited.

  A method of adding a slip agent (lubricant) to suppress the stickiness of this material is conventionally known. For example, Patent Document 3 specifically describes a technique of adding a higher fatty acid amide or higher fatty acid ester to a propylene elastomer. Is disclosed.

  However, a polyethylene resin composition or a polypropylene resin composition added with a fatty acid amide or the like is pelletized into pellets; when trying to extrude the pellets, in a heated extruder cylinder, compared to polyethylene resins and polypropylene resins The low melting point fatty acid amide melts first; for this reason, the pellets that are still in a solid state slip in the extruder and may not be normally conveyed (called discharge pulsation or surging). In addition, fatty acid amides have a low molecular weight as compared with polyethylene resins and the like, and there is a problem of emitting oily smoke and odor at high temperatures. In addition, fatty acid amides may bleed out in the molded product of the resin composition.

  Furthermore, in the polyethylene resin composition and the polypropylene resin composition to which an AB agent such as silica is added, the AB agent excessively bleeds over time or in a high temperature environment, and as a result, the transparency may be lowered. Therefore, the amount of these AB agents added is limited, and a sufficient anti-blocking effect has not been obtained.

  Therefore, an additive that prevents blocking of a molded product and imparts releasability by adding to polyethylene resin or polypropylene resin is desired.

  On the other hand, a technique of adding a wax made of a low molecular weight polyolefin to a resin is known. Polypropylene wax and polyethylene wax are known as such wax. When such a wax is blended with a resin, the compatibility between the resin and the wax is important.

  For example, since a polyethylene wax is incompatible with a propylene elastomer, the transparency of a molded product made of these may be greatly reduced. On the other hand, even if the compatibility between the wax and the resin is too good, the wax cannot effectively localize near the surface of the molded product, so that the effect as a wax (blocking prevention, improved releasability, anti-sticking effect) Etc.) may not be obtained sufficiently.

  On the other hand, olefin polymers containing 4-methyl-1-pentene (hereinafter also referred to as 4-methyl-1-pentene polymers) have heat resistance as well as transparency, gas permeability, chemical resistance, and peelability. As an excellent resin, it is used in various fields such as medical instruments, heat-resistant electric wires, heat-resistant tableware, and stripping materials. In particular, a low molecular weight 4-methyl-1-pentene polymer is excellent in releasability.

  Such a 4-methyl-1-pentene polymer is generally produced using a catalyst comprising a transition metal compound and an organoaluminum compound, that is, a so-called Ziegler type catalyst (Patent Document 4). However, a polymer using a Ziegler-type catalyst may have problems such as stickiness because the composition of the molecular weight of the polymer is not uniform and the content of the low molecular region of the molecular weight distribution is large.

  On the other hand, a 4-methyl-1-pentene polymer obtained by using a metallocene catalyst has been reported (Patent Document 5), and although the molecular weight and composition of the polymer are uniform, thermal properties such as heat resistance, It was characterized by high molecular weight for the purpose of improving the balance of various physical properties such as mechanical properties.

  As a method for obtaining a low molecular weight 4-methyl-1-pentene polymer, a higher molecular weight 4-methyl-1-pentene polymer can be thermally decomposed (Patent Document 6), but the width of the molecular weight distribution However, since it also contains components with low stereoregularity, there are problems such as blocking and stickiness.

Japanese Patent Laid-Open No. 9-309982 International Publication No. 2004/087775 JP 2005-325194 A Japanese Patent Publication No. 5-88250 International Publication No. 2005/121192 Japanese Patent Publication No. 3-76325

  An object of this invention is to provide the polyethylene resin composition and polypropylene resin composition which have high transparency and a softness | flexibility, while having the outstanding mold release property and antiblocking property. Thereby, it aims at providing molded articles, such as a film, in which the sticky feeling was suppressed under the wide environment from room temperature to high temperature.

  First, in the present invention, by adding a low molecular weight 4-methyl-1-pentene polymer to a base resin made of polyethylene resin or polypropylene resin, the resulting resin composition has releasability and antiblocking property. We considered giving. However, it has become clear that the base resin and the low molecular weight 4-methyl-1-pentene polymer are hardly compatible, and the transparency and flexibility of the resin composition are lowered. Therefore, in order to improve the compatibility, the blending of various additives was examined. As a result, good releasability is achieved by using a specific compatibilizer in combination with a base resin made of polyethylene resin or polypropylene resin and a low molecular weight 4-methyl-1-pentene polymer. However, it has been clarified that a decrease in transparency and flexibility of the resin composition can be suppressed.

  Therefore, the present invention includes a base resin made of polyethylene resin or polypropylene resin, a low molecular weight 4-methyl-1-pentene polymer and a compatibilizing agent, and has excellent release properties and antiblocking properties. In addition, a resin composition having high flexibility and transparency is provided.

That is, the first of the present invention relates to the following resin composition.
[1] Base resin (A1) containing 100 parts by mass of polyethylene resin; 0.1 to 5 parts by mass of 4-methyl-1-pentene polymer (B); polyethylene wax, polypropylene wax and A resin composition comprising a compatibilizer (C) selected from the group consisting of petroleum resins,
Resin having an intrinsic viscosity [η] (dl / g) of the 4-methyl-1-pentene polymer (B) measured in a decalin solvent at 135 ° C. in the range of 0.01 or more and less than 0.50 Composition.
[2] Base resin (A2) containing 100 parts by mass of polypropylene resin; 0.1 to 10 parts by mass of 4-methyl-1-pentene polymer (B); polyethylene wax, polypropylene wax and A resin composition comprising a compatibilizer (C) selected from the group consisting of petroleum resins,
Resin having an intrinsic viscosity [η] (dl / g) of the 4-methyl-1-pentene polymer (B) measured in a decalin solvent at 135 ° C. in the range of 0.01 or more and less than 0.50 Composition.

（上記式（Ｉ）におけるＡは、前記４−メチル−１−ペンテン系重合体（Ｂ）中の成分のうち、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定されるポリスチレン換算の分子量が１０００以下である成分の含有割合（質量％）である） [3] The intrinsic viscosity [η] (dl / g) of the 4-methyl-1-pentene polymer (B) measured at 135 ° C. in a decalin solvent satisfies the relationship of the following formula (I): The resin composition according to [1] or [2].

(A in the above formula (I) has a polystyrene-reduced molecular weight of 1000 or less as measured by gel permeation chromatography (GPC) among the components in the 4-methyl-1-pentene polymer (B). (The content ratio of a certain component (% by mass))

[4] The ratio of the structural unit derived from 4-methyl-1-pentene to the total structural unit of the 4-methyl-1-pentene polymer (B) is 50 to 100% by mass, and 4-methyl- The total proportion of structural units derived from at least one olefin selected from olefins having 2 to 20 carbon atoms other than 1-pentene is 0 to 50% by mass,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the 4-methyl-1-pentene polymer (B) measured by gel permeation chromatography (GPC) is: In the range of 1.0 to 5.0,
The melting point (Tm) of the 4-methyl-1-pentene polymer (B) measured with a differential scanning calorimeter is in the range of 120 to 245 ° C.,
The resin composition according to any one of [1] to [3], wherein a critical surface tension of the 4-methyl-1-pentene polymer (B) is in a range of 22 to 28 mN / m.
[5] The amount of terminal double bonds calculated by ¹ H-NMR of the 4-methyl-1-pentene polymer (B) is 0.001 or more and 0.5 or less per 1000 carbons. The resin composition according to any one of [1] to [4].
[6] The method according to any one of [1] to [5], wherein the 4-methyl-1-pentene polymer (B) is a 4-methyl-1-pentene polymer polymerized by a metallocene catalyst. Resin composition.

  [7] The content of the compatibilizer (C) is 1 to 100 parts by mass with respect to 100 parts by mass of the 4-methyl-1-pentene polymer (B). [1] to [6] The resin composition as described in any one of these.

2nd of this invention is related with the film etc. which are shown below.
[8] A film molded article comprising the resin composition according to any one of [1] to [7].
[9] A surface protective film having a surface layer constituting one surface and an adhesive layer constituting the other surface, wherein the surface layer is the resin composition according to any one of [1] to [7] Surface protective film made of objects.
[10] The surface protective film according to [9], wherein the surface layer and the adhesive layer are coextruded from a T-die.

  The polyethylene resin composition or polypropylene resin composition of the present invention has high flexibility and transparency while having excellent releasability and antiblocking properties.

  The resin composition of the present invention comprises a base resin (A1) containing a polyethylene resin or a base resin (A2) containing a polypropylene resin; a 4-methyl-1-pentene polymer (B); a compatibilizing agent (C) And containing. By adding the 4-methyl-1-pentene polymer (B) to the base resin (A1) or (A2), release properties and antiblocking properties are imparted; and a compatibilizing agent (C) is added. Therefore, it can be considered that transparency and flexibility are maintained.

About Base Resin The resin composition of the present invention contains a base resin (A1) containing a polyethylene resin or a base resin (A2) containing a polypropylene resin.

  The base resin (A1) contains a polyethylene resin as a main component, and usually contains 50% by mass or more, preferably 80% by mass or more of polyethylene resin. Examples of the polyethylene resin constituting the base resin (A1) include high pressure method low density polyethylene (LDPE), linear short chain branched polyethylene (LLDPE), medium and low pressure method high density polyethylene (HDPE), and linear short chain. Branched polyethylene (LLDPE) and the like are included.

More specifically, as the polyethylene resin, density 940-980 high-density polyethylene is in the range of (kg / ^{m 3),} low density polyethylene is in a range of less than the density nine hundred to nine hundred and forty (kg / m ^3), medium density polyethylene, Examples thereof include linear low density polyethylene, ultra low density polyethylene, and blends thereof. Although not particularly limited, low density polyethylene excellent in balance between transparency and processability is preferable. The density of the polyethylene resin is measured according to the density gradient tube method of JIS K7112.

  The melt index (MI) of the polyethylene resin is preferably in the range of 0.01 to 100 g / 10 minutes. MI is measured in accordance with JIS K7210 under conditions of 190 ° C. and a test load of 21.18N.

  The polyethylene resin refers to an ethylene homopolymer, a copolymer of ethylene and a small amount of α-olefin, or a blend thereof. The copolymer component of the copolymer is preferably 50 mol% or less, more preferably 20 mol% or less of all monomer units. Examples of copolymerization components of the copolymer include other olefin monomers, preferably olefins having 2 to 20 carbon atoms; for olefins having 2 to 20 carbon atoms, linear or branched α -Olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functionalized vinyl compounds and the like. Specific examples of the olefin having 2 to 20 carbon atoms are the same as those of the copolymerization monomer in the 4-methyl-1-pentene polymer (B) described later.

  On the other hand, the base resin (A2) contains a polypropylene resin as a main component and usually contains 50% by mass or more, preferably 80% by mass or more of polypropylene resin. The polypropylene resin constituting the base resin (A2) refers to a propylene homopolymer, a block copolymer or a random copolymer of propylene and an α-olefin other than propylene, or a blend thereof. Although not particularly limited, a homopolymer having a high melting point and rigidity is preferred from the viewpoint of suppressing the sticky feeling of the resin composition.

The density of the polypropylene resin is usually in the range of 900 to 910 (kg / m ³ ). The density of the polypropylene resin is measured according to the density gradient tube method of JIS K7112.

  The melt index (MI) of the polypropylene resin is preferably in the range of 0.01 to 100 g / 10 minutes. MI is measured according to JIS K7210 at 230 ° C. and a test load of 21.18 N.

4-Methyl-1-pentene polymer (B) The 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is such that at least a part of the structural unit is 4-methyl-1 -A polymer that is a structural unit derived from pentene.

  The intrinsic viscosity [η] (dl / g) of the 4-methyl-1-pentene polymer (B) measured at 135 ° C. in a decalin solvent is 0.01 or more and less than 0.50, preferably 0.8. It is 02-0.45, More preferably, it is the range of 0.03-0.40, Most preferably, it is the range of 0.05-0.20. When the intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (B1) is within this range, a release effect is imparted to the resin composition of the present invention as a resin modifier.

  The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (B) can be lowered, for example, by increasing the amount of hydrogen introduced during the polymerization reaction. It can also be controlled by the polymerization reaction catalyst type, polymerization temperature, and the like. For example, when a 4-methyl-1-pentene polymer is used with a metallocene catalyst, the polymerization temperature is usually in the range of −50 to 400 ° C .; 4-methyl having a suitable intrinsic viscosity [η] as described above. From the viewpoint of producing a -1-pentene polymer (B), the polymerization temperature is preferably in the range of 10 to 300 ° C, more preferably in the range of 10 to 250 ° C.

The number average molecular weight of the 4-methyl-1-pentene polymer (B) is preferably 5 × 10 ² to 2 × 10 ⁴ , more preferably 7 × 10 ² to 1 × 10 ⁴ , it is particularly preferably ^{1 × 10 3 ~5 × 10 3} . By reducing the intrinsic viscosity of the 4-methyl-1-pentene polymer (B) or lowering the number average molecular weight, the base resin (A) and the 4-methyl-1-pentene polymer (B) The compatibility of can be increased.

  In the case where the 4-methyl-1-pentene polymer (B) having a suitable intrinsic viscosity [η] described above is produced by thermally decomposing a 4-methyl-1-pentene polymer having a higher molecular weight. The thermal decomposition temperature should just be 200 to 500 degreeC, it is preferable to set it as the range of 250-480 degreeC, and it is more preferable to set it as the range of 300-450 degreeC.

  The ratio of the structural unit derived from 4-methyl-1-pentene to the total structural unit of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is 50 to 100% by mass. It is preferable that it is 60 to 100% by mass, and more preferably 70 to 100% by mass. Further, the total proportion of structural units derived from olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene relative to all structural units of 4-methyl-1-pentene polymer (B) is 0. It is preferably ˜50 mass%, more preferably 0 to 40 mass%, and further preferably 0 to 30 mass%.

  Examples of the olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene contained as a structural unit in the 4-methyl-1-pentene polymer (B) include linear or branched α- Examples include olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, and functionalized vinyl compounds.

  Specific examples of the linear or branched α-olefin contained as a structural unit in the 4-methyl-1-pentene polymer (B) include ethylene, propylene, 1-butene, 1-pentene, 1- Linear α-carbon having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene Olefin; 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl- Preferably 5-20, more preferably 5-10 branched α-olefins such as 1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like are included.

  Specific examples of the cyclic olefin contained as a structural unit in the 4-methyl-1-pentene polymer (B) include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane. , Cyclic olefins having 3 to 20 carbon atoms, preferably 5 to 15 carbon atoms are included.

  Specific examples of the aromatic vinyl compound contained as a structural unit in the 4-methyl-1-pentene polymer (B) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methyl. Mono- or polyalkylstyrenes such as styrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene are included.

  Examples of conjugated dienes contained as structural units in the 4-methyl-1-pentene polymer (B) include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4 Conjugated dienes having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as -methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene and 1,3-octadiene are included.

  Specific examples of the non-conjugated polyene contained as a structural unit in the 4-methyl-1-pentene polymer (B1) include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4- Octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropyl Non-conjugated polyenes having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms, such as lidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene are included. .

  Examples of the functionalized vinyl compound contained as a structural unit in the 4-methyl-1-pentene polymer (B) include a hydroxyl group-containing olefin; a halogenated olefin; acrylic acid, propionic acid, 3-butenoic acid, 4-pentene. Unsaturated carboxylic acids such as acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid and 9-decenoic acid; unsaturated amines such as allylamine, 5-hexenamine and 6-heptenamine; (2,7-octadienyl) succinic anhydride, pentapropenyl succinic anhydride and unsaturated acid anhydrides such as compounds in which the carboxylic acid group is replaced with a carboxylic acid anhydride group in the unsaturated carboxylic acids In the examples of compounds in the above unsaturated carboxylic acids, unsaturated carbons such as compounds in which the carboxylic acid group is replaced with a carboxylic acid halide group Acid halides: 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-heptene, 8-epoxy-1-octene, 9-epoxy-1 And unsaturated epoxy compounds such as -nonene, 10-epoxy-1-decene, and 11-epoxy-1-undecene.

  The hydroxyl group-containing olefin contained as a structural unit in the 4-methyl-1-pentene polymer (B) is not particularly limited as long as it is a hydroxyl group-containing olefin compound, and examples thereof include terminal hydroxylated olefin compounds. Specific examples of the terminal hydroxylated olefin compound include vinyl alcohol, allyl alcohol, hydroxylated 1-butene, hydroxylated 1-pentene, hydroxylated 1-hexene, hydroxylated 1-octene, and hydroxylated 1- Decene, hydroxyl-1-dodecene, hydroxyl-1-tetradecene, hydroxyl-1-hexadecene, hydroxyl-1-octadecene, hydroxyl-1-octodecene, hydroxyl-1-eicosene, etc. 2-20, preferably 2 10 linear hydroxylated α-olefins; hydroxylated 3-methyl-1-butene, hydroxylated 4-methyl-1-pentene, hydroxylated 3-methyl-1-pentene, hydroxylated-3- Ethyl-1-pentene, hydroxyl-4,4-dimethyl-1-pentene, hydroxyl-4-methyl-1-hexene, hydroxyl-4,4-dimethyl-1-hexene, hydroxyl-4-ethyl hydroxide 1-hexene, hydroxy-3-ethyl-1-hexene, etc., preferably 5 to 20, more preferably 5 to 1 It includes branched hydroxide α- olefins.

  Specific examples of the halogenated olefin contained as a structural unit in the 4-methyl-1-pentene polymer (B) include halogenated α-olefins having a group 17 atom of the periodic table such as chlorine, bromine and iodine, such as halogen Vinyl halide, halogenated-1-butene, halogenated-1-pentene, halogenated-1-hexene, halogenated-1-octene, halogenated-1-decene, halogenated-1-dodecene, halogenated-1- Linear halogenated α-olefins having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as tetradecene, halogenated-1-hexadecene, halogenated-1-octadecene, halogenated-1-eicosene; -3-methyl-1-butene, halogenated-4-methyl-1-pentene, halogenated-3-methyl-1-pentene, halogenated-3-ethyl-1-pentene, halogenated-4,4-dimethyl -1-pe Ten, halogenated-4-methyl-1-hexene, halogenated-4,4-dimethyl-1-hexene, halogenated-4-ethyl-1-hexene, halogenated-3-ethyl-1-hexene, etc. Preferably 5-20, more preferably 5-10 branched halogenated α-olefins are included.

  Particularly preferred examples of olefins contained as a structural unit together with 4-methyl-1-pentene include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3-methyl- 1-pentene, 3-ethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3- Examples include ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, vinylcyclohexane, styrene and the like. The 4-olefin-1-pentene polymer (B) may contain one olefin or a combination of two or more olefins as a constituent unit together with 4-methyl-1-pentene. .

  The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention determined by gel permeation chromatography (GPC) The ratio (Mw / Mn) is preferably 1.0 to 5.0; more preferably 1.0 to 4.5; still more preferably 1.0 to 4.0; 1 It is especially preferable that it is 0.0-3.5. When the ratio (Mw / Mn) is within the above range, the content of the low molecular weight region component of the molecular weight distribution is reduced, and when used as a resin modifier, stickiness of the molded product of the resin composition can be suppressed. it can. Further, when the ratio (Mw / Mn) is within the above range, the content of the high molecular weight component is reduced, the dispersibility in the molded product is excellent, and the influence on the mechanical properties is reduced.

  The molecular weight distribution having the above ratio (Mw / Mn) can be realized by controlling the conditions under which the higher molecular weight 4-methyl-1-pentene polymer is thermally decomposed; The 1-pentene polymer (B) is preferably obtained by polymerizing a 4-methyl-1-pentene composition using a Ziegler catalyst, more preferably a metallocene catalyst described later.

  The melting point (Tm) measured by a differential scanning calorimeter of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is preferably 120 to 245 ° C., preferably 130 to More preferably, it is 240 degreeC, and it is further more preferable that it is 140-235 degreeC. When the melting point (Tm) is within this range, the balance between the molding processability of the resin composition of the present invention and the blocking resistance during storage of the molded product of the resin composition of the present invention (such as a film molded product) is excellent.

  When the 4-methyl-1-pentene polymer (B) is a homopolymer of 4-methyl-1-pentene, the melting point of the 4-methyl-1-pentene polymer (B) is a number average. Depends on molecular weight (Mn). For example, the melting point of 4-methyl-1-pentene homopolymer having a low molecular weight is low. On the other hand, when 4-methyl-1-pentene polymer (B) is a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms, 4-methyl-1-pentene The melting point of the polymer (B) depends on the size of the number average molecular weight (Mn) and can be controlled by the content of the olefin having 2 to 20 carbon atoms relative to 4-methyl-1-pentene and the kind thereof. . For example, increasing the amount of olefin used relative to 4-methyl-1-pentene can lower the melting point of the resulting polymer.

  The measurement of the melting point of 4-methyl-1-pentene polymer (B) was performed using a differential scanning calorimeter (Diamond DSC, manufactured by PerkinElmer), and about 5 mg of a sample was packed in an aluminum pan at 10 ° C. / Heated to 280 ° C in minutes; held at 280 ° C for 5 minutes; cooled to 30 ° C at 10 ° C / minute; after held at 30 ° C for 5 minutes; when heated to 280 ° C at 10 ° C / minute The endothermic peak is taken as the melting point.

  The critical surface tension of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is preferably 22 to 28 mN / m, more preferably 23 to 27.5 mN / m. 24 to 27.5 mN / m, more preferably 24.5 to 27.5 mN / m. When the critical surface tension is within this range, excellent release properties can be imparted to the molded product of the resin composition.

  The critical surface tension of the 4-methyl-1-pentene polymer (B) depends on the ratio of the 4-methyl-1-pentene constituent unit to the total constituent units of the 4-methyl-1-pentene polymer. In order to obtain a desired critical surface tension, the proportion of the constituent unit of 4-methyl-1-pentene may be 50 to 100% by mass, preferably 60 to 100% by mass, and 70 to 100% by mass. It is more preferable that it is 80-100 mass%.

The 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention preferably has a molecular weight and an intrinsic viscosity [η] that satisfy the relationship represented by the following formula (I).

  [Η] in the above formula (I) is the intrinsic viscosity (dl / g) of the 4-methyl-1-pentene polymer (B) measured at 135 ° C. in a decalin solvent. Of the components in the 4-methyl-1-pentene polymer (B), A in the above formula (I) has a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of 1000 or less. It is a content ratio (mass%) of a component.

  The resin composition of the present invention containing the 4-methyl-1-pentene polymer (B) that satisfies the condition of the above formula (I) has a high mold releasability of the molded product (film, etc.), and The mechanical properties are not impaired.

  The 4-methyl-1-pentene polymer (B) satisfying the relationship of the above formula (I) is obtained by purifying 4-methyl-1-pentene polymer by solvent fractionation, etc., and mainly having a molecular weight of 1,000 or less. It is obtained by removing the components. In addition, since a polymer having a narrow molecular weight distribution tends to be obtained when a metallocene catalyst described later is used, a 4-methyl-1-pentene system satisfying the relationship of the formula (I) can be obtained without purification by solvent fractionation. A polymer (B) is often obtained.

  As described above, the resin composition of the present invention contains a base resin (A) made of a polyethylene and / or polypropylene resin and a 4-methyl-1-pentene polymer (B) as a resin modifier. It is characterized by doing. When molding a resin composition containing both, a relatively low molecular weight 4-methyl-1-pentene polymer (B) is melted and is near the inner wall surface of a molding machine such as a screw, barrel or die. It tries to reduce the shearing force of the molding machine. Further, since the localized state of the 4-methyl-1-pentene polymer is maintained in the process of solidifying the molded product, the 4-methyl-1-pentene polymer is formed on the surface layer of the obtained resin molded product. It is considered that uneven distribution tends to occur and the release property of the molded product is enhanced.

  However, while the releasability of the resin molded product is increased, the 4-methyl-1-pentene polymer itself may be blocked or the mechanical properties of the molded product may be impaired. Moreover, the mold release effect of the obtained molded product may not be sufficient. As a result of investigating the cause, it was found that this problem is likely to occur when the ratio of “component having a molecular weight of 1000 or less” contained in the 4-methyl-1-pentene polymer added as a resin modifier is high. In addition, it has been found that the appropriate proportion can be defined in relation to the intrinsic viscosity. The above formula (I) is a relational expression that defines the allowable value of the component content with a molecular weight of 1000 or less, taking into consideration the influence of the molecular weight of the 4-methyl-1-pentene polymer (B).

  Although the detailed mechanism is not clear, it is considered that a component having a molecular weight of 1000 or less particularly gives stickiness to the resin composition among 4-methyl-1-pentene polymers. Therefore, it is presumed that the release effect cannot be sufficiently obtained unless the component having a molecular weight of 1000 or less in the 4-methyl-1-pentene polymer (B) is made a certain ratio or less. It is also considered that the 4-methyl-1-pentene polymer (B) itself tends to block. Furthermore, a low molecular weight component having a molecular weight of 1000 or less is estimated to cause a decrease in mechanical properties. In particular, the lower the molecular weight of the 4-methyl-1-pentene polymer (B), the greater the influence of components having a molecular weight of 1000 or less.

The amount of terminal double bonds in the 4-methyl-1-pentene polymer calculated by ¹ H-NMR of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention. Is preferably 0.001 or more and 100 or less per 1000 carbons, more preferably 0.001 or more and 0.5 or less, and 0.001 or more and 0.4 or less. More preferably, it is 0.001 or more and 0.3 or less.

  In order to control the amount of the terminal double bond in the 4-methyl-1-pentene polymer (B) as described above, the 4-methyl-1-pentene polymer (B) can be controlled with a higher molecular weight 4- The conditions for obtaining the methyl-1-pentene polymer by thermal decomposition may be adjusted; however, preferably using a Ziegler catalyst, more preferably a metallocene catalyst described later, Control is achieved by producing the coalescence (B).

  The iodine value of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is preferably 0.001 g / 100 g or more and 180 g / 100 g or less, and 0.001 g / 100 g or more and 0. 9.9 g / 100 g or less is more preferable, 0.001 g / 100 g or more and 0.7 g / 100 g or less is more preferable, and 0.001 g / 100 g or more and 0.5 g / 100 g or less is still more preferable.

The density of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is usually in the range of 820 to 840 (kg / m ³ ). The density of the 4-methyl-1-pentene polymer (B) is measured according to the density gradient tube method of JIS K7112.

  The 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention tends to localize on the surface of the resin molded product. For this reason, when the 4-methyl-1-pentene polymer (B1) has many unsaturated bonds, it is expected that the 4-methyl-1-pentene polymer is easily deteriorated by oxygen in the atmosphere. Since 4-methyl-1-pentene polymer (B) has a low molecular weight, it is considered that the tendency is further strong. Therefore, the iodine value of the 4-methyl-1-pentene polymer (B) is preferably in the above range.

  The 4-methyl-1-pentene polymer (B) having such an iodine value may be obtained by thermally decomposing a high molecular weight 4-methyl-1-pentene polymer; It is obtained by polymerizing 4-methyl-1-pentene using a metallocene catalyst.

ここで、ＡとＢは、それぞれ試料と空実験で滴定に要したチオ硫酸ナトリウムのｍｌ数、Ｃは試料のｇ数である。 The iodine value of the 4-methyl-1-pentene polymer (B) is measured by the following method. That is, 2 g of 4-methyl-1-pentene polymer (B) was dissolved in 100 ml of decalin at 150 ° C .; left at room temperature until 50 ° C .; 20 ml of acetic acid in which 1 mmol of iodine monochloride was dissolved was added. Left in the dark for 30 minutes with occasional stirring; 20 ml of 10% aqueous potassium iodide solution added; titrated with 0.1N aqueous sodium thiosulfate solution. The iodine value indicating the number of g of iodine added to a 100 g sample was calculated by the following formula.

Here, A and B are the number of ml of sodium thiosulfate required for titration in the sample and the blank experiment, respectively, and C is the number of grams of the sample.

  The amount of n-decane soluble component at 10 ° C. of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is preferably 0.01% by mass or more and 99% by mass or less. It is more preferably 0.01% by mass or more and 80% by mass or less, and further preferably 0.01% by mass or more and 40% by mass or less. Here, the whole 4-methyl-1-pentene polymer (B) is taken as 100% by mass.

  The amount of soluble n-decane is about 3 g of 4-methyl-1-pentene polymer (B) added to 450 ml of n-decane; dissolved at 145 ° C .; cooled to 10 ° C .; n-decane insoluble part by filtration The n-decane soluble part is recovered from the filtrate.

  In order to control the amount of n-decane soluble component of the 4-methyl-1-pentene polymer (B), the 4-methyl-1-pentene polymer (B) is changed to a higher molecular weight 4-methyl-1 -The temperature conditions for pyrolyzing the pentene polymer may be adjusted, or 4-methyl-1-pentene may be produced by polymerization using a Ziegler catalyst; preferably, a metallocene catalyst described later Manufactured by.

The isodyad tacticity calculated by ¹³ C-NMR of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is preferably 70% to 99%, preferably 80 to It is more preferably 99%, further preferably 90 to 99%, and particularly preferably 93 to 99%.

  The 4-methyl-1-pentene polymer (B) having such an isodyad tacticity is prepared by adjusting the temperature conditions when pyrolyzing a higher molecular weight 4-methyl-1-pentene polymer. Preferably, it can be produced by polymerizing a 4-methyl-1-pentene composition using a Ziegler-type catalyst such as a magnesium compound-supported titanium catalyst, more preferably a metallocene catalyst described later. it can.

The isodyad tacticity of the 4-methyl-1-pentene polymer (B) is obtained by expressing any two head-to-tail linked 4-methyl-1-pentene unit chains in the polymer chain in a planar zigzag structure. , Defined as the proportion of isobutyl branching directions that are the same. Isodyad tacticity is determined from the ¹³ C-NMR spectrum according to the following formula.

In the above formula, m and r represent the absorption intensity derived from the main chain methylene of 4-methyl-1-pentene units bonded in the head-to-tail manner represented by the following formula.

The ¹³ C-NMR spectrum of the 4-methyl-1-pentene polymer (B) is measured using a nuclear magnetic resonance apparatus (for example, a GX-500 type NMR measurement apparatus manufactured by JEOL Ltd.) having a resonance frequency of 400 MHz. In an NMR sample tube (5 mmφ), the sample is completely dissolved in about 0.5 ml of hexachlorobutadiene, o-dichlorobenzene, or 1,2,4-trichlorobenzene; 05 ml was added; measurement was performed at 120 ° C. by the proton complete decoupling method (the number of integration was 10,000 or more). As measurement conditions, a flip angle of 45 ° and a pulse interval of 5 sec or more are selected. The chemical shift was set at 127.7 ppm of benzene, and the chemical shifts of other carbon peaks were based on this.

  NMR measurement may be performed as follows. That is, 0.35 g of a sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. After this solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added and charged into an NMR tube having an inner diameter of 10 mm. The following is the same as described above.

  A peak region is divided into a first region on the high magnetic field side and a second region on the low magnetic field side by dividing the region of 41.5 to 43.3 ppm by the minimum point of the peak profile. In the first region, the main chain methylene in the 2-chain 4-methyl-1-pentene unit represented by (m) resonates, but the methylene peak connected to the comonomer also overlaps. The integrated value obtained by subtracting twice the peak area derived from ˜35.5 ppm comonomer is defined as “m”. In the second region, the 4-methyl-1-pentene unit 2-chain main chain methylene represented by (r) resonates, and the integrated value is defined as “r”.

  The content of the 4-methyl-1-pentene polymer (B) in the resin composition of the present invention may vary depending on the base resin. For example, when the content of polyethylene resin in the base resin is high, the upper limit of the content of 4-methyl-1-pentene polymer (B) is set lower; the content of polypropylene resin in the base resin is high In that case, the upper limit of the content of the 4-methyl-1-pentene polymer (B) is set higher. This is because the polypropylene resin is more compatible with the 4-methyl-1-pentene polymer (B) than the polyethylene resin.

  For example, the resin composition of the present invention has a 4-methyl-1-pentene polymer (B) having a content of 0.1 parts by mass or more and less than 5 parts by mass with respect to a base resin (A1) containing 100 parts by mass of a polyethylene resin. ) Is preferably included. Further, the resin composition of the present invention is a 4-methyl-1-pentene polymer (B) having a content of 0.1 parts by mass or more and less than 10 parts by mass with respect to a base resin (A2) containing 100 parts by mass of a polypropylene resin. ) Is preferably included. In any case, the content of the 4-methyl-1-pentene polymer (B) is preferably set so as to be compatible with the base resin.

  Further, the content of the 4-methyl-1-pentene polymer (B) in the master batch (such as pellets before molding) of the resin composition of the present invention is not particularly limited, and a higher concentration of 4-methyl-1 -A pentene polymer (B) may be blended.

4. Preparation of 4-methyl-1-pentene polymer (B) The 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention may be produced directly by polymerizing olefins. Well; high molecular weight 4-methyl-1-pentene polymers may be prepared by thermal decomposition. In addition, the 4-methyl-1-pentene polymer (B1) may be purified by a method such as solvent fractionation that is fractionated based on a difference in solubility in a solvent, or molecular distillation that is fractionated based on a difference in boiling point.

  When the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is directly produced by a polymerization reaction, for example, 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms are used. The melting point, stereoregularity and molecular weight, intrinsic viscosity [η], and the like are controlled by adjusting the amount charged, the type of polymerization catalyst, the polymerization temperature, the amount of hydrogenation during polymerization, and the like.

  On the other hand, when the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention is produced by thermally decomposing a higher molecular weight 4-methyl-1-pentene polymer. The desired molecular weight and intrinsic viscosity [η] are controlled by controlling the temperature and time of thermal decomposition.

  For the production of the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention, a conventionally known polymerization catalyst can be used. Conventionally known polymerization catalysts include, for example, JP-A-57-63310, JP-A-58-83006, JP-A-3-706, JP-A-3476793, JP-A-4-218508, and JP-A-4-218508. Magnesium-supported titanium catalyst described in 2003-105022, etc .; International Publication No. 01/53369 pamphlet, International Publication No. 01/27124 pamphlet, Japanese Patent Laid-Open No. 3-193796 or Japanese Patent Laid-Open No. 2-41303 The metallocene catalysts described in the above are preferably used. As the magnesium-supported titanium catalyst, a catalyst containing a polyether as an electron donor component is particularly preferable because a polymer having a relatively narrow molecular weight distribution tends to be obtained.

Thus, the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention can be produced using a metallocene catalyst. As the metallocene catalyst, an olefin polymerization catalyst using a metallocene compound represented by the following general formula (1) or (2) is preferably used.

In the above general formula (1) or (2), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ is selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different. R ¹ to R ⁴ adjacent to each other may be bonded to each other to form a ring; R ⁵ to R ¹² adjacent to each other may be bonded to each other to form a ring.

  A in the general formula (2) is a divalent hydrocarbon group having 2 to 20 carbon atoms which may partially contain an unsaturated bond and / or an aromatic ring. A may contain two or more ring structures including a ring formed with Y.

  M in the general formula (1) or (2) is a metal selected from Group 4 of the periodic table. Y may be carbon or silicon, Q may be selected from halogen, hydrocarbon group, anionic ligand or neutral ligand capable of coordinating with a lone pair, in the same or different combination, and j is 1 to 4 It is an integer.

Preferred examples of the hydrocarbon group represented by R ^{1 to} R ¹⁴ in the general formula (1) or (2) include an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms or an alkylaryl group having 7 to 20 carbon atoms is included, and may contain one or more ring structures. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methyl. Propyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1 -Cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl, etc. Is included.

Preferred examples of the silicon-containing hydrocarbon group represented by R ^{1 to} R ¹⁴ in the general formula (1) or (2) include an alkylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, or An arylsilyl group is included. Specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like.

In the general formula (1) or (2), R ¹ and R ³ are preferably hydrogen, and R ² is preferably a hydrocarbon group or a silicon-containing hydrocarbon group. R ² is more preferably a sterically bulky substituent, and R ² is particularly preferably a substituent having 4 or more carbon atoms.

Of the substituents R ⁵ to R ¹² on the fluorene ring in the above general formula (1) or (2), the adjacent substituents may be bonded to each other to form a ring. That is, the substituted fluorenyl group in the general formula (1) or (2) can be benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl, or the like.

In the general formula (1) or (2), the substituents R ⁵ to R ¹² on the fluorene ring are symmetrical from the viewpoint of synthesis, that is, R ⁵ = R ¹² , R ⁶ = R ¹¹ , R ⁷ = R ¹⁰ and R ⁸ = R ⁹ are preferred. That is, the fluorenyl group in the general formula (1) or (2) is unsubstituted fluorenyl, 3,6-disubstituted fluorenyl, 2,7-disubstituted fluorenyl, or 2,3,6,7-tetrasubstituted fluorenyl. Is more preferable (here, the 3-position, 6-position, 2-position and 7-position on the fluorene ring correspond to R ⁷ , R ¹⁰ , R ⁶ and R ¹¹ , respectively).

R ¹³ and R ¹⁴ in the general formula (1) are selected from hydrogen and a hydrocarbon group, and may be the same or different from each other. Specific examples of preferred hydrocarbon groups include the same hydrocarbon groups represented by R ^{1 to} R ¹⁴ .

Y in the general formula (1) is carbon or silicon, and is bonded to R ¹³ and R ¹⁴ to form a substituted methylene group or a substituted silylene group as a bridging portion. Preferred examples of substituted methylene groups include methylene, dimethylmethylene, diisopropylmethylene, methyl tert-butylmethylene, dicyclohexylmethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, methylnaphthylmethylene, dinaphthylmethylene; Preferred examples of the silylene group include dimethylsilylene, diisopropylsilylene, methyl tert-butylsilylene, dicyclohexylsilylene, methylcyclohexylsilylene, methylphenylsilylene, diphenylsilylene, methylnaphthylsilylene, dinaphthylsilylene and the like.

  Y in the general formula (2) is carbon or silicon and is bonded to a divalent hydrocarbon group A having 2 to 20 carbon atoms which may contain an unsaturated bond and / or an aromatic ring, and is a cycloalkylidene group Alternatively, it constitutes a cyclomethylenesilylene group or the like. Specific examples of preferred cycloalkylidene groups include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, bicyclo [3.3.1] nonylidene, norbornylidene, adamantylidene, tetrahydronaphthylidene Examples of preferred cyclomethylenesilylene groups include cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, cycloheptamethylenesilylene. Etc. are included.

  M in the general formulas (1) and (2) is a metal element selected from Group 4 of the periodic table, and may be titanium, zirconium, hafnium, or the like.

Q in the general formulas (1) and (2) is the same or different from halogen, a hydrocarbon group having 1 to 20 carbon atoms, an anionic ligand, or a neutral ligand capable of coordinating with a lone pair of electrons. Chosen by Specific examples of halogen include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include the same hydrocarbon groups represented by R ^{1 to} R ¹⁴ . Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine; or tetrahydrofuran, diethyl ether, dioxane, 1,2- Ethers such as dimethoxyethane are included. Among these, Q may be the same or different combinations, but at least one is preferably a halogen or an alkyl group.

  Specific examples of the metallocene compound in the present invention include the compounds exemplified in WO01 / 27124, but the scope of the present invention is not particularly limited thereby. Among these, the metallocene compound represented by the general formula (1) is preferable from the viewpoint of molecular weight distribution and terminal structure.

As described above, the 4-methyl-1-pentene polymer (B) contained in the resin composition of the present invention can be produced using a metallocene catalyst. In this case, the catalyst composition contains the following components. It is preferable.
Component (i): Metallocene compound represented by the above general formula (1) or (2) Component (ii): (ii-1) organometallic compound, (ii-2) organoaluminum oxy compound, and (ii-3) ) At least one compound selected from compounds that react with the metallocene compound (i) to form an ion pair. Component (iii): particulate carrier (not essential component but included as necessary)

  These catalyst compositions have been used conventionally, and are described in, for example, WO 01/27124.

  The polymerization for obtaining the 4-methyl-1-pentene polymer (B) using the metallocene catalyst is either a liquid phase polymerization method such as a solution polymerization method or a suspension polymerization method, or a gas phase polymerization method. Also good. In the liquid phase polymerization method, an inert hydrocarbon solvent may be used. Specific examples of the inert hydrocarbon solvent include aliphatic carbonization such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Hydrogen; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, or mixtures thereof In addition, olefins containing 4-methyl-1-pentene as a polymerization monomer can be used as a solvent.

The amount of component (i) is usually 10 ⁻⁸ to 10 ⁻² mol, preferably 10 ⁻⁷ to 10 ⁻³ mol per liter of the polymerization reaction volume.

  In the catalyst composition, the molar ratio [(ii-1) / M] of the component (ii-1) and the transition metal atom (M) in the component (i) is usually 0.01 to 5000. , Preferably 0.05 to 2000. In the catalyst composition, the molar ratio [(ii-2) / M] of the aluminum atom of component (ii-2) and the transition metal atom (M) in component (i) is usually 10 to 5000, preferably 20-2000. In the catalyst composition, the molar ratio [(ii-3) / M] of the component (ii-3) and the transition metal atom (M) in the component (i) is usually 1 to 10, preferably 1 to 5. To be.

  The temperature of the polymerization reaction for obtaining the 4-methyl-1-pentene polymer (B) using the metallocene catalyst is usually −50 to 400 ° C., preferably 10 to 300 ° C., more preferably 10 to 250 ° C. It is a range. If the polymerization temperature is too low, the polymerization activity per unit catalyst is lowered, which is not industrially preferable.

  The polymerization pressure is usually under normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions.

  In addition, by introducing hydrogen gas into the polymerization reaction system, the polymerization activity can be controlled, and the molecular weight and intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (B) can be adjusted. it can. The amount of hydrogen gas introduced is suitably about 0.001 to 100,000 NL per kg of olefin.

Compatibilizer (C) The resin composition of the present invention comprises a base resin (A) comprising a polyethylene resin and / or a polypropylene resin, a 4-methyl-1-pentene polymer (B), and a compatibilizer. (C).

  When 4-methyl-1-pentene polymer (B) is blended with base resin (A), 4-methyl-1-pentene polymer (B) is mixed with base resin (A) under high temperature conditions (for example, melt kneading). Even under temperature conditions). In particular, the blending amount of 4-methyl-1-pentene polymer (B) with respect to the base resin (A) is high, or the molecular weight of the 4-methyl-1-pentene polymer (B) is large. Then, it is often difficult to achieve compatibility. For this reason, the resin composition containing the base resin (A) and the 4-methyl-1-pentene polymer (B) and the molded product thereof often have reduced transparency and flexibility.

  The compatibilizing agent (C) in the resin composition of the present invention improves the compatibility of the base resin (A) and the 4-methyl-1-pentene polymer (B), thereby improving the transparency of the resin composition. In addition, the mold releasability can be further improved while maintaining flexibility.

  It has been found that when the compatibilizing agent (C) has a low molecular weight or has a bulky skeleton in the molecular chain, it has the effect of improving the transparency and releasability of the resin composition. In particular, when the compatibilizer (C) is selected from the group consisting of polyethylene wax, polypropylene wax and petroleum resin, it has been found that these effects are high.

  Although the detailed mechanism is not clear, compatibilizers having a low molecular weight or a bulky skeleton in the molecular chain (polyethylene wax, polypropylene wax, petroleum resin, etc.) have a low molecular weight and a bulky skeleton in the molecular chain. Easy to mix with -methyl-1-pentene polymer. Therefore, when the resin composition of the present invention is molded, the 4-methyl-1-pentene polymer and the compatibilizer can be dissolved in the base resin, and 4-methyl-1-pentene in the base resin can be dissolved. It is considered that the dispersibility of the polymer is increased.

  Furthermore, even when the resin composition is solidified from the molten state, if no compatibilizer is used, the 4-methyl-1-pentene polymer is united to cause poor dispersion and accompanying transparency deterioration. easy. On the other hand, the compatibilizer added to the resin composition tends to be present at the interface between the 4-methyl-1-pentene polymer and the base resin. Therefore, it is considered that the high transparency of the base resin can be maintained without the 4-methyl-1-pentene polymer finally being unevenly distributed. Further, when the dispersibility of the 4-methyl-1-pentene polymer in the base resin is increased, it is suggested that the 4-methyl-1-pentene polymer effectively covers the surface of the molded product. Thereby, it is thought that the good mold release property of a molded article can be obtained.

  The component and blending amount of the compatibilizer (C) should be selected mainly depending on the composition of the base resin (A) and the blending amount of the 4-methyl-1-pentene polymer (B). . The amount of the compatibilizer (C) used as a standard is 1 to 100 parts by weight, preferably 10 to 70 parts, particularly preferably 100 parts by weight of the 4-methyl-1-pentene polymer (B). Is 30-60 parts by mass.

  The density of the compatibilizer (C) is preferably between the density of the base resin (A) and the density of the 4-methyl-1-pentene polymer. It is considered that substances having similar densities tend to be mixed with each other. Therefore, when the density of the compatibilizer (C) is between the density of the base resin (A) and the density of the 4-methyl-1-pentene polymer, the effect as the compatibilizer is further increased. It is thought.

Moreover, the difference between the density of the density and the compatibilizer of the base resin (A) (C) is preferably smaller than 50 kg / ^{m 3,} more preferred is less than 20 kg / ^{m 3.} When the density difference is in the above range, the effect as a compatibilizing agent is further enhanced, and both the releasability and transparency of the resin composition can be achieved.

  The polyethylene wax contained in the compatibilizing agent (C) in the present invention may be obtained by direct polymerization of ethylene alone or by direct polymerization of ethylene and α-olefin; It may be obtained by decomposition. The preferred polyethylene wax is preferably directly polymerized. In addition, the polyethylene wax may be purified by a method such as solvent fractionation that is fractionated based on a difference in solubility in a solvent or molecular distillation that is fractionated based on a difference in boiling point. Examples of preferable polyethylene wax are described in, for example, JP-A-2009-144146, and will be briefly described below.

  The polyethylene wax as the compatibilizing agent (C) is, for example, a homopolymer of ethylene or a copolymer of ethylene and α-olefin. Examples of the α-olefin include α-olefins having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like; preferably propylene, 1-butene, 1- Includes hexene, 4-methyl-1-pentene.

The density of the polyethylene wax as the compatibilizing agent (C) measured according to the density gradient tube method of JIS K7112 (1999) is preferably 890 to 980 kg / m ³ , more preferably 900 to 980 kg / m. ³ . When the density of the polyethylene wax as the compatibilizer (C) is within such a range, the dispersibility of the polyethylene wax with respect to the base resin (particularly, the polyethylene resin) is improved.

  For example, when the polyethylene wax is a copolymer of ethylene and α-olefin, the density of the polyethylene wax should be controlled by adjusting the ratio of α-olefin to ethylene and selecting the type of α-olefin. Can do. For example, the density of polyethylene wax can be lowered by increasing the amount of α-olefin used relative to ethylene. The density of the polyethylene wax can also be adjusted by the polymerization temperature in production.

  The number average molecular weight in terms of standard polyethylene measured by gel permeation chromatography of polyethylene wax is preferably 700 to 4000, more preferably 1500 to 4000.

  The polyethylene wax having a number average molecular weight (Mn) of 700 to 4000 can be appropriately dispersed in the base resin (A) when the resin composition of the present invention is molded. Moreover, the extrusion load at the time of shaping | molding extrusion can be reduced. As a result, the productivity of the molded product can be improved.

  The number average molecular weight (Mn) of the polyethylene wax can be adjusted, for example, by the polymerization temperature in production.

  The polyethylene wax as the compatibilizing agent (C) preferably has a weight average molecular weight (Mw) in terms of standard polyethylene measured by gel permeation chromatography of 1000 to 9000, more preferably 1500 to 8000. .

  The polyethylene wax has a melt viscosity at 140 ° C. of preferably 10 to 10,000 mPa · s, more preferably 200 to 9000 mPa · s. The melt viscosity of polyethylene wax can be measured, for example, by a method such as a Brookfield viscometer, a strain control type or a stress control type rheometer.

  The melting point of the polyethylene wax is preferably 70 to 130 ° C, more preferably 90 to 130 ° C. Moreover, it is preferable that the crystallization temperature of polyethylene wax is 60-120 degreeC, More preferably, it is 80-120 degreeC.

  When the base resin (A) includes a polypropylene resin, the compatibilizer (C) is preferably a polypropylene wax. A preferred polypropylene wax is described below.

  The polypropylene wax as the compatibilizing agent (C) is a propylene homopolymer obtained by copolymerizing propylene and other monomers as required in the presence of a stereospecific catalyst, or propylene. It may be a main copolymer; it may be obtained by thermally decomposing high molecular weight polypropylene. The polypropylene wax may be purified using a method such as solvent fractionation, which is fractionated based on a difference in solubility in a solvent, or molecular distillation, which is fractionated based on a difference in boiling point. Examples of other monomers include ethylene, 1-butene, 1,3-butadiene, 1-hexene, 3-hexene, 1-octene, 4-octene and the like.

The density of the polypropylene wax measured according to the density gradient tube method of JIS K7112 is preferably 900 to 910 kg / m ³ . When the density of the polypropylene wax is within such a range, the dispersibility of the polypropylene wax with respect to the base resin (particularly polypropylene resin) is improved.

The number average molecular weight in terms of standard polypropylene measured by gel permeation chromatography of polypropylene wax is 50000 or less, preferably 100 to 30000, more preferably 1000 to 20000, and particularly preferably 2000 to 15000. .

  Further, the compatibilizer (C) may be a petroleum resin. Examples of the petroleum resin include, for example, an aliphatic petroleum resin whose main raw material is a C5 fraction of tar naphtha, an aromatic petroleum resin whose main raw material is a C9 fraction, and a copolymer petroleum resin thereof. That is, C5 petroleum resin (resin obtained by polymerizing C5 fraction of naphtha cracked oil), C9 petroleum resin (resin obtained by polymerizing C9 fraction of naphtha cracked oil), C5C9 copolymerized petroleum resin (C5 fraction of naphtha cracked oil) And a C9 fraction copolymerized resin).

  The petroleum resin as the compatibilizing agent (C) is preferably not subjected to hydrogenation treatment (hydrogenation treatment). Petroleum resins that have not been hydrotreated are generally excellent in heat resistance. Therefore, the function as the compatibilizing agent is not impaired even after the thermal process of the molding process.

  Examples of petroleum resins include coumarone indene resins containing styrenes, indenes, coumarone, and other dicyclopentadiene from the tar naphtha fraction; represented by condensates of p-tertiarybutylphenol and acetylene. Also included are xylene resins obtained by reacting o-xylene, p-xylene or m-xylene with formalin.

  Of the petroleum resins, vinyl aromatic petroleum resins are preferable. The vinyl aromatic petroleum resin is a vinyl aromatic hydrocarbon homopolymer; or an arbitrary selected from vinyl aromatic hydrocarbons and fractions having 4 and 5 carbon atoms produced as a by-product during petroleum refining and petroleum decomposition It is preferable that it is a copolymer resin with this fraction.

  In vinyl aromatic petroleum resins, examples of vinyl aromatic hydrocarbons include isopropenyl toluene, styrene, vinyl toluene, α-methyl styrene, etc., alone or in combination of two or more. Toluene is preferred.

Fraction of carbon number 4 and 5 to be copolymerized with a vinyl aromatic hydrocarbon (hereinafter referred to as C ₄ fraction and C ₅ fraction) are oil refining are those by-produced during oil decomposition; normal The boiling point under pressure is -15 ° C to + 45 ° C, and 1-butene, 2-butene, isobutene, butadiene, 1-pentene, 2-pentene, cyclopentene, 1,3-piperylene, isoprene, cyclopentadiene, 2-methyl It contains polymerizable monomers such as -1-butene, 2-methyl-2-butene, and 3-methyl-1-butene.

Fraction of carbon number 4 and 5 to be copolymerized with the vinyl aromatic hydrocarbon is any fraction selected from C ₄ and C ₅ fractions, C ₄ fraction and C ₅ fraction is, of course, C ₄ fraction obtained by removing butadiene, C ₅ fraction excluding isoprene, may be a C ₅ fraction obtained by removing cyclopentadiene.

  The polymerization reaction for obtaining the vinyl aromatic petroleum resin may be performed in the presence of a polymerization catalyst. The polymerization catalyst is, for example, a commonly used Friedel-Crafts catalyst. Examples of Friedel-Crafts catalysts include aluminum chloride, aluminum bromide, ethyldichloroaluminum, boron trifluoride, boron trifluoride complexes, and the like. Is included. The polymerization reaction may be performed in a suitable solvent. Examples of suitable solvents include hydrocarbon solvents such as pentane, hexane, octane, kerosene, cyclopentane, cyclohexane, methylcyclohexane, toluene, xylene, ethylbenzene, mesitylene. The polymerization reaction temperature is usually −50 ° C. to + 80 ° C.

  The softening point (ring and ball method) of the petroleum resin is preferably in the range of 70 ° C to 150 ° C, more preferably 105 ° C to 150 ° C, and further preferably 110 ° C to 140 ° C.

The density measured in accordance with the density gradient tube method of JIS K7112 of petroleum resin is preferably 950 to 1100 kg / m ³ . When the density of the petroleum resin is within such a range, the dispersibility of the petroleum resin with respect to the base resin is improved.

About Optional Components The resin composition of the present invention may contain an optional additive in an effective expression amount as necessary within a range that does not impair the object and effect of the present invention. Examples of optional additives include flame retardants such as brominated bisphenol, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, triphenyl phosphate, phosphonic acid amide and red phosphorus; antimony trioxide and sodium antimonate Flame retardant aids; heat stabilizers such as phosphate esters and phosphites; antioxidants such as hindered phenols; heat-resistant agents; weathering agents; light stabilizers; mold release agents; flow modifiers; Lubricant; Antistatic agent; Crystal nucleating agent; Plasticizer; Foaming agent; Weather resistance stabilizer; Heat resistance stabilizer; Anti-slip agent; Anti-blocking agent; Anti-fogging agent; Nucleating agent; Dye; Contains copper damage prevention agents.

  The resin composition of the present invention may contain a known wax such as a silicone-modified polyolefin wax, a silicone-polyethylene block copolymer, a silicone-based release agent, a release agent, and the like. A preferable blending amount of these components is 0 to 50% by mass, more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass.

  Furthermore, the resin composition of the present invention may contain a polymer other than the base resin (A) as an optional component as long as the object of the present invention is not impaired. Although there is no restriction | limiting in particular in a compounding quantity, It is preferable that it is about 0.1-30 mass parts with respect to 100 mass parts of base resin (A).

About the manufacturing method of the resin composition of this invention The resin composition of this invention is not restrict | limited especially as long as the effect of this invention is acquired. For example, the base resin (A), 4-methyl-1-pentene polymer (B), the compatibilizer (C), and other optional components may be mixed simultaneously or in any order. Mixing can be performed using a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, a single-screw or twin-screw extruder, and the like.

  The base resin (A) and the 4-methyl-1-pentene polymer (B) may be mixed in one step. On the other hand, first, a resin composition (also referred to as a master batch) having a high ratio of the 4-methyl-1-pentene polymer (B) to the base resin (A) is prepared; An additional base resin (A) may be mixed to obtain the resin composition of the present invention.

  In the master batch, the content of the 4-methyl-1-pentene polymer (B) with respect to 100 parts by mass of the base resin (A) is 1 to 900 parts by mass, preferably 3 to 300 parts by mass, more preferably 5 to 5 parts by mass. 100 parts by mass, particularly preferably 5 to 50 parts by mass. The masterbatch may contain the above-described compatibilizer (C) and known additives.

  Even when the base resin (A) and the 4-methyl-1-pentene polymer (B) are mixed, the 4-methyl-1-pentene polymer (B) is sufficiently dispersed in the resin (A). When not doing, it is preferable to manufacture the resin composition of this invention by a masterbatch method.

  The case where the 4-methyl-1-pentene polymer (B) is not sufficiently dispersed means that the molecular weight and molding temperature between the resin (A) and the 4-methyl-1-pentene polymer (B) are different. In the case where the difference in melt viscosity is large; and the addition amount of the 4-methyl-1-pentene polymer (B) is small. If the 4-methyl-1-pentene polymer (B) is not sufficiently dispersed, the effects expected from the addition of the 4-methyl-1-pentene polymer (B) (improvement of release properties, etc.) are sufficient. In some cases, it could not be obtained.

  In addition, when the base resin (A) and the 4-methyl-1-pentene polymer (B) are mixed in one step to obtain a resin composition, the discharge rate of the molding machine is not stable and the productivity is increased. There was also a problem. Furthermore, when the resin composition pellets obtained by mixing in one stage are pumped or sucked to be transported in the pipe and supplied to the mixer, the extruder hopper, etc., the resin is formed on the inner wall of the transport pipe member. There may be a problem that the low molecular weight component in the composition is fused, fixed and adhered. According to the masterbatch method, these problems can be solved.

About the molded article and use of the resin composition of the present invention The resin composition of the present invention can be molded into various molded articles depending on the purpose. For example, the resin composition of the present invention can be formed into a sheet, film, pipe, tube, bottle, fiber, tape, etc .; preferably a sheet, film, pipe, tube; particularly preferably formed into a sheet or film Is done.

  The molded article of the resin composition of the present invention is excellent in transparency, gas permeability, chemical resistance, releasability, releasability, and heat resistance. Further, since the 4-methyl-1-pentene polymer (B) is considered to be localized on the surface layer of the molded product of the resin composition of the present invention, the molded product has a sticky feeling in a wide range of environments from room temperature to high temperature. It is suppressed. This is because the 4-methyl-1-pentene polymer (B) has excellent heat resistance and low tack.

  Taking advantage of the above characteristics, the molded product of the resin composition of the present invention can be used as a substrate in various fields such as semiconductor processes, medical instruments, heat-resistant electric wires, heat-resistant tableware, and stripping materials. Examples of more specific uses of the molded product of the resin composition of the present invention are not particularly limited, but include cap liners, gaskets, glass interlayers, doors, door frames, window frames, peripheral edges, baseboards, opening frames. , Flooring materials, ceiling materials, wallpaper, stationery, office supplies, non-slip sheets, building material skin materials, pipes, electric wires, sheaths, wire harnesses, protective film adhesive layers, hot-melt adhesive materials, sanitary products, medical bags and tubes , Non-woven fabric, elastic material, fiber, shoe sole, shoe midsole, inner sole, sole, sandals, packaging film, sheet, food packaging film (outer layer, inner layer, sealant, single layer), stretch film, wrap film, Tableware, retort containers, stretched films, breathable films and the like are included.

  As a use of the film molded product of the resin composition of the present invention, a use utilizing the high melting point is preferable. Specific examples include a semiconductor process film.

  It is also preferable that the film molded product of the resin composition of the present invention is used for applications utilizing these release properties. Specifically, an adhesive layer can be formed on the film molded product of the resin composition of the present invention and used as an adhesive film. The pressure-sensitive adhesive layer is an acrylic pressure-sensitive adhesive layer, an ester-based pressure-sensitive adhesive layer, an olefin-based pressure-sensitive adhesive layer, a urethane-based pressure-sensitive adhesive layer, or the like, and a material having an adhesive force suitable for a substrate to be bonded may be used.

  Furthermore, a multilayer film comprising the film molded product of the resin composition of the present invention, a protective layer such as a polarizing plate or FPD (flat panel display), and the pressure-sensitive adhesive layer includes a polarizing plate protective film, a protective film for FPD, and the like. Can be used.

  The molding process of the resin composition of the present invention is performed by a known molding method such as an extrusion molding method, an injection molding method, a solution casting method, an inflation molding method, etc., but it is particularly preferably performed by an extrusion molding method.

  More specifically, the molding process of the resin composition of the present invention is performed by molding the resin composition in a molten state with shearing and / or uniaxial, biaxial, and plane stretching flows. Here, the molten state refers to a range from the melting point of the resin composition to less than 350 ° C., preferably from 170 ° C. to 350 ° C., particularly preferably from 200 to 250 ° C. Specific examples of molding involving shear flow include known molding methods such as extrusion molding, injection molding, and melt blown molding. Specific examples of the molding method involving uniaxial, biaxial, and plane extension flow include known methods such as T-die (film) molding, blow molding, and stretching.

  Further, the molding process of the resin composition of the present invention is performed by obtaining a primary molded product by primary molding such as extrusion molding, injection molding, solution casting, etc .; and further molding the primary molded product by a method such as blow molding or stretching. May be. For example, when obtaining a film-like or sheet-like molded product, a primary molded product obtained by molding the resin composition of the present invention into a sheet shape by a T-die extrusion method or the like is uniaxially stretched or biaxially stretched. May be obtained.

  Furthermore, the molding process of the resin composition of the present invention may be performed by directly molding the resin composition of the present invention; when molding the resin composition of the present invention, a 4-methyl-1-pentene polymer May be additionally added. For example, when the above-mentioned master batch is molded with a molding machine (extruder), a 4-methyl-1-pentene polymer may be fed into the molding machine (extruder).

Surface protective film The surface protective film of the present invention has at least two layers of a surface layer and an adhesive layer, and may optionally have three layers of a surface layer, a base material layer, and an adhesive layer, Furthermore, you may have a separate layer. In any case, the adhesive layer is disposed on one surface of the surface protective film, and the surface layer is disposed on the other surface.

  The surface layer of the surface protective film of the present invention is characterized by comprising the above-described resin composition of the present invention. On the other hand, the pressure-sensitive adhesive layer of the surface protective film of the present invention may be composed of a known pressure-sensitive adhesive (that is, olefin-based elastomer, styrene-based elastomer, acrylic pressure-sensitive adhesive, etc.), and the pressure-sensitive adhesive is not particularly limited.

  Examples of the olefin-based elastomer include an α-olefin polymer or copolymer having 2 to 20 carbon atoms; a copolymer of ethylene and an unsaturated carboxylic acid or an unsaturated carboxylic acid ester. The melting point of the olefin elastomer is preferably 110 ° C. or less, more preferably 100 ° C. or less, still more preferably 80 ° C. or less, or no melting point is observed.

  Specific examples of olefin elastomers include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, ethylene / 4-methylpentene-1 copolymers, ethylene / 1- Octene copolymer, propylene homopolymer, propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, 1-butene homopolymer, 1-butene / ethylene copolymer, 1-butene / propylene Copolymer, 4-methylpentene-1 homopolymer, 4-methylpentene-1, propylene copolymer, 4-methylpentene-1, 1-butene copolymer, 4-methylpentene-1, propylene, 1 -Butene copolymer, propylene / 1-butene copolymer, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, ethylene / methyl methacrylate copolymer Etc. are included. From the viewpoint of the temporal stability of adhesive strength, a propylene homopolymer, a propylene / ethylene copolymer, and a propylene / 1-butene copolymer are preferable. More preferred is a propylene / ethylene / 1-butene copolymer.

  The styrene elastomer may be a known styrene elastomer having a polystyrene phase as a hard segment. Specific examples of styrene elastomers include styrene / butadiene copolymer (SBR), styrene / isoprene / styrene copolymer (SIS), styrene / butadiene / styrene copolymer (SBS), styrene / ethylene / butadiene / styrene. Copolymers (SEBS) and their hydrides, styrene / isobutylene / styrene triblock copolymers (SIBS), styrene / isobutylene diblock copolymers (SIB) and the like are included. Preferred are styrene / isobutylene / styrene triblock copolymer (SIBS) and styrene / isobutylene diblock copolymer (SIB).

  The pressure-sensitive adhesive in the pressure-sensitive adhesive layer of the surface protective film of the present invention may be an olefin-based elastomer and / or a styrene-based elastomer alone or a blend of components having different compositions. Further, the pressure-sensitive adhesive of the pressure-sensitive adhesive layer of the surface protective film of the present invention is a resin modifier such as a polyolefin such as polyethylene or polypropylene, an acid-modified polyolefin, a polyester or a polyamide, or an antistatic agent, as long as the characteristics of the present invention are not impaired. In addition, various additives such as a crystal nucleating agent and an antioxidant may be included. Thereby, the adhesive force can be controlled.

  As an example of an acrylic pressure-sensitive adhesive, as a monomer component, a main monomer for developing adhesiveness; a comonomer that increases cohesion; a monomer having a functional group for improving adhesion and reacting with a crosslinking agent And a copolymer thereof. It can also be crosslinked using a crosslinking agent.

  Examples of the main monomer include ethyl acrylate, n-butyl acrylate, n-octyl acrylate, etc., alkyl acrylates having 2 to 14 carbon atoms in the alkyl group; isobutyl methacrylate, n-octyl methacrylate, etc. , Methacrylic acid alkyl ester having 4 to 14 carbon atoms in the alkyl group, and the like may be used in combination of two or more.

  Examples of comonomers for increasing the cohesive force include methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc., alkyl acrylates and alkyl methacrylates having 1 to 8 carbon atoms in the alkyl group; Examples thereof include styrene, vinyl acetate, acrylonitrile, methacrylonitrile, acrylamide and the like. Two or more of these may be combined.

  The surface protective film of the present invention may have at least one base material layer between the surface layer and the adhesive layer. The base material layer can control the mechanical strength and transparency of the film, and can act as an adhesive layer when the adhesive force between the surface layer and the adhesive layer is insufficient. When the adhesive layer is used, a polyolefin resin, an adhesive resin, or an adhesive is used.

  The base material layer is not particularly limited, but generally, a crystalline polyolefin such as polypropylene or polyethylene having a melting point of 100 ° C. or higher; polyester, polyamide, polyolefin elastomer, and the like can be used. When the base material layer is used as an adhesive layer, modified polyolefin, polyolefin elastomer, styrene elastomer, polyester elastomer or the like is used. Among these, it is preferable to use polypropylene or polyolefin elastomer as an intermediate layer from the viewpoint of productivity and transparency.

  The surface protective film of the present invention can be produced by laminating a surface layer, an adhesive layer, and, if necessary, a base material layer. The lamination method is not particularly limited, and is a method of laminating by a known lamination method such as extrusion lamination or extrusion coating on a surface layer film obtained by T-die molding or inflation molding in advance; a base material layer and an adhesive layer. There may also be a method of laminating each film by dry lamination after independently forming the film. However, from the viewpoint of productivity, the surface protective film of the present invention is preferably produced by coextrusion molding in which each component of the surface layer, the base material layer, and the adhesive layer is subjected to molding using a multilayer extruder.

  The thickness of the surface layer (A) of the surface protective film of the present invention is 0.1 to 100 μm, preferably 0.3 to 50 μm, more preferably 0.5 to 30 μm, and further preferably 1 to 20 μm. The thickness of the pressure-sensitive adhesive layer (X) is 0.1 to 50 μm, preferably 0.3 to 40 μm, more preferably 0.5 to 30 μm. The thickness of the surface protective film of the present invention is 1 to 300 μm, preferably 2 to 200 μm, more preferably 3 to 100 μm.

  Since the surface protective film of the present invention can have excellent transparency, it can be suitably used particularly for optical applications. As preferable transparency of the surface protective film of the present invention, haze measured with a thickness of 50 μm is 20% or less, more preferably 8% or less, and further preferably 7% or less.

  The protective film of the present invention can be stored in a roll shape. That is, it is stored in a state where the surface layer and the adhesive layer are alternately overlapped. When a film having a conventional surface layer and an adhesive layer is stored in a roll shape, the surface layer and the adhesive layer are blocked; as a result, it is difficult to unwind the film from the roll film. There was a thing. For this purpose, a film having a conventional surface layer and adhesive layer is formed in a roll shape with a release film interposed therebetween.

  On the other hand, since the surface layer of the protective film of the present invention has excellent releasability, it is said that the surface layer and the adhesive layer do not block even if it is rolled without sandwiching the release film. Has an effect.

  In the following, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited thereto.

The base resin (A) used in the examples and comparative examples is as follows.
LDPE-1: High-pressure low-density polyethylene (Novatech LD LC620, manufactured by Nippon Polyethylene) Density 922, MFR7 (190 ° C), melting point 110 ° C
LDPE-2: High-pressure method low-density polyethylene (Novatech LD LC520, manufactured by Nippon Polyethylene) Density 923, MFR 3.6, melting point 111 ° C
Homo PP: Propylene homopolymer (Prime Polypro F107DV, Prime Polypro Co., Ltd.) Density 910, MFR7 (230 ° C)

  The 4-methyl-1-pentene polymer (B) used in Examples and Comparative Examples was obtained by the following Synthesis Examples 1 to 3.

[Synthesis Example 1]
Synthesis of 4-methyl-1-pentene polymer (B1)
150 g of 4-methyl-1-pentene polymer (DX310 manufactured by Mitsui Chemicals) was charged into a 500 ml branched polymerization flask, and heated to 350 ° C. using a sand bath while flowing nitrogen. After confirming that the polymer on the flask wall surface was melted, the 4-methyl-1-pentene polymer was thermally decomposed by continuing stirring for 2 hours while maintaining the temperature. Thereafter, by cooling to room temperature, a thermal decomposition product of 4-methyl-1-pentene polymer having the following physical properties was obtained.

Intrinsic viscosity [η] = 0.16 dl / g
A value = 4.55
0.2 × [η] ^(−1.5) = 3.13
4-methyl-1-pentene constituent unit = 89.2 wt%, C16 and C18 constituent units = 10.8 wt%
Mw measured by GPC = 18300, Mn = 3660, Mw / Mn = 4.99
Melting point = 208 ° C
Critical surface tension = 25.0 mN / m
Terminal double bond amount = 4.8 / 1000 carbons Density = 832 kg / m ³

[Synthesis Example 2]
Synthesis of 4-methyl-1-pentene polymer (B2)
150 g of 4-methyl-1-pentene polymer (DX820, manufactured by Mitsui Chemicals) was charged into a 500 ml branched polymerization flask and heated to 370 ° C. using a sand bath while flowing nitrogen. After confirming that the polymer on the flask wall surface was melted, the 4-methyl-1-pentene polymer was thermally decomposed by continuing stirring for 2 hours while maintaining the temperature. Thereafter, by cooling to room temperature, a thermal decomposition product of 4-methyl-1-pentene polymer having the following physical properties was obtained.

Intrinsic viscosity [η] = 0.08 dl / g
A value = 11.96
0.2 × [η] ^(−1.5) = 8.84
4-methyl-1-pentene structural unit = 93.1 wt%, C10 structural unit = 6.9 wt%
Mw measured by GPC = 8030, Mn = 2000, Mw / Mn = 4.01
Melting point = 197 ° C.
Critical surface tension = 25.9 mN / m
Terminal double bond amount = 7.9 pieces / 1000 carbons Density = 831 kg / m ³

[Synthesis Example 3]
Synthesis of 4-methyl-1-pentene polymer (B3)
[Preparation of catalyst solution]
Add 1 μmol of isopropyl (3-t-butyl-5-methylcyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride to a glass flask thoroughly purged with nitrogen as a co-catalyst. A catalyst solution was obtained by adding 0.5 mmol of hexane solution of MMAO (product name: MMAO-3A) manufactured by Tosoh Finechem Co. in terms of Al atom.

[polymerization]
A 1-liter glass autoclave equipped with a stirrer and thoroughly purged with nitrogen was mixed with decane 561 ml, 4-methyl-1-pentene 180 ml, a mixture of high-purity hexadecene and octadecene, dialen D168 (manufactured by Mitsubishi Chemical Corporation). (Registered trademark) (9 ml) was charged. Hydrogen (6 liters / hour) was passed through this, and the mixture was allowed to stand at 30 ° C. for 10 minutes. Thereafter, 0.375 mmol of triisobutylaluminum was added, and then the catalyst solution prepared above was added to initiate polymerization. Hydrogen (6 liters / hour) was continuously supplied, and polymerization was performed at 30 ° C. under normal pressure for 1 hour, and then a small amount of methanol was added to stop the polymerization. The polymerization solution was poured into 4 liters of a methanol / acetone mixture (volume ratio 4/1), and the polymer was recovered by filtration. The recovered polymer was dried at 80 ° C. under reduced pressure for 10 hours to obtain 37.6 g of a polymer having the following physical properties.

Intrinsic viscosity [η] = 0.13 dl / g
A value = 2.86
0.2 × [η] ^(−1.5) = 4.27
4-methyl-1-pentene structural unit = 93.5 wt%, C16 and C18 structural units = 6.5 wt%
Mw measured by GPC = 15900, Mn = 4010, Mw / Mn = 3.97
Melting point = 192 ° C.
Critical surface tension = 27.0 mN / m
Terminal double bond amount = 0.2 / 1000 carbon density = 832 kg / m ³

The compatibilizing agent (C) used in Examples and Comparative Examples is as follows.
PE wax (C2 / C4): polyethylene wax (copolymer of polyethylene and polypropylene) (Excellex 48070BT), density 902, number average molecular weight 3400, melting point 90 ° C.
PP wax 1 (C3): polypropylene wax (high wax NP055) density 900, number average molecular weight 3300, melting point 136 ° C.
PP wax 2 (C3): polypropylene wax (high wax NP505) density 903, number average molecular weight 9600, melting point 143 ° C.
St petroleum resin: Styrene petroleum resin (FTR8120, Mitsui Chemicals), homopolymer of isopropenyltoluene, density 1020, number average molecular weight 1100, softening point 120 ° C

In the present invention and examples, the properties were measured as follows unless otherwise specified in the specification.
[Intrinsic viscosity]
About 20 mg of the sample was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135 ° C. The decalin solution was diluted by adding 5 ml of decalin solvent, and the specific viscosity ηsp was measured in the same manner. This dilution operation and specific viscosity measurement were further repeated twice. The value of ηsp / C when the concentration (C) was extrapolated to 0 was defined as the intrinsic viscosity.
[Η] = lim (ηsp / C) (C → 0 [molecular weight])

[composition]
^It was determined by analysis of ¹³ C-NMR spectrum.

[Molecular weight distribution]
The ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) was determined from GPC measurement. The measurement was performed under the following conditions. The weight average molecular weight and number average molecular weight were determined based on the following conversion method by preparing a calibration curve using commercially available monodisperse standard polystyrene.

Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene Column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: o-dichlorobenzene solution (0.15 mg / mL)
Temperature: 140 ° C
Molecular weight conversion: PS conversion / General calibration method

The coefficient of the Mark-Houwink viscosity formula shown below was used for calculation of general-purpose calibration.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 ⁻⁴ , aPE = 0.70

[Melting point of 4-methyl-1-pentene polymer]
Using a differential scanning calorimeter (Diamond DSC, manufactured by Perkin Elmer), about 5 mg of a sample was packed in an aluminum pan, heated to 280 ° C. at 10 ° C./min; held at 280 ° C. for 5 minutes; After cooling to 30 ° C./min; holding at 30 ° C. for 5 min; endothermic peak when the temperature is raised to 280 ° C. at 10 ° C./min is defined as the melting point.

[Critical surface tension]
Test samples for critical surface tension measurement were prepared as follows. A 4-methyl-1-pentene polymer was cast on a SUS plate. Casting was performed by heating and melting a 4-methyl-1-pentene polymer on a SUS plate under a nitrogen atmosphere at 250 ° C. for 5 minutes, and then returning to normal temperature and solidifying. The critical surface tension was measured on the surface of the obtained test sample.

  Using an image processing type / solid-liquid interface analysis system (Dropmaster 500, manufactured by Kyowa Interface Science Co., Ltd.), at the temperature of 23 ° C and 50% RH, on the surface of the test sample, four types of liquid mixture for wetting tension test (ethylene glycol) Monoethyl ether / formamide and the surface tension of each test mixture were 31, 34, 37 and 40 mN / m), and the contact angle was measured. The contact angle was measured for five test samples, and the average value was obtained.

  The points (five or more) obtained from cos θ (Y axis) calculated from the average contact angle θ and the surface tension (X axis) of the test liquid mixture were plotted on XY coordinates. The surface tension (X axis) corresponding to the intersection of the straight line obtained by the least square method of these points and cos θ = 1 was defined as the critical surface tension (mN / m).

[Terminal double bond content]
The terminal double bond of 4-methyl-1-pentene polymer is classified into vinyl type, vinylidene type, disubstituted internal olefin type and trisubstituted internal olefin type double bond, and the total amount is ¹ H-NMR. Measured by In the ¹ H-NMR spectrum of the 4-methyl-1-pentene polymer, the peak for two protons (H1) out of the peak for three protons derived from the vinyl group is around 4.8 to 5.0 ppm. The remaining one proton (H1 ′) is observed in the vicinity of 5.7 to 5.9 ppm. Further, a peak (H2) for two protons derived from the vinylidene group is observed in the vicinity of 4.7 ppm. Further, a peak for two protons (H3) derived from a disubstituted internal olefin was observed in the vicinity of 5.2 to 5.4 ppm, and a peak for one proton derived from a trisubstituted internal olefin (H4) was 5.0. It is observed around ~ 5.2 ppm.

When the integral value of all protons is Ha, the terminal double bond amount L (number / 1000 carbons) is calculated by the following formula.
L = [2 × (H1 + H1 ′) + 3 × (H2 + H3) + 6 × H4] × 1000 / 3Ha

^{The 1} H-NMR measurement uses a JNM-ECX400P type nuclear magnetic resonance apparatus manufactured by JEOL. A sample of 20 mg was completely dissolved in about 0.5 ml of deuterated o-dichlorobenzene in an NMR sample tube (5 mmφ), and then measured at 120 ° C.

[density]
It was measured according to the density gradient tube method of JIS K7112.

[Buts]
The amount of gelled product present in the films obtained in Examples 1 to 7 and Comparative Examples 1 to 6 described later was visually evaluated.
◎: No gelled product ○: Slightly gelled product exists ×: A large amount of gelated product exists

[All haze, internal haze]
According to JIS K7105, the total haze and internal haze of the film obtained by the below-mentioned Example and the comparative example were measured.

[Adhesive releasability 1]
An acrylic adhesive tape (manufactured by Nitto Denko Corporation, No. 31B) was superposed on the surface of the films obtained in Examples 1 to 7 and Comparative Examples 1 to 6 which will be described later and in contact with the chill roll. The laminate was reciprocated twice with a 2 kg hand-type rubber roller for pasting. It was cut into a width of 25 mm and cured for 1 hour under the condition of 23 ° C. Thereafter, 180 ° peel strength (N / 50 mm) was measured at 23 ° C. under a test speed of 300 mm / min using an Intesco peel tester.

[Suji-Mura]
The amount of streaks present in the films obtained in Example 8 and Comparative Examples 7 to 10 described later was visually evaluated.
◎: No streaks or unevenness ○: Slight streaks or unevenness exists △: Vertical streaks or obvious unevenness along the flow exist ×: Many streaks or unevenness exist

[Adhesive releasability 2]
In accordance with ASTM D1893, the film obtained in Examples and Comparative Examples described later were superposed so that the surface in contact with the chill roll and the adhesive layer surface of the film having the following adhesive layer were in contact. The laminate was bonded by reciprocating twice with a 2 kg hand-type rubber roller. It was cut into a width of 25 mm and left at 23 ° C. for 20 minutes. Thereafter, 180 ° peel strength (N / 50 mm) was measured at 23 ° C. under a test speed of 200 mm / min using an Intesco peel tester.

Composition of adhesive layer PEBR: propylene / ethylene / 1-butene copolymer (ethylene content 13 mol%, butene content 19 mol%, melting point not observed, MFR = 7 g / 10 min) 45 wt%
SIBS: Styrene-isobutylene-styrene triblock copolymer (trade name: Shibster, brand name: 062T, MFR = 8.0 g / 10 min, manufactured by Kaneka Corporation) 35% by weight
SEBS: Styrene-butadiene copolymer hydrogenated product (trade name: Tuftec, brand name: H1221, MFR = 4.5 g / 10 min, manufactured by Asahi Kasei Corporation) 10% by weight
PP-3: Homopolypropylene (brand name: F107BV, melting point = 160 ° C., MFR = 7 g / 10 min, manufactured by Prime Polymer Co., Ltd.) 10% by weight

[Examples 1-7 and Comparative Examples 1-6]
According to the formulation shown in Table 1 (Examples 1 to 7) and Table 2 (Comparative Examples 1 to 6), a base resin (A) made of a polyethylene resin and a 4-methyl-1-pentene polymer (B ) And the compatibilizer (C) were mixed (dry blended). On the other hand, a T die having a lip width of 240 mm was installed in a 20 mmφ single screw extruder (manufactured by Tanaka Iron Works). The cylinder temperature of the single screw extruder was set to 220 ° C, and the die temperature was set to 220 ° C. The obtained mixture was added to an extruder, and the melt-kneaded product was extruded from a T die. Thereafter, the extruded film was taken out at a chill roll temperature of 40 ° C. and a take-up speed of 1.5 m / min, thereby obtaining a cast film having a thickness of 50 μm.

  The physical properties of the cast films obtained in Examples 1 to 7 and Comparative Examples 1 to 6 were evaluated by the methods described above.

As shown in Table 1, in Examples 1 to 7 containing an appropriate amount of a base resin (A) made of polyethylene, a 4-methyl-1-pentene polymer (B), and a compatibilizer (C), It can be seen that the releasability is high (180 ° peel strength is 5.1 N / 50 mm or less); and haze is low and transparent.
On the other hand, as shown in Table 2, it can be seen that Comparative Examples 1 and 2 consisting only of the polyethylene resin (A) have low adhesive release properties (high 180 ° peel strength). Further, in Comparative Examples 3 to 5 including the polyethylene resin (A) and the 4-methyl-1-pentene polymer (B), is the adhesive release property not sufficiently improved (Comparative Example 3) or haze is increased? Increased and transparency is inhibited (Comparative Examples 4 and 5). Further, in Comparative Example 6 containing a large amount of 4-methyl-1-pentene polymer (B), film formation itself was difficult.

[Example 8 and Comparative Examples 7 to 10]
As shown in Table 3, a mixture of a base resin (A) made of a polypropylene resin, a 4-methyl-1-pentene polymer (B), and a compatibilizer (C) was mixed with a twin-screw extruder ( KTX30-SS (manufactured by Kobe Steel) was melt kneaded at 220 ° C. to obtain a kneaded product. This melt-kneaded product was used as a master batch pellet.

  A 20 mmφ single screw extruder (manufactured by Tanaka Iron Works Co., Ltd.) equipped with a T die with a lip width of 240 mm was set to 220 ° C. and the die temperature was set to 220 ° C., and master batch pellets were added to this extruder. The melt-kneaded product was extruded from the die. Thereafter, the extruded product was taken out at a chill roll temperature of 35 ° C. and a take-up speed of 1.5 m / min, thereby obtaining a cast film having a thickness of 50 μm.

  About the obtained cast film, it measured or evaluated similarly to Examples 1-7 and Comparative Examples 1-6.

In Example 8 containing appropriate amounts of a base resin (A) made of polypropylene, a 4-methyl-1-pentene polymer (B), and a compatibilizer (C), the adhesive release property is high (180 ° peeling). It can be seen that the strength is 1.0 N / 50 mm); the haze is low and it is transparent.
On the other hand, in Comparative Example 7 consisting only of the base resin (A) made of polypropylene, it can be seen that the adhesive release property is low (180 ° peel strength is 2.3 N / 50 mm). In Comparative Examples 8 and 9 including the base resin (A) made of polypropylene and the 4-methyl-1-pentene polymer (B), the adhesive release property is not sufficiently improved or the transparency is lowered. Furthermore, in Comparative Example 10 containing a large amount of 4-methyl-1-pentene polymer (B), film formation was not possible.

Since the resin composition of the present invention has high releasability and antiblocking properties, it can be used as various functional films by film forming. Furthermore, the laminated film having the layer of the resin composition of the present invention and the adhesive layer can be stored in a roll shape without sandwiching a separate release film. That is, the film can be fed out from the roll-shaped product, although the release film is not sandwiched in the roll shape. If a release film is not required, it is preferable in terms of cost and work efficiency.

Claims (10)

A base resin (A1) containing 100 parts by mass of a polyethylene resin; 0.1 to 5 parts by mass of a 4-methyl-1-pentene polymer (B); from polyethylene wax, polypropylene wax and petroleum resin A compatibilizing agent (C) selected from the group consisting of:
Resin having an intrinsic viscosity [η] (dl / g) of the 4-methyl-1-pentene polymer (B) measured in a decalin solvent at 135 ° C. in the range of 0.01 or more and less than 0.50 Composition. The base resin (A2) containing 100 parts by weight of a polypropylene resin; 0.1 4-methyl-1-pentene polymer of the parts by mass or more than 10 parts by mass (B); or polyethylene wax and polypropylene wax scan Ranaru A resin composition comprising a compatibilizer (C) selected from the group,
The 4-methyl-1-pentene-based polymer (B), an intrinsic viscosity measured at 135 ° C. in decalin solvent [η] (dl / g) is Ri range near less than 0.01 to 0.50,
The resin composition in which the difference between the density of the base resin (A2) and the density of the compatibilizer (C) is less than 50 kg / m ³ . The intrinsic viscosity [η] (dl / g) of the 4-methyl-1-pentene polymer (B) measured at 135 ° C. in a decalin solvent satisfies the relationship of the following formula (I). Or the resin composition of 2.

[A in the above formula (I) has a polystyrene equivalent molecular weight of 1000 or less as measured by gel permeation chromatography (GPC) among the components in the 4-methyl-1-pentene polymer (B). It is the content ratio (% by mass) of a certain component] The ratio of the structural unit derived from 4-methyl-1-pentene to the total structural unit of the 4-methyl-1-pentene polymer (B) is 50 to 100% by mass, and 4-methyl-1-pentene The total proportion of structural units derived from at least one olefin selected from olefins having 2 to 20 carbon atoms other than 0 to 50% by mass,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the 4-methyl-1-pentene polymer (B) measured by gel permeation chromatography (GPC) is: In the range of 1.0 to 5.0,
The melting point (Tm) of the 4-methyl-1-pentene polymer (B) measured with a differential scanning calorimeter is in the range of 120 to 245 ° C.,
The resin composition according to any one of claims 1 to 3, wherein a critical surface tension of the 4-methyl-1-pentene polymer (B) is in a range of 22 to 28 mN / m.   The terminal double bond amount calculated by 1H-NMR of the 4-methyl-1-pentene polymer (B) is 0.001 or more and 0.5 or less per 1000 carbons. 5. The resin composition according to any one of 4 above.   The resin composition according to any one of claims 1 to 5, wherein the 4-methyl-1-pentene polymer (B) is a 4-methyl-1-pentene polymer polymerized by a metallocene catalyst. object. The content of the compatibilizer (C) is, the 4-methyl-1-pentene polymer (B) with respect to 100 parts by weight, 1 to 100 parts by weight, any of claims 1 to 6 one The resin composition according to item.   The film molded product which consists of a resin composition as described in any one of Claims 1-7. A surface protective film having a surface layer constituting one surface and an adhesive layer constituting the other surface,
The said surface layer is a surface protection film which consists of a resin composition as described in any one of Claims 1-7. The surface protective film according to claim 9, wherein the surface layer and the adhesive layer are coextruded from a T die.