JP2015025051A - Water-repellent film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film excellent in water repellency and oil repellency.SOLUTION: A water-repellent film is provided, which is formed of a resin composition comprising a thermoplastic resin and a silylated polyolefin, and shows a contact angle of 100 degrees or more with water on a surface thereof.

Description

  The present invention relates to a water repellent film, and more particularly to a water repellent film comprising a resin composition comprising a thermoplastic resin and a silylated polyolefin.

  In many product fields such as food, beverages, pharmaceuticals, and chemicals, packaging materials corresponding to their contents have been developed. In particular, as a packaging material for contents having viscous bodies such as liquids, semi-solids, and gel substances, plastic materials having excellent water resistance, oil resistance, gas barrier properties, light weight, flexibility, and design properties are used. It functions to protect the contents required for materials.

  As one of the functions of the packaging material, there is a demand for a function of preventing the content having a viscous material such as a liquid, a semi-solid, or a gel substance from adhering to the inner surface of the packaging material, that is, remaining in the packaging body. For example, it has been proposed to provide a heat seal resin layer containing hydrophobic fine particles such as silicone particles on one surface of a substrate (see Patent Document 1). It has also been proposed to provide a water-repellent coating layer containing hydrophobic fine particles on one side of a substrate (see Patent Document 2). Alternatively, it has also been proposed to provide a thermal adhesive layer containing hydrophobic oxide fine particles such as hydrophobic silica as the outermost layer of the lid (see Patent Document 3).

  Furthermore, it has been proposed to provide an olefin resin layer containing an ethylenebis fatty acid amide, which is a lubricant component, on the inner surface of a packaging container filled with highly viscous contents (see Patent Document 4).

JP 2013-18533 A JP2012-228787A Japanese Patent No. 4348401 Japanese Patent No. 5105035

  When the present inventors provide a heat seal layer containing hydrophobic fine particles or the like as the outermost layer of the packaging material as proposed in Patent Documents 1 to 3, the coating material may fall off and be mixed into the contents. The problem that heat sealability is impaired was discovered. In addition, when a resin layer in which a lubricant component is kneaded is provided on the inner surface of the packaging container as proposed in the invention of Patent Document 4, the additive does not easily fall off but has sufficient water repellency. In order to achieve this, it is necessary to add a certain amount or more of an expensive additive to bleed out a certain amount or more of the additive component on the surface, leading to an increase in cost. Moreover, even if it was a thermoplastic resin film, since the heat sealability was impaired, the subject that it was not suitable for a lid | cover material use was discovered. Furthermore, in the inventions of Patent Documents 1 to 4, water repellency and oil repellency were not sufficient.

  The present invention has been made in view of the above-described background art and newly discovered problems, and an object thereof is to provide a film excellent in water repellency and oil repellency.

That is, according to one aspect of the present invention,
There is provided a water-repellent film comprising a resin composition comprising a thermoplastic resin and a silylated polyolefin and having a water contact angle of 100 ° or more on the surface.

  In the embodiment of the present invention, the contact angle of oil on the surface of the water repellent film is preferably 20 degrees or more.

  In the aspect of this invention, it is preferable that content of the said silylated polyolefin is 0.1-40 mass% with respect to the said resin composition.

  In the aspect of the present invention, the thermoplastic resin is preferably a polyolefin resin.

  In the embodiment of the present invention, the silylated polyolefin is a reaction between a raw material compound (1) containing one or more structural units (1) represented by the following general formula and a raw material compound (2) containing one or more vinyl groups (provided that Silylated polyolefin [A] produced by the structural unit (1) in the raw material compound (1) and the reaction when the vinyl compound in the raw material compound (2) is plural is preferred.

  In the embodiment of the present invention, the number average molecular weight of the silylated polyolefin [A] is preferably 100 to 1,000,000.

  In the embodiment of the present invention, the raw material compound (1) is preferably represented by the following general formula (2).

  In an embodiment of the present invention, the portion other than the vinyl group of the raw material compound (2) of the silylated polyolefin [A] is selected from the group consisting of an ethylene homopolymer chain, a propylene homopolymer chain, or an olefin having 2 to 50 carbon atoms. It is preferably a group having a number average molecular weight of 100 to 500,000.

  In the embodiment of the present invention, the portion other than the vinyl group of the starting compound (2) of the silylated polyolefin [A] is a linear ethylene homopolymer chain having 3 to 200 carbon atoms that does not contain a double bond. preferable.

In the aspect of this invention, it is preferable that the raw material compound (2) of the silylated polyolefin [A] is an unmodified olefin resin (B) satisfying the following (B1) to (B6).
(B1) A copolymer obtained by copolymerizing ethylene and at least one diene, or at least one olefin selected from ethylene and an α-olefin having 3 to 12 carbon atoms and at least one diene. A copolymer obtained by copolymerization.
(B2) The unsaturated group content per molecule is 0.5 to 3.0.
(B3) The density is 870 to 980 kg / m ³ .
(B4) Melting point is 70-130 ° C.
(B5) Number average molecular weight (Mn) is 400-5,000.
(B6) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4.0 or less.

  In the embodiment of the present invention, the diene of (B1) is preferably vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene).

  In the embodiment of the present invention, the water repellent film is preferably extruded.

  In the aspect of the present invention, the extrusion molding is preferably performed by a T-die method or an inflation method.

According to another aspect of the invention,
A packaging material comprising the above water-repellent film is provided.

  According to the present invention, a film excellent in water repellency and oil repellency can be provided. Since the surface of the water-repellent film according to the present invention is excellent in water repellency and oil repellency, when used in a packaging material such as a lid or a packaging container, it is possible to suppress adhesion and remaining of contents.

Water-repellent film The water-repellent film according to the present invention comprises a resin composition comprising a thermoplastic resin (excluding silylated polyolefin) and a silylated polyolefin. The content of the silylated polyolefin is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, still more preferably 1 to 30% by mass, and even more preferably, based on the resin composition. Is 1-20 mass%.

  In the water-repellent film according to the present invention, the contact angle of water on the surface of the first resin layer is 100 degrees or more, preferably 105 degrees or more, more preferably 110 degrees or more and 180 degrees or less. The contact angle can be measured using a commercially available contact angle measuring machine.

  In the water-repellent film according to the present invention, the contact angle of oil on the surface of the first resin layer is preferably 20 degrees or more, more preferably 30 degrees or more, still more preferably 40 degrees or more, and even more preferably 45 degrees or more and 180 degrees. It is as follows. In the present invention, soybean oil is used as the oil. The contact angle can be measured using a commercially available contact angle measuring machine.

The thermoplastic resin contained in the thermoplastic resin composition does not include the following silylated polyolefin. The thermoplastic resin contained in the resin composition includes low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, linear low-density polyethylene resin, and ethylene-α olefin polymerized using a metallocene catalyst. Polymer resin, ethylene-polypropylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methacrylic acid copolymer resin, ethylene -Graft polymerization of unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, ester monomer to methyl methacrylate copolymer resin, ethylene-maleic acid copolymer resin, ionomer resin, polyolefin resin, or Copolymerized resin and maleic anhydride into polyolefin resin. Can be used bets modified resin. These materials can be used alone or in combination. In the present invention, it is preferable to use a polyolefin resin (excluding silylated one) as the thermoplastic resin.

The silylated polyolefin contained in the silylated polyolefin resin composition is preferably the following silylated polyolefin [A]. The raw material compound in the case of producing silylated polyolefin [A] via Step 1 and Step 2 will be described below.

Raw material compound of silylated polyolefin [A] (1)
The structural unit (1) contained in the hydrosilane that is the raw material compound (1) of the silylated polyolefin [A] used in the present invention will be described in more detail.

上記一般式（１）中、Ｒ^１は、水素原子、ハロゲン原子、炭化水素基、酸素含有基またはケイ素含有基を表し、それぞれ同一であっても異なっていてもよく、また炭化水素基、酸素含有基、ケイ素含有基は１つ以上のヘテロ原子を含んでいてもよく、Ｙ^１はＯ、ＳまたはＮＲ（Ｒは水素原子または炭化水素基を表す）である。好ましくは、Ｒ^１は、水素原子、ハロゲン原子、炭化水素基であり、Ｙ^１はＯ、ＳまたはＮＲである。

In the general formula (1), R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group or a silicon-containing group, which may be the same or different from each other. The containing group and the silicon-containing group may contain one or more hetero atoms, and Y ¹ is O, S or NR (R represents a hydrogen atom or a hydrocarbon group). Preferably, R ¹ is a hydrogen atom, a halogen atom or a hydrocarbon group, and Y ¹ is O, S or NR.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, and octadecyl group. A linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a norbornyl group; and an arylalkyl group such as a benzyl group, a phenylethyl group, and a phenylpropyl group.

Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group.
Examples of the aryl group include phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group and the like.

Examples of the oxygen-containing group include an alkoxy group and an aryloxy group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, a benzyloxy group, and a 2-phenylethoxy group.

Examples of the aryloxy group include a phenoxy group, a tolyloxy group, a biphenyloxy group, and a naphthyloxy group.
Silicon-containing groups include alkylsilyl groups, alkenylsilyl groups, arylsilyl groups, alkylsiloxy groups, alkenylsiloxy groups, arylsiloxy groups, alkoxysilyl groups, aryloxysilyl groups, alkoxysiloxy groups, aryloxysiloxy groups, polysiloxyls, etc. Is mentioned. The polysiloxyl group is a group having two or more siloxane repeating units, and may be linear or branched.

  The hydrocarbon group, oxygen-containing group, and silicon-containing group described above may contain one or more heteroatoms. Specifically, a group in which at least one hydrogen of these groups is substituted with a group containing a halogen atom, oxygen, nitrogen, silicon, phosphorus, or sulfur is included.

Of the atoms or groups listed above as R ¹ of the structural unit (1), a hydrogen atom, a halogen atom, a polysiloxyl group having 1 to 50 silicon atoms, an alkoxy group having 1 to 4 carbon atoms, and a phenyl group. It is preferable that at least one atom or group selected from among R ^{1 in} the raw material compound (1) is a polysiloxyl group having 1 to 50 silicon atoms. When R ¹ is a polysiloxyl group having 1 to 50 silicon, exudation from the resin and bleeding can be suppressed without losing good releasability of the resin.

  Moreover, as one aspect of the present invention, the hydrosilane compound of the raw material compound (1) containing one or more structural units (1) represented by the above general formula may be represented by the following general formulas (5) and (6). A compound having a plurality of Si—H bonds as represented is also preferably used.

上記一般式（５）および（６）において、Ｒ^１は前記一般式で表わされる構造単位（１）におけるＲ^１と同様の基である。Ｒ^１１は水素原子、ハロゲン原子、ケイ素数１〜１０のケイ素含有基、炭素数１〜４のアルコキシ基、フェニル基およびアルキル基からなる群から選ばれる１種以上の原子または基であり、好ましくはケイ素数１〜１０のケイ素含有基、炭素数１〜４のアルコキシ基、フェニル基または炭素数１〜４のアルキル基である。ｍは１〜５００の数であり、ｎは１〜５０の数である。ハロゲン原子、ケイ素含有基、アルコキシ基およびアルキル基は前記構造単位（１）におけるＲ^１について例示したものが用いられる。
さらに、一般式（２）で表わされるような化合物が特に好ましい態様として挙げられる。

In the general formulas (5) and (6), R ¹ is the same group as R ¹ in the structural unit (1) represented by the general formula. R ¹¹ is one or more atoms or groups selected from the group consisting of a hydrogen atom, a halogen atom, a silicon-containing group having 1 to 10 silicon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group and an alkyl group, Is a silicon-containing group having 1 to 10 silicon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an alkyl group having 1 to 4 carbon atoms. m is a number from 1 to 500, and n is a number from 1 to 50. As the halogen atom, silicon-containing group, alkoxy group and alkyl group, those exemplified for R ¹ in the structural unit (1) can be used.
Further, a compound represented by the general formula (2) is particularly preferable.

式（２）中、Ｒ^１およびＲ^３は水素原子、ハロゲン原子、炭化水素基、酸素含有基またはケイ素含有基を表し同一でも異なっていても良く、またＲ^１およびＲ^３が複数存在する場合はそれぞれ同一でも異なっていても良く、Ｒ^２およびＲ^４は水素原子、ハロゲン原子、炭化水素基、酸素含有基または一般式（３）で表される基を表し同一でも異なっていても良く、Ｙ^１およびＹ^２はＯ、ＳまたはＮＲ（Ｒは水素原子または炭化水素基を表す）を表し同一でも異なっていても良く、またＹ^１およびＹ^２が複数存在する場合はそれぞれ同一でも異なっていても良く、ｍは１〜２０の整数、ｎは０〜２０の整数であり、Ｚはｎが１以上の場合は一般式（４）で表される２価の連結基を表し、ｎが０の場合はＹ^１とＲ^４との直接結合を表す。

In formula (2), R ¹ and R ³ represent a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group or a silicon-containing group, and may be the same or different, and when there are a plurality of R ¹ and R ³ Each may be the same or different, and R ² and R ^{4 each} represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group or a group represented by the general formula (3), and may be the same or different, Y ¹ and Y ² represent O, S or NR (R represents a hydrogen atom or a hydrocarbon group), which may be the same or different, and when a plurality of Y ¹ and Y ² are present, they are the same or different. M is an integer of 1 to 20, n is an integer of 0 to 20, Z is a divalent linking group represented by the general formula (4) when n is 1 or more, and n is In the case of 0, it represents a direct bond between Y ¹ and R ⁴ .

式（３）中、Ｒ^２１は水素原子、ハロゲン原子または炭化水素基を表し、複数存在するＲ^２１はそれぞれ同一でも異なっていても良く、ｘは０〜１０の整数である。

In the formula (3), R ²¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, a plurality of R ²¹ may be the same or different, and x is an integer of 0 to 10.

式（４）中、Ｒ^１１は水素原子、ハロゲン原子または炭化水素基を表し、複数存在するＲ^１１はそれぞれ同一でも異なっていても良く、ｌは０〜５００の整数である。）
上記一般式（２）（３）（４）において、ハロゲン原子、炭化水素基、酸素含有基またはケイ素含有基は前記構造単位（１）におけるＲ^１について例示したものが用いられる。

In the formula (4), R ¹¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of R ¹¹ may be the same or different, and l is an integer of 0 to 500. )
In the general formulas (2), (3), and (4), those exemplified for R ¹ in the structural unit (1) are used as the halogen atom, hydrocarbon group, oxygen-containing group, or silicon-containing group.

Raw material compound of silylated polyolefin [A] (2)
The polyolefin that is the raw material compound (2) of the silylated polyolefin [A] used in the present invention has a structure containing one or more vinyl groups.
The portion excluding the vinyl group of the raw material compound (2) is an ethylene chain or a copolymer chain of two or more olefins selected from the group consisting of olefins having 2 to 50 carbon atoms, and has a number average molecular weight Is an ethylene homopolymer chain, a propylene homopolymer chain, or ethylene, propylene, butene, vinyl norbornene, a cyclic polyene having two or more double bonds, and two or more duplexes. It is preferably a copolymer chain of two or more olefins selected from the group consisting of a chain polyene having a bond, particularly an ethylene homopolymer chain, a propylene homopolymer chain, or an olefin and diene copolymer chain, A copolymer chain of ethylene and propylene and a copolymer chain of ethylene and norbornene are preferable.

  In the above case, the number average molecular weight of the raw material compound excluding the vinyl group is preferably 100 to 500,000, and more preferably 100 to 100,000. If the group becomes shorter than this, the possibility that the obtained silylated polyolefin [A] will bleed from the resin becomes stronger, and if it becomes longer, the dispersibility in the resin becomes worse.

In the case of a copolymer, a plurality of vinyl groups are contained. In this case, the number average molecular weight of the raw material compound (2) is preferably 100 to 100,000, and preferably 200 to 10,000. More preferably, it is more preferably 400 to 5,000, still more preferably 400 to 4,000, still more preferably 400 to 3,000, and 1,500 to 2,500. Most preferably it is.
The polyolefin polymer chain excluding the vinyl group of the raw material compound (2) containing one or more vinyl groups will be described below.

(Polyolefin having ethylene homopolymer chain)
(E1) The polyolefin having an ethylene homopolymer chain can be produced, for example, by the following method.

(A) A transition metal compound having a salicylaldoimine ligand as shown in JP 2000-239312 A, JP 2001-27331 A, JP 2003-73412 A, or the like is used as a polymerization catalyst. Polymerization method.
(B) A polymerization method using a titanium-based catalyst comprising a titanium compound and an organoaluminum compound.
(C) A polymerization method using a vanadium catalyst comprising a vanadium compound and an organoaluminum compound.
(D) A polymerization method using a Ziegler-type catalyst comprising a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane).

(Polyolefin having propylene homopolymer chain)
(E2) The polyolefin having a propylene homopolymer chain can be produced, for example, by the following method.
(A) A method of polymerizing propylene in the presence of a supported titanium-based catalyst such as a magnesium-supported titanium-based catalyst or a metallocene catalyst as disclosed in JP-A-2004-262993.
(B) a compound that forms an ionic complex by reacting with a transition metal in a metal compound as disclosed in JP-A-2000-191862, JP-A-2002-097325, or the like, an organoaluminum compound And a method of polymerizing propylene in the presence of a metallocene catalyst comprising aluminoxane.

(Olefin having 2 to 50 carbon atoms)
(E3) In a polyolefin having a copolymer chain of two or more olefins selected from the group consisting of olefins having 2 to 50 carbon atoms, specific examples of the olefin having 2 to 50 carbon atoms constituting the copolymer chain include And ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, and 3,4-dimethyl-1. -Pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1-pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3 , 4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexa Α-olefins such as; olefins containing internal double bonds such as cis-2-butene, trans-2-butene, etc .; isobutene, 2-methyl-1-pentene, 2,4-dimethyl-1-pentene, 2, 4-dimethyl-1-hexene, 2,4,4-trimethyl-1-pentene, 2,4-dimethyl-1-heptene, 2-methyl-1-butene, 2-methyl-1-hexene, 2-methyl- 1-heptene, 2-methyl-1-octene, 2,3-dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,3-dimethyl-1- Octene, 2,3,3-trimethyl-1-butene, 2,3,3-trimethyl-1-pentene, 2,3,3-trimethyl-1-hexene, 2,3,3-trimethyl-1-octene, 2,3,4-tri Til-1-pentene, 2,3,4-trimethyl-1-hexene, 2,3,4-trimethyl-1-octene, 2,4,4-trimethyl-1-hexene, 2,4,4-trimethyl- Vinylidene such as 1-octene, 2-methyl-3-cyclohexyl-1-propylene, vinylidenecyclopentane, vinylidenecyclohexane, vinylidenecyclooctane, 2-methylvinylidenecyclopentane, 3-methylvinylidenecyclopentane, 4-methylvinylidenecyclopentane Compound; Aryl vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene; α-methylstyrene , Α-ethylstyrene, 2-methyl-3 Aryl vinylidene compounds such as phenylpropylene; methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-cyanopropylene, Functional group-substituted vinylidene compounds such as 2-aminopropylene, 2-hydroxymethylpropylene, 2-fluoropropylene, 2-chloropropylene; cyclobutene, cyclopentene, 1-methyl-1-cyclopentene, 3-methyl-1-cyclopentene, 2- Methyl-1-cyclopentene, cyclohexene, 1-methyl-1-cyclohexene, 3-methyl-1-cyclohexene, 2-methyl-1-cyclohexene, cycloheptene, cyclooctene, norbornene, - methyl-2-norbornene, tetracyclododecene, 5,6-dihydro-dicyclopentadiene, 3a, 4,5,6,7,7a-hexahydro -1H-indene, tricyclo [6.2.1.0 ^{2, 7} ] An aliphatic cyclic olefin containing an internal double bond such as undec-4-ene, cyclopentadiene, dicyclopentadiene; cyclopent-2-enylbenzene, cyclopent-3-enylbenzene, cyclohex-2-enylbenzene, cyclohexa-3 -Cyclic olefins containing aromatic rings such as enylbenzene, indene, 1,2-dihydronaphthalene, 1,4-dihydronaphthalene, 1,4-methino 1,4,4a, 9a tetrahydrofluorene; butadiene, isoprene, 4- Methyl-1,3-pentadiene, 4-methyl-1,4-penta Ene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 5,9- Examples thereof include cyclic polyenes having two or more double bonds and chain polyenes having two or more double bonds, such as dimethyl-1,4,8-decatriene.

Moreover, the C2-C50 olefin may have a functional group containing atoms, such as oxygen, nitrogen, and sulfur. For example, unsaturated carboxylic acids such as acrylic acid, fumaric acid, itaconic acid, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid, and sodium, potassium, lithium and zinc salts thereof Unsaturated carboxylic acid metal salt such as magnesium salt, calcium salt; unsaturated carboxylic acid such as maleic anhydride, itaconic anhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride Acid anhydride; methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-tert-butyl, acrylic acid-2-ethylhexyl, etc. Unsaturated carboxylic acid esters; vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, Vinyl phosphoric acid, vinyl stearate, vinyl esters such as vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, unsaturated glycidyl esters, such as itaconic acid monoglycidyl ester;
Halogenated olefins such as vinyl chloride, vinyl fluoride and allyl fluoride; unsaturated cyano compounds such as acrylonitrile and 2-cyano-bicyclo [2.2.1] hept-5-ene; unsaturated compounds such as methyl vinyl ether and ethyl vinyl ether Saturated ether compounds; unsaturated amides such as acrylamide, methacrylamide, N, N-dimethylacrylamide;
Functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene; and N-vinylpyrrolidone .

(Polyolefins having a copolymer chain of olefin and diene)
(E3 ′) A polyolefin having a copolymer chain of olefin and diene is a copolymer of (F1) olefin and (F2) diene.
Examples of (F1) olefins include ethylene and α-olefins having 3 to 12 carbon atoms.

  Examples of the α-olefin having 3 to 12 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1. -Pentene, 1-octene, 1-decene, 1-dodecene and the like. Among these, preferably an α-olefin having 3 to 10 carbon atoms, more preferably an α-olefin having 3 to 8 carbon atoms, particularly preferably propylene, 1-butene, 1-hexene, 4-methyl-1- Penten is preferred.

  (F2) Diene includes butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene, vinylnorbornene (5-vinylbicyclo [2.2.1] hept- 2-ene), dicyclopentadiene, 2-methyl-1,4-hexadiene, 2-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7 -Nonadiene, 5,9-dimethyl-1,4,8-decatriene, etc. are mentioned. Among these, vinyl norbornene, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, butadiene, isoprene, 2-methyl-1,4-hexadiene or 2-methyl-1,6-octadiene is preferable. Vinyl norbornene is particularly preferable because it has a bulky skeleton, so that the wax can be hardened even at a low density and the wax product is hardly blocked.

  The polyolefin having a copolymer chain of olefin and diene is a copolymer of ethylene and diene as described above, or at least one α-olefin and diene selected from ethylene and an α-olefin having 3 to 12 carbon atoms. And a copolymer thereof.

  The polyolefin having a copolymer chain of olefin and diene used in the present invention contains a constituent unit derived from diene in a proportion of 0.01 to 6.0 mol%, preferably 0.1 to 4.0 mol%. Is desirable. Further, when the polyolefin having a copolymer chain of olefin and diene contains a structural unit derived from an α-olefin having 3 to 12 carbon atoms, the content is 0.01 to 15 mol%, preferably 0.8. 1-12 mol% is desirable.

When the polyolefin having a copolymer chain of olefin and diene used in the present invention contains a structural unit derived from diene in a proportion within the above range, the polymerization activity is also moderately high.
Further, when a structural unit derived from an α-olefin having 3 to 12 carbon atoms is contained in a proportion within the above range, a molding resin composition having less surface tackiness and excellent mechanical properties and impact properties is obtained. Can do.

  The polyolefin having a copolymer chain of olefin and diene used in the present invention has an average of 0.5 to 3.0 / molecule, preferably 0.5 to 2.0 molecules / molecule, and more preferably 1.0 to 2. It is desirable to have an unsaturated group content in the range of 0 / molecule. When the unsaturated group content in the polyolefin having a copolymer chain of olefin and diene is within the above range, since the silicone is added to the polyolefin having a copolymer chain of olefin and diene, the silylated polyolefin has A molding resin composition that effectively acts on the inorganic reinforcing material and has excellent mechanical properties and impact properties can be obtained.

The unsaturated group content of the polyolefin having a copolymer chain of olefin and diene is measured as follows. ^The number M of unsaturated groups per 1,000 carbons can be obtained by comparing the peak area of the unsaturated portion carbon by ¹³ C-NMR with the peak area of all carbon. The unsaturated group content per molecule can be calculated by Mn × M / 14,000 using the number average molecular weight Mn. In the present invention, the number M of unsaturated groups per 1,000 carbons is 1.4 to 105, preferably 1.4 to 70, and more preferably 2.8 to 70.

Polyolefins having olefin copolymer chain of diene used in the present invention, the density measured by a density gradient tube method is 870 kg / ^{m 3} or more, preferably 890 kg / ^{m 3} or more, more preferably 910 kg / ^{m 3} or more and, It is desirable that it is 980 kg / m ³ or less, preferably 970 kg / m ³ or less, more preferably 960 kg / m ³ or less. When the density of the polyolefin having a copolymer chain of olefin and diene is within the above range, there is little tackiness and excellent dispersibility in the resin, so that a molding resin composition having excellent releasability is obtained. Can do.

  The polyolefin having a copolymer chain of olefin and diene used in the present invention has a melting point measured by a differential scanning calorimeter (DSC) of 70 ° C. or higher, preferably 80 ° C. or higher, more preferably 90 ° C. or higher, particularly preferably 100 ° C. The temperature is 130 ° C. or lower, preferably 125 ° C. or lower, more preferably 120 ° C. or lower. When the melting point of the polyolefin having a copolymer chain of olefin and diene is within the above range, there is little tackiness and excellent dispersibility in the resin, so that a molding resin composition having excellent releasability is obtained. Can do.

  The polyolefin having a copolymer chain of olefin and diene used in the present invention has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 400 to 5,000, preferably 400 to 4000, more preferably 400. It is desirable to be in the range of ˜3000, particularly preferably in the range of 1,500 to 2,500. When the Mn of the polyolefin having a copolymer chain of olefin and diene is within the above range, there is little tackiness and excellent dispersibility in the resin, so that a molding resin composition having excellent releasability is obtained. Can do.

  The polyolefin having a copolymer chain of olefin and diene used in the present invention has a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight measured by GPC of 4.0 or less, preferably 3.5 or less, more preferably Is desirably 3.0 or less.

  In addition, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are polystyrene conversion values measured by gel permeation chromatography (GPC). Here, the measurement by GPC is performed under the conditions of temperature: 140 ° C. and solvent: orthodichlorobenzene.

  The polyolefin having a copolymer chain of olefin and diene used in the present invention has a penetration hardness of 15 dmm (dmm = 0.1 mm) or less, preferably 10 dmm or less, more preferably 3 dmm or less, and particularly preferably 1 dmm or less. desirable. The penetration hardness can be measured according to JIS K2207. When the penetration hardness of the polyolefin having a copolymer chain of olefin and diene is within the above range, the mold release property of the molding resin composition is excellent.

The polyolefin having a copolymer chain of olefin and diene according to the present invention has (ii) an unsaturated group content of 0.5 to 3.0 molecules / molecule, and (iii) a density of 870 to 980 kg / m ³ . And (iv) the melting point is 70 to 130 ° C., (v) the number average molecular weight (Mn) is 400 to 5,000, and (vi) Mw / Mn (Mw: weight average molecular weight) is 4.0 or less. It is desirable that It is also desirable that the (vii) penetration hardness is 15 dmm or less.

Further, the polyolefin having a copolymer chain of olefin and diene according to the present invention is copolymerized using vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene) as a diene. In some cases, the polyolefin having a copolymer chain of olefin and diene has (viii) an unsaturated group content of 0.5 to 2.0 / molecule, and (ix) a density of 890 to 980 kg / m ³ . Yes, (x) Melting point is 80 to 130 ° C, (xi) Number average molecular weight (Mn) is 400 to 5,000, (xii) Mw / Mn (Mw: weight average molecular weight) is 4.0 or less It is desirable that It is also desirable that (xiii) penetration hardness is 15 dmm or less.

The polyolefin having a copolymer chain of olefin and diene has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.04 to 0.47 dl · g ⁻¹ , preferably 0.04 to 0.30 dl · g ^{−. 1,} more preferably 0.04~0.20dl · ^{g -1,} even more preferably it is preferably in the range of 0.05~0.18dl · ^{g -1.}

  The polyolefin having a copolymer chain of olefin and diene as described above comprises, for example, a metallocene compound of a transition metal selected from Group 4 of the periodic table, an organoaluminum oxy compound and / or an ionized ionic compound, as follows: It can be produced using a metallocene catalyst. Suitable metallocene catalysts in the present invention include Japanese Patent Application Laid-Open No. 2001-002731 or PCT applications already published internationally, WO / 2007/114102, WO / 2007/1055483, WO / 2007/114409, WO / 2007 / For example, (A) a metallocene compound of a transition metal selected from Group 4 of the periodic table, (B) (b-1) an organoaluminum oxy compound, (b-2) the bridged metallocene compound ( A catalyst for olefin polymerization comprising at least one compound selected from a compound that reacts with A) to form an ion pair and (b-3) an organoaluminum compound can be given.

Specific examples of (A) metallocene compounds of transition metals selected from Group 4 of the periodic table used in the present invention include bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-Methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, dimethyl (t-butylamide) (tetramethyl-η ⁵ − Cyclopentadienyl) silane) titanium dichloride and the like.

  Also, (B) (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound used in the present invention. Specific examples of at least one compound selected from: N, N-dimethylanilinium tetraphenylborate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, triphenylcarbenium tetrakis (pentafluorophenyl) borate, trimethylaluminum, triisobutylaluminum and the like.

Production of Silylated Polyolefin [A] Silylated polyolefin [A] used in the present invention may be produced by any method, but preferably, the following [Step 1] and [Step 2] are performed sequentially. It is obtained by doing.

[Step 1]: In the step [Step 1] of obtaining the transition metal catalyst composition (C), the hydrosilane containing the structural unit (1) represented by the above general formula and the halogenated transition metal are mixed and stirred. The obtained suspension solution is filtered to obtain a transition metal catalyst composition (C) as a filtrate.

The halogenated transition metal is a halide of a transition metal from Group 3 to Group 12 of the periodic table, and preferably from Group 8 to Group 10 of the periodic table from the viewpoint of availability and economy. More preferred are halides of platinum, rhodium, iridium, ruthenium, osmium, nickel and palladium. More preferred is a platinum halide. Further, it may be a mixture of two or more transition metal halides.
Examples of the halogen of the halogenated transition metal include fluorine, chlorine, bromine, and iodine. Among these, chlorine is preferable from the viewpoint of easy handling.

  Specific examples of the transition metal halide used in [Step 1] include platinum dichloride, platinum tetrachloride, platinum dibromide, platinum diiodide, rhodium trichloride, rhodium tribromide, rhodium triiodide, three Iridium chloride, iridium tetrachloride, iridium tribromide, iridium triiodide, ruthenium trichloride, ruthenium tribromide, ruthenium triiodide, osmium trichloride, osmium tribromide, osmium triiodide, nickel dichloride, two Examples include nickel fluoride, nickel dibromide, nickel diiodide, palladium dichloride, palladium dibromide, and palladium diiodide. Among these, platinum dichloride, palladium dichloride, ruthenium trichloride, rhodium trichloride. Iridium trichloride is preferred, and platinum dichloride is most preferred.

  The halogenated transition metal used in [Step 1] is usually a powdery solid, and the particle size is preferably 1000 μm or less, more preferably 500 μm or less. As the particle size increases, the preparation time of the transition metal catalyst composition (C) becomes longer.

  The amount of hydrosilane and transition metal halide used in [Step 1] is not particularly limited as long as the amount of hydrosilane is 1 equivalent or more relative to the transition metal halide, but is preferably twice or more equivalent. When the amount of hydrosilane is small, stirring necessary for catalyst preparation becomes difficult.

  The mixing and stirring of the hydrosilane and the transition metal halide in [Step 1] is not limited as long as this is possible, but an appropriate amount of the transition metal halide is charged into a reaction vessel equipped with a stirrer under a nitrogen stream. Hydrosilane is added to and stirred. In the case of a small amount, a stirrer chip may be put in a sample tube and charged in the same manner and stirred.

  The mixing and stirring time of hydrosilane and transition metal halide is usually 10 hours or more, preferably 20 hours or more, more preferably 60 hours or more, and further preferably 80 hours or more. If the reaction time is short, the production rate of the isomeric vinylene derivative which is an impurity in the silylated polyolefin [A] obtained in the next [Step 2] increases, which is not preferable. Although there is no particular upper limit for the mixing and stirring time, it is generally within one month from an economical viewpoint.

  The temperature of mixing and stirring the hydrosilane and the transition metal halide is not particularly limited as long as it is not higher than the boiling point of the hydrosilane, but is usually in the range of 0 to 50 ° C, preferably in the range of 10 to 30 ° C. In addition, the pressure can be usually performed at normal pressure, but can be performed under pressure or under reduced pressure as necessary.

  In [Step 1], a solvent may be used as necessary. The solvent used can be inert to the starting hydrosilane and transition metal halide. Specific examples of the solvent that can be used include aliphatic hydrocarbons such as n-hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, acetone, Examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and methyl propyl ketone; ethers such as tetrahydrofuran and 1,4-dioxane; halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane, tetrachloroethane, and perchloroethane. . Of these, aromatic hydrocarbons such as toluene and xylene are particularly preferable.

  When the solvent is used, the amount of the solvent used affects the solubility of the raw material, but is preferably 100 times by mass or less, more preferably 20 times by mass or less with respect to the raw material. In the present invention, it is most preferable to carry out without solvent.

  Next, the suspended solution obtained by the reaction is filtered to remove solids, and a transition metal catalyst composition (C) is obtained as a filtrate. There is no restriction | limiting in particular as a filtration method, General methods, such as natural filtration, pressure filtration, and reduced pressure filtration, can be used. The filter used for filtration is not particularly limited, and cellulose filter paper, glass fiber filter, membrane filter made of fluororesin or cellulose acetate, etc. can be used as appropriate, but the pore size uniformity, low moisture absorption, chemical stability From the point of view, it is preferable to use a fluororesin membrane filter. The filter used for filtration is preferably an eye filter smaller than 10 μm, and more preferably an eye filter of 1 μm or less. If a larger filter than this is used, the solid content of the unreacted transition metal halide is mixed in the catalyst and the catalyst becomes heterogeneous, which increases the amount of vinylene derivative that is an impurity of the synthesis target. Cause. Further, during filtration, the solid content can be washed using the above-mentioned solvent.

  The solid content removed by filtration, that is, the amount of the unreacted transition metal halide is usually 50% by mass or less, preferably 10% by mass or less, based on the amount of the transition metal halide used. The reaction rate of the transition metal halide can be adjusted mainly by the preparation time.

  The transition metal catalyst composition (C) thus prepared contains a transition metal compound in the form of a nanocolloid, hydrosilane, and a solvent used as necessary. This transition metal catalyst composition (C) can be used as it is in the next [Step 2], but is used in [Step 2] after removing the solvent, concentrating and diluting as necessary. You can also. Moreover, the hydrosilane of the general formula (1) can be added and diluted to adjust the catalyst concentration.

  Instead of carrying out [Step 1], a commercially available transition metal catalyst, for example, platinum alone (platinum black), chloroplatinic acid, platinum-olefin complex, platinum-alcohol complex, or a platinum carrier on a carrier such as alumina or silica. Although what was carry | supported is mentioned, You may use this for [process 2].

[Step 2]: In the step [Step 2] of reacting the terminal double bond-containing polyolefin and hydrosilane , one or more vinyl groups are added in the presence of the transition metal catalyst composition (C) obtained in the above [Step 1]. The raw material compound (2) and the hydrosilane (raw material compound (1)) containing the structural unit (1) represented by the above general formula are reacted (however, the structural unit (1) and the raw material compound in the raw material compound (1)) (Excluding the reaction in the case where there are a plurality of vinyl groups in (2)), to obtain silylated polyolefin [A].

  Moreover, the hydrosilane (raw material compound (1)) containing the structural unit (1) represented by the general formula used in [Step 2] may be different from the hydrosilane used in [Step 1]. Preferably, the same one as used in [Step 1] is used.

  The amount ratio when the terminal double bond-containing polyolefin as the raw material compound (2) is reacted with hydrosilane containing one or more structural units (1) represented by the general formula varies depending on the purpose, but the terminal double bond is contained. The equivalent ratio of the terminal double bond in the polyolefin and the Si—H bond in the hydrosilane is in the range of 0.01 to 10 equivalent times, preferably in the range of 0.1 to 2 equivalent times. Here, the amount of hydrosilane is the total amount of the portion used in [Step 1] and included in the transition metal catalyst composition (C) and the portion newly added in [Step 2]. When the entire amount of hydrosilane required in [Step 1] is used, [Step 2] can be carried out without adding hydrosilane.

The reaction between the terminal double bond-containing polyolefin and hydrosilane is carried out in the presence of the transition metal catalyst composition (C) prepared in [Step 1]. The amount ratio of the transition metal catalyst composition (C) to the terminal double bond-containing polyolefin is the equivalent of the terminal double bond in the terminal double bond-containing polyolefin and the transition metal content in the transition metal catalyst composition (C). The ratio is in the range of 10 ⁻¹⁰ to 10 ⁻¹ equivalent times, preferably in the range of 10 ⁻⁷ to 10 ⁻³ equivalent times.

  The reaction method in the reaction between the terminal double bond-containing polyolefin and hydrosilane may be a final reaction, and the method is not limited. For example, the reaction is performed as follows. The terminal double bond-containing polyolefin is charged into a reaction vessel, and hydrosilane and a transition metal catalyst composition (C) are charged under a nitrogen atmosphere. The reactor is set and stirred in an oil bath whose internal temperature has been raised in advance to the melting point of the polyolefin containing terminal double bonds. After the reaction, the oil bath is removed and the mixture is cooled to room temperature, and the resulting reaction mixture is taken out in a poor solvent such as methanol or acetone and stirred for 2 hours. Thereafter, the obtained solid is collected by filtration, washed with the above poor solvent, and dried under reduced pressure at 60 ° C. and 2 hPa or less to obtain the target product.

  The reaction between the terminal double bond-containing polyolefin and hydrosilane in [Step 2] is preferably carried out at a temperature higher than the melting point of the terminal double bond-containing polyolefin to be reacted. More preferred. A reaction temperature lower than 100 ° C. is not preferable because the reaction efficiency may be lowered. In addition, the pressure can be usually performed at normal pressure, but can be performed under pressure or under reduced pressure as necessary.

  In [Step 2], a solvent may be used as necessary. The solvent used can be inert to the raw material hydrosilane and the terminal double bond-containing polyolefin. When the reaction is performed under normal pressure, it is preferable to use one having a boiling point equal to or higher than the melting point of the terminal double bond-containing polyolefin to be reacted. Specific examples of the solvent that can be used include aliphatic hydrocarbons such as n-hexane, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate, acetone, Examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and methyl propyl ketone; ethers such as tetrahydrofuran and 1,4-dioxane; halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethane, tetrachloroethane, and perchloroethane. . Of these, aromatic hydrocarbons such as toluene and xylene are particularly preferable.

  When the solvent is used, the amount of the solvent used affects the solubility of the raw material, but is preferably 100 times by mass or less, more preferably 20 times by mass or less with respect to the raw material. In the present invention, it is most preferable to carry out without solvent.

  As described above, by reacting a terminal double bond-containing polyolefin and hydrosilane in the presence of the transition metal catalyst composition (C), a silylated polyolefin containing the structural unit (1) represented by the above general formula [ A reaction mixture containing A] is obtained.

  The reaction mixture containing the silylated polyolefin [A] after the reaction contains, in addition to the silylated polyolefin [A], an unreacted terminal double bond-containing polyolefin and a by-product vinylene derivative. In some cases, unreacted hydrosilane may be contained.

  The proportion of the structural unit (1) in the silylated polyolefin [A] is not particularly limited as long as the target function of the silylated polyolefin [A] is expressed, but is usually 5 to 99% by weight, preferably Is 10 to 95% by weight. If the structural unit is small, the releasability function cannot be expressed, and if it is large, it becomes oily and causes troubles such as bleed out.

  In the above method, since the transition metal catalyst composition (C) having a high activity and selectivity obtained in [Step 1] is used, the terminal double bond-containing polyolefin of [Step 2] and hydrosilane are used. The reaction proceeds efficiently. Therefore, the double bond reaction rate of the terminal double bond-containing polyolefin is usually 90% or more, preferably 95% or more, and the amount of vinylene derivative produced as a by-product is larger than that of the silylated polyolefin [A]. The amount is usually 10% by weight or less, preferably 5% by weight or less.

  Silylated polyolefin [A] can be taken out of the reaction mixture by reprecipitation into a poor solvent or sludge. The poor solvent may be appropriately selected as long as it has low solubility of silylated polyolefin [A], and preferably can remove the above impurities. Specific examples of the poor solvent include acetone, methanol, ethanol, n-propanol, isopropanol, acetonitrile, ethyl acetate, n-hexane, and n-heptane. Among these, acetone and methanol are preferable.

  Specific examples of the silylated polyolefin [A] are preferably those represented by the following general formulas (7) to (10), but are not limited thereto.

（上記一般式中のｍ，ｎ，ｏ，ｐ，ｑは１以上の整数を表す。）

(M, n, o, p, q in the above general formula represent an integer of 1 or more.)

Additives Additives that do not impair the purpose and effect of the present invention, such as brominated bisphenol, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, triphenyl phosphate, phosphonic acid amide and red phosphorus Flame retardants, flame retardant aids such as antimony trioxide and sodium antimonate, thermal stabilizers such as phosphate esters and phosphites, antioxidants such as hindered phenols, heat resistance agents, weathering agents, A light stabilizer, a release agent, a flow modifier, a colorant, a pigment, a lubricant, an antistatic agent, a crystal nucleating agent, a plasticizer, a foaming agent, and the like may be blended in an effective expression amount as necessary.

  In the present invention, commercially available silylated polyolefins can also be used. For example, Exfola manufactured by Mitsui Chemicals, Inc., BY27-201C and BY27-202H manufactured by Toray Dow Corning Co., Ltd., and the like can be mentioned.

Manufacturing method of water-repellent film The manufacturing method of the water-repellent film according to the present invention is not particularly limited, and can be manufactured by a conventionally known method. In the present invention, extrusion molding is preferable, and extrusion molding is more preferably performed by a T-die method or an inflation method.

  For example, the resin film can be formed by extrusion molding by the following method. After drying the resin composition described above, the resin composition is supplied to a melt extruder heated to a temperature not lower than the melting point of the thermoplastic resin (Tm) to Tm + 70 ° C. to melt the resin composition. A film can be formed by extruding into a sheet form from the die and rapidly solidifying the extruded sheet form with a rotating cooling drum or the like. As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

  The heating temperature is preferably 170 to 230 ° C., more preferably 180 to 220 ° C. in the inflation method, and preferably 180 to 300 ° C., more preferably 210 to 270 ° C. in the T-die method.

  The resin composition is, for example, 1 to 30 g / 10 minutes, preferably 1 to 8 g / 10 minutes and 1 to 6 g / 10 minutes in the inflation method, and preferably 4 to 20 g / 10 minutes and more preferably in the T-die method. Has a melt flow rate (MFR) of 6 to 15 g / 10 min. The melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. If the MFR of the resin composition is 1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if MFR of a resin composition is 30 g / 10min or less, the mechanical strength of the resin film which consists of this resin composition can be raised.

  The thickness of the resin film obtained as described above is arbitrary depending on the application, but is usually about 5 to 500 μm, preferably about 5 to 200 μm. Further, the resin film may be used as a single layer film, or may be used as a laminated film by laminating a plurality of sheets.

Packaging Material A packaging material according to the present invention is composed of the above water-repellent film. Specifically, it can be used for lids, packaging containers, and the like. By forming the packaging material so that the water-repellent film is located on the inner surface (content side) of the packaging material, the contents having a viscous material such as a liquid, semi-solid, or gel substance adhere to or remain on the inner surface of the packaging material. Can be suppressed.

Example 1
Silylated polyolefin (Mitsui Chemicals, trade name: EXFORA) and linear low density polyethylene resin (LLDPE resin, Prime Polymer Co., trade name: Evolue SP2020) in a ratio of 30:70 To obtain a resin composition. Next, the resin composition was used to form a film with a lab inflation film forming machine to obtain a film having a thickness of 100 μm.

  Subsequently, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) are measured using a contact angle measuring machine (manufactured by Kyowa Interface Science Co., Ltd., trade name: Drop Mater 700). ). The liquid drop amount was 1.5 μl, and measurement was performed 60 seconds after the drop. The measurement results are shown in Table 1.

Example 2
1:99 ratio of silylated polyolefin (Mitsui Chemicals Co., Ltd., trade name: EXFORA) and linear low density polyethylene resin (LLDPE resin, Prime Polymer Co., Ltd., trade name: Evolue SP2020) A film having a thickness of 100 μm was obtained by carrying out film formation in the same manner as in Example 1 except that the resin composition was prepared by mixing in step 1. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Example 3
Silylated polyolefin (manufactured by Mitsui Chemicals, Inc., trade name: EXFORA) and linear low density polyethylene resin (LLDPE resin, manufactured by Prime Polymer Co., Ltd., trade name: Evolue SP2020) are 0.5: 99. A film having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the resin composition was prepared by mixing at a ratio of 0.5. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Example 4
Silylated polyolefin (Mitsui Chemicals, trade name: EXFORA) and linear low density polyethylene resin (LLDPE resin, Prime Polymer Co., trade name: Evolue SP2020) 0.3: 99 A film having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the resin composition was prepared by mixing at a ratio of 0.7. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Example 5
Silylated polyolefin (Mitsui Chemicals Co., Ltd., trade name: EXFORA) and polypropylene resin (PP resin, Sun Allomer Co., Ltd., trade name: Novatec PF380A) are mixed at a ratio of 30:70 to obtain a resin composition. A film having a thickness of 100 μm was obtained by performing film formation in the same manner as in Example 1 except that the product was manufactured. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Example 6
Silylated polyolefin (Mitsui Chemicals Co., Ltd., trade name: EXFORA) and polypropylene resin (PP resin, Sun Allomer Co., Ltd., trade name: Novatec PF380A) are mixed at a ratio of 1:99 to obtain a resin composition. A film having a thickness of 100 μm was obtained by performing film formation in the same manner as in Example 1 except that the product was manufactured. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Example 7
Silylated polyolefin (Mitsui Chemicals: Exfora) and polypropylene resin (PP resin, manufactured by Sun Allomer Co., Ltd., trade name: Novatec PF380A) are mixed at a ratio of 0.5: 99.5 to prepare a resin composition. Except for the above, a film was formed in the same manner as in Example 1 to obtain a film having a thickness of 100 μm. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Example 8
Silylated polyolefin (Mitsui Chemicals: EXFORA) and polypropylene resin (PP resin, manufactured by Sun Allomer Co., Ltd., trade name: Novatec PF380A) are mixed at a ratio of 0.3: 99.7 to prepare a resin composition. Except for the above, a film was formed in the same manner as in Example 1 to obtain a film having a thickness of 100 μm. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Example 9
Silylated polyolefin (manufactured by Toray Dow Corning Co., Ltd., trade name: BY27-202H) and linear low density polyethylene resin (LLDPE resin, Prime Polymer Co., Ltd., trade name: Evolu SP2020) are 30: Except that the resin composition was prepared by mixing at a ratio of 70, a film was formed in the same manner as in Example 1 to obtain a film having a thickness of 100 μm. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Example 10
Silylated polyolefin (made by Toray Dow Corning Co., Ltd., trade name: BY27-201C) and polypropylene resin (PP resin, made by Sun Allomer Co., Ltd., trade name: Novatec PF380A) were mixed at a ratio of 30:70. A film having a thickness of 100 μm was obtained by performing film formation in the same manner as in Example 1 except that the resin composition was prepared. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Comparative Example 1
A linear low density polyethylene resin (LLDPE resin, manufactured by Prime Polymer Co., Ltd., trade name: Evolue SP2020) was formed using a lab inflation film forming machine to obtain a film having a thickness of 100 μm. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Comparative Example 2
A polypropylene resin (PP resin, manufactured by Sun Allomer Co., Ltd., trade name: Novatec PF380A) was formed with a lab inflation film forming machine to obtain a film having a thickness of 100 μm. Subsequently, in the same manner as in Example 1, the water contact angle of the film after film formation and the contact angle of oil (soybean oil, manufactured by Junsei Chemical Co., Ltd.) were measured. The measurement results are shown in Table 1.

Packaging Material Performance Evaluation Using the films obtained in the above examples and comparative examples, a packaging material was produced. The water repellency and oil repellency of the packaging material contents (liquid: water, oil) were visually evaluated according to the following evaluation criteria. The evaluation results are shown in Table 2.
Evaluation criteria ( circle): Water-repellent performance and oil-repellent performance were favorable.
Δ: Water repellency and oil repellency were normal.
X: Water repellency and oil repellency were insufficient.

Claims (14)

  A water repellent film comprising a resin composition comprising a thermoplastic resin and a silylated polyolefin, wherein the contact angle of water on the surface is 100 degrees or more.   The water repellent film according to claim 1, wherein a contact angle of oil on the surface of the water repellent film is 30 degrees or more.   The water repellent film according to claim 1 or 2, wherein a content of the silylated polyolefin is 0.1 to 40% by mass with respect to the resin composition.   The water-repellent film according to any one of claims 1 to 3, wherein the thermoplastic resin is a polyolefin resin. The silylated polyolefin is a reaction of a raw material compound (1) containing one or more structural units (1) represented by the following general formula and a raw material compound (2) containing one or more vinyl groups (however, in the raw material compound (1)) It is silylated polyolefin [A] manufactured by the structural unit (1) and the raw material compound (2) except for the reaction when both vinyl groups are plural). Water repellent film.

(In the formula, R ¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and Y ¹ represents O, S or NR (R represents a hydrogen atom or a hydrocarbon group).)   The water repellent film according to claim 5, wherein the silylated polyolefin [A] has a number average molecular weight of 100 to 1,000,000. The water-repellent film according to claim 5 or 6, wherein the raw material compound (1) is represented by the following general formula (2).

(Wherein R ¹ and R ³ represent a hydrogen atom, a halogen atom or a hydrocarbon group, and may be the same or different, and when there are a plurality of R ¹ and R ^3, they may be the same or different; ² and R ⁴ represent a hydrogen atom, a halogen atom, a hydrocarbon group or a group represented by the general formula (3), which may be the same or different, and Y ¹ and Y ² are O, S or NR (R is hydrogen Represents an atom or a hydrocarbon group, and may be the same or different, and when a plurality of Y ¹ and Y ² are present, they may be the same or different, m is an integer of 1 to 20, and n is 0 When n is 1 or more, Z represents a divalent linking group represented by the general formula (4), and when n is 0, R ⁴ represents a hydrogen atom or a hydrocarbon group. Z is a divalent compound represented by the general formula (4). It represents a direct bond between Yuimoto or ^{Y 1} and ^{R 4.)}

(In the formula, R ²¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of R ²¹ may be the same or different, and x is an integer of 1 to 10).

(In the formula, R ¹¹ represents a hydrogen atom, a halogen atom or a hydrocarbon group, and a plurality of R ¹¹ may be the same or different, and l is an integer of 0 to 500.)   Two or more olefins selected from the group consisting of an ethylene homopolymer chain, a propylene homopolymer chain, or an olefin having 2 to 50 carbon atoms, other than the vinyl group of the raw material compound (2) of the silylated polyolefin [A] The water-repellent film according to any one of claims 5 to 7, which is a copolymer chain having a number average molecular weight of 100 to 500,000.   The part other than the vinyl group of the raw material compound (2) of the silylated polyolefin [A] is a linear ethylene homopolymer chain having 3 to 200 carbon atoms that does not contain a double bond. The water repellent film according to one item. The water repellency according to any one of claims 5 to 9, wherein the starting compound (2) of the silylated polyolefin [A] is an unmodified olefin resin (B) satisfying the following (B1) to (B6). the film.
(B1) A copolymer obtained by copolymerizing ethylene and at least one diene, or at least one olefin selected from ethylene and an α-olefin having 3 to 12 carbon atoms and at least one diene. A copolymer obtained by copolymerization.
(B2) The unsaturated group content per molecule is 0.5 to 3.0.
(B3) The density is 870 to 980 kg / m ³ .
(B4) Melting point is 70-130 ° C.
(B5) Number average molecular weight (Mn) is 400-5,000.
(B6) The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 4.0 or less.   The water repellent film according to claim 10, wherein the diene of (B1) is vinyl norbornene (5-vinylbicyclo [2.2.1] hept-2-ene).   The water-repellent film according to any one of claims 1 to 11, wherein the water-repellent film is extruded.   The water repellent film according to claim 12, wherein the extrusion molding is performed by a T-die method or an inflation method.   A packaging material comprising the water repellent film according to any one of claims 1 to 13.