Modifier for polyolefin resin, polyolefin resin composition, polyolefin resin film, and laminated film

Abstract

The present invention provides a modifier for a polyolefin resin, which contains a compound (A) represented by formula (1) and a compound (B) represented by formula (2). Compound (A) # imgabs0 # (In formula (1), R1 and R3 each represents a hydrocarbon group having 5-21 carbon atoms. R2 is a residue obtained by removing all hydroxyl groups from a (poly) oxyalkylene glycol having 2 to 100 carbon atoms, and the (poly) oxyalkylene glycol having 2 to 100 carbon atoms has a (poly) oxyalkylene group comprising an oxyalkylene unit having 2 to 4 carbon atoms in the molecule thereof. ) Compound (B) # imgabs1 # (In formula (2), R4 represents a hydrocarbon group having 5-21 carbon atoms. R5 is a residue obtained by removing all hydroxyl groups from a (poly) oxyalkylene glycol having 2 to 100 carbon atoms, and the (poly) oxyalkylene glycol having 2 to 100 carbon atoms has a (poly) oxyalkylene group comprising an oxyalkylene unit having 2 to 4 carbon atoms in the molecule thereof. )

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is based on Japanese Patent Application No. 2023-104620 filed with the Japan Patent Office on June 27, 2023, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present disclosure relates to a modifier for a polyolefin-based resin, a polyolefin-based resin composition, a polyolefin-based resin film, and a laminated film. Background Art

[0004] As a film for food packaging, films made of polyolefin resins are widely used. However, polyolefin resins are hydrophobic. Therefore, water evaporated from food adheres to the inner surface of the film to form fine water droplets. As a result, the problem of film fogging occurs. Therefore, various films that are given anti-fogging properties by using modifiers formulated to prevent film fogging have been proposed.

[0005] For example, Japanese Patent Application Laid-Open No. 2007-45855 discloses a film containing an antifogging agent and a polyolefin resin. The antifogging agent is composed of (A) a fatty acid ester of a trivalent or higher polyol, (B) a polyoxyethylene alkyl ether, and (C) a polyalkylene glycol fatty acid ester.

[0006] Japanese Patent Publication No. 2002-20555 discloses a film comprising: a linear low-density polyethylene resin, (A) an ester obtained from polyglycerol and a fatty acid, (B) an ethylene oxide adduct of a fatty acid, and (C) an ethylene oxide adduct of an ester obtained from sorbitan and a fatty acid. In addition, according to Japanese Patent Publication No. 2002-20555, by mixing the components of the film at a prescribed ratio, excellent stability during molding is achieved.

[0007] Such modifiers are transported and stored in the form of masterbatches containing the modifiers at high concentrations. Therefore, in general, when manufacturing a film, the masterbatch is mixed with a resin to make the film. However, the existing masterbatch containing a high concentration of modifiers sometimes has problems such as demolding during manufacturing. Or sometimes, the masterbatch may stick due to the modifier seeping out during storage, resulting in inconvenient operation.

[0008] Therefore, according to an embodiment of the present disclosure, a polyolefin resin modifier is provided, which can impart excellent anti-fogging properties and manufacturability to a polyolefin resin film, improve the manufacturability of a masterbatch, and inhibit blocking. In addition, a polyolefin resin composition, a polyolefin resin film, and a laminated film containing the modifier can also be provided. Summary of the invention

[0009] The polyolefin-based resin modifier according to the embodiment of the present disclosure contains a compound (A) represented by the following formula (1) and a compound (B) represented by the following formula (2).

[0010] Compound (A)

[0011]

[0012] (Where R 1 and R 3 is a hydrocarbon group having 5 to 21 carbon atoms. 2 A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule.

[0013] Compound (B)

[0014]

[0015] (Where R 4 is a hydrocarbon group having 5 to 21 carbon atoms. 5 A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule. DETAILED DESCRIPTION

[0016] In the detailed description below, for the purpose of explanation, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. However, it is apparent that one or more embodiments may be implemented without these specific details. In other cases, well-known structures and devices are schematically illustrated to simplify the drawings.

[0017] The embodiments of the present disclosure for solving the above-mentioned problems relate to the following polyolefin resin modifier, polyolefin resin composition, polyolefin resin film, and laminated film.

[0018] [1] A modifier for a polyolefin resin, comprising a compound (A) represented by the following formula (1) and a compound (B) represented by the following formula (2).

[0019] Compound (A)

[0020]

[0021] (Where R 1 and R 3 is a hydrocarbon group having 5 to 21 carbon atoms. 2A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule.

[0022] Compound (B)

[0023]

[0024] (Where R 4 is a hydrocarbon group having 5 to 21 carbon atoms. 5 A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule.

[0025] [2] The polyolefin resin modifier according to [1], wherein R 1 , R 3 and R 4 It is a hydrocarbon group having 7 to 17 carbon atoms.

[0026] [3] The polyolefin resin modifier according to [1], wherein R 2 and R 5 It is a residue obtained by removing all hydroxyl groups from a polyoxyalkylene glycol having 4 to 50 carbon atoms, wherein the polyoxyalkylene glycol having 4 to 50 carbon atoms has a polyoxyalkylene group containing an oxyalkylene unit having 2 carbon atoms in its molecule.

[0027] [4] The polyolefin resin modifier according to [1], wherein the modifier contains 20 to 80 parts by mass of the compound (A) and 20 to 80 parts by mass of the compound (B), based on 100 parts by mass of the total of the compound (A) and the compound (B).

[0028] [5] The polyolefin resin modifier according to [1], further comprising a nonionic surfactant (C).

[0029] [6] The polyolefin resin modifier according to [5], wherein the nonionic surfactant (C) is a partial ester of a 3-6-valent polyol and an aliphatic carboxylic acid having 6 to 22 carbon atoms.

[0030] [7] The polyolefin resin modifier according to [5], wherein the nonionic surfactant (C) is contained in an amount of 20 to 400 parts by mass based on 100 parts by mass of the total of the compound (A) and the compound (B).

[0031] [8] A polyolefin resin composition comprising a polyolefin resin and the polyolefin resin modifier according to any one of [1] to [7].

[0032] [9] A polyolefin resin film comprising the polyolefin resin composition according to [8].

[0033]

[10] A laminated film comprising two or more laminated layers, wherein at least one outermost layer of the two or more layers is the polyolefin resin film according to [9].

[0034] In addition, the numerical range represented by "Y to Z" in the present disclosure means a range including the upper limit and the lower limit. That is, "Y to Z" means "Y or more and Z or less".

[0035] Modifiers for polyolefin resins

[0036] The modifier for polyolefin resin (hereinafter also referred to as "modifier") contains a compound (A) represented by the following general formula (1) and a compound (B) represented by the following general formula (2). In addition, the modifier preferably further contains a nonionic surfactant (C).

[0037] Compound (A)

[0038]

[0039] (Where R 1 and R 3 is a hydrocarbon group having 5 to 21 carbon atoms. 2 A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule.

[0040] Compound (B)

[0041]

[0042] (Where R 4 is a hydrocarbon group having 5 to 21 carbon atoms. 5 A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule.

[0043] Compound (A)

[0044] Compound (A) is a diester represented by the above general formula (1). Examples of compound (A) include: 1) esters of alkylene oxides having 2 to 4 carbon atoms and aliphatic carboxylic acids having 6 to 22 carbon atoms added to one or more aliphatic carboxylic acids having 6 to 22 carbon atoms; and 2) diesters of aliphatic carboxylic acids having 6 to 22 carbon atoms and (poly)oxyalkylene glycols having (poly)oxyalkylene units consisting of 2 to 4 carbon atoms. One compound (A) may be used alone. Alternatively, two or more compounds (A) may be used in combination.

[0045] The hydrocarbon group of the aliphatic carboxylic acid with 6 to 22 carbon atoms as the raw material of compound (A) can be any of a saturated hydrocarbon group and an unsaturated hydrocarbon group. In addition, the hydrocarbon group can be any of a straight chain structure, a branched structure and a ring structure. As examples of such aliphatic carboxylic acids, caproic acid, sorbic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, undecenoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, isostearic acid, arachidic acid, heneicosanoic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, erucic acid, 12-hydroxystearic acid and ricinoleic acid can be cited. As two aliphatic carboxylic acids with 6 to 22 carbon atoms as the raw materials of compound (A), the same aliphatic carboxylic acid can be used. Alternatively, different aliphatic carboxylic acids can be used.

[0046] Examples of alkylene oxides having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and 1,2-butylene oxide. When two or more alkylene oxides are used, examples of the form of the alkylene oxide added to the aliphatic carboxylic acid having 6 to 22 carbon atoms include random copolymerization, block copolymerization, and random-block copolymerization. The number of moles of alkylene oxide added to 1 mole of the aliphatic carboxylic acid having 6 to 22 carbon atoms is determined so that the total number of carbon atoms of the alkylene oxide is in the range of 2 to 100.

[0047] Examples of (poly)oxyalkylene glycols having (poly)oxyalkylene groups composed of oxyalkylene units having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, and polyethylene glycol-polypropylene glycol block polymers. The amount of (poly)oxyalkylene glycol used relative to 1 mol of aliphatic carboxylic acid having 6 to 22 carbon atoms is determined so that the total number of carbon atoms of the (poly)oxyalkylene glycol is in the range of 2 to 100.

[0048] Compound (B)

[0049] Compound (B) is a monoester represented by the above general formula (2). Examples of compound (B) include monoesters of aliphatic carboxylic acids having 6 to 22 carbon atoms and (poly)oxyalkylene glycols having (poly)oxyalkylene units composed of 2 to 4 carbon atoms. One compound (B) may be used alone. Alternatively, two or more compounds (B) may be used in combination.

[0050] As the aliphatic carboxylic acid having 6 to 22 carbon atoms, the alkylene oxide having 2 to 4 carbon atoms, and the (poly)oxyalkylene glycol having a (poly)oxyalkylene group consisting of oxyalkylene units having 2 to 4 carbon atoms, which are the raw materials of the compound (B), the same compounds as the raw materials of the compound (A) can be used.

[0051] It should be noted that R 1 and R 3 , and R of compound (B) 4 It is preferably a hydrocarbon group having 7 to 17 carbon atoms. 2 , and R of compound (B) 5 Preferably, it is a residue obtained by removing all hydroxyl groups from a polyoxyalkylene glycol having 4 to 50 carbon atoms, wherein the polyoxyalkylene glycol having 4 to 50 carbon atoms has a polyoxyalkylene group containing an oxyalkylene unit having 2 carbon atoms in its molecule. 2 , and R of compound (B) 5 More preferably, it is a residue obtained by removing all hydroxyl groups from a polyoxyalkylene glycol having 4 to 30 carbon atoms, wherein the polyoxyalkylene glycol having 4 to 30 carbon atoms has a polyoxyalkylene group containing an oxyalkylene unit having 2 carbon atoms in its molecule.

[0052] Nonionic surfactant (C)

[0053] As the nonionic surfactant (C), any known compound other than compound (A) and compound (B) can be used. One or more nonionic surfactants (C) can be used alone. Alternatively, two or more nonionic surfactants (C) can be used in combination. Preferred examples of nonionic surfactants (C) include partial esters of 3-6-valent polyols and aliphatic carboxylic acids having 6 to 22 carbon atoms.

[0054] Examples of trivalent to hexavalent polyols include: 1) polyols containing glycerol, pentaerythritol, sorbitol and glucose, 2) cyclic ether polyols obtained by dehydrating sorbitol such as sorbitan or sorbitan, 3) (poly)ether tetraols containing diglycerol and ethylene glycol diglycerol ether, 4) (poly)ether pentaols containing triglycerol and trimethylolpropane diglycerol ether, and 5) (poly)ether hexanols containing tetraglycerol and dipentaerythritol. On the other hand, as the aliphatic carboxylic acid having 6 to 22 carbon atoms, the same aliphatic carboxylic acid having 6 to 22 carbon atoms as the raw material of compound (A) can be used.

[0055] Content ratio

[0056] The modifier contains compound (A) and compound (B) in a desired ratio. It should be noted that, in the modifier, when the total of compound (A) and compound (B) is set to 100 parts by mass, it is preferred to contain 5 to 95 parts by mass of compound (A) and 5 to 95 parts by mass of compound (B). It is more preferred to contain 20 to 80 parts by mass of compound (A) and 20 to 80 parts by mass of compound (B). It is further preferred to contain 30 to 70 parts by mass of compound (A) and 30 to 70 parts by mass of compound (B).

[0057] When the modifier contains a nonionic surfactant (C), the contents of compound (A), compound (B) and nonionic surfactant (C) may be set to a desired ratio. It should be noted that, when the total of compound (A) and compound (B) is 100 parts by mass, it is preferred that 10 to 500 parts by mass, more preferably 20 to 400 parts by mass, and even more preferably 20 to 200 parts by mass of nonionic surfactant (C) are contained.

[0058] Polyolefin resin composition

[0059] The polyolefin resin composition (hereinafter also referred to as "resin composition") contains a modifier and a polyolefin resin. The resin composition also includes a molded product of the resin composition including a masterbatch and a polyolefin resin film.

[0060] Polyolefin resin

[0061] Examples of polyolefin resins include: 1) α-olefin homopolymers including polyethylene and polypropylene obtained from one α-olefin having 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene; 2) α-olefin copolymers including ethylene·propylene copolymers, ethylene·1-butene copolymers and ethylene·1-hexene copolymers obtained from two or more α-olefins having 2 to 8 carbon atoms; 3) copolymers obtained from ethylene and vinyl acetate; 4) ethylene·vinyl alcohol copolymers obtained by saponifying copolymers obtained from ethylene and vinyl acetate; 5) ethylene·acrylic acid copolymers obtained from ethylene and at least one selected from acrylic acid, methyl acrylate and ethyl acrylate; and 6) ethylene·methacrylic acid copolymers composed of ethylene and at least one selected from methacrylic acid and methyl methacrylate. One polyolefin resin may be used alone. Alternatively, two or more polyolefin resins may be used in combination.

[0062] Content ratio

[0063] The content ratio of the modifier and the polyolefin resin in the resin composition is not particularly limited. The content ratio can be appropriately set based on the form of the resin composition. Usually, when the total of the modifier and the polyolefin resin is set to 100 parts by mass, the resin composition preferably contains 0.1 to 30 parts by mass of the modifier. It should be noted that when the resin composition is a masterbatch, it is preferably 2.5 to 25 parts by mass, and more preferably 5 to 20 parts by mass of the modifier relative to the total of 100 parts by mass of the modifier and the polyolefin resin.

[0064] Method for producing resin composition

[0065] The resin composition is not particularly limited and can be produced by a known method. For example, when the resin composition is a masterbatch, the following methods (1), (2), (3) and (4) can be used.

[0066] (1) A mixture of a polyolefin resin and a modifier pre-mixed by a mixer such as a tumble mixer, a high-speed mixer or a Henschel mixer is melt-kneaded and pelletized by an extruder such as a single-screw extruder or a multi-screw extruder.

[0067] (2) A polyolefin resin melted by a single screw extruder or a multi-screw extruder is mixed with a modifier added by side feeding or liquid injection, and melt-kneaded and granulated.

[0068] (3) Using a feeder, the polyolefin resin and the modifier supplied to an extruder such as a single-screw extruder or a multi-screw extruder are melt-kneaded and granulated.

[0069] (4) A polyolefin-based resin supplied to an extruder such as a single-screw extruder or a multi-screw extruder and a modifier introduced by side feeding or liquid injection are supplied to the extruder by a feeder, melt-kneaded and pelletized.

[0070] Then, the particles of the obtained resin composition are melt-kneaded with a polyolefin resin using any of the methods (2) to (4). Thus, a molding resin composition containing a polyolefin resin and a modifier in the same ratio as a polyolefin resin film described later can be obtained. It should be noted that the molding resin composition can be supplied to the molding method of the resin film described later in a molten state. In addition, the molding resin composition can be manufactured by directly mixing the modifier with the polyolefin resin without going through a masterbatch.

[0071] As described above, examples of methods for mixing the polyolefin resin, compound (A), compound (B) and nonionic surfactant (C) which will become the raw materials include mixing using a mixer such as a drum mixer, a high-speed mixer or a Henschel mixer, side feeding and liquid injection. Among these methods, which method to use can be determined according to the state of the polyolefin resin, compound (A), compound (B) and nonionic surfactant (C). When the raw material is solid, mixing using a mixer such as a drum mixer, a high-speed mixer or a Henschel mixer, or side feeding is used. In addition, when the raw material is liquid, liquid injection or mixing using a high-speed mixer or a Henschel mixer is used. After the solid raw material is dissolved or dispersed in the liquid raw material, the liquid or liquid raw material can be mixed as a whole.

[0072] Polyolefin resin film

[0073] The polyolefin resin film (hereinafter also referred to as "resin film") contains a resin composition, that is, a polyolefin resin and a modifier. The content ratio of the modifier to the polyolefin resin in the resin film is not particularly limited. When the total of the modifier and the polyolefin resin is set to 100 parts by mass, it is preferably contained in 0.1 to 5 parts by mass, and more preferably contains 0.25 to 3.0 parts by mass of the modifier. It should be noted that when the film is a single-layer resin film, it is further preferred to contain 0.25 to 1.0 parts by mass of the modifier relative to the total of 100 parts by mass of the modifier and the polyolefin resin. In addition, when the film is a laminated film described later, in the resin film, it is further preferred to contain 1.25 to 3.0 parts by mass of the modifier relative to the total of 100 parts by mass of the modifier and the polyolefin resin.

[0074] Resin film forming method

[0075] The resin film can be manufactured by molding a molding resin composition containing a polyolefin resin and a modifier in a specified ratio using a known molding method. As an example of a molding method for the resin film, there can be cited inflation molding including air-cooled inflation molding, air-cooled secondary inflation molding, air-cooled tertiary inflation molding and water-cooled inflation molding, T-die molding using a straight manifold type T-die, a hanger type T-die or a combination of these T-dies, calendering molding, and compression molding. Any of unstretched resin film and stretched resin film can be used. As an example of a stretching method, successive biaxial stretching, simultaneous biaxial stretching and tubular biaxial stretching can be cited. It should be noted that the subject of this embodiment is to improve the manufacturability of the masterbatch and suppress adhesion. The resin film involved in this embodiment also includes a film manufactured by a modifier and a polyolefin resin without undergoing a masterbatch. The laminated film described later is also the same.

[0076] additive

[0077] The modifier, resin composition, resin film and laminated film may contain other additives according to the purpose. Examples of the additives include heat stabilizers, antioxidants, neutralizers, lubricants, weathering agents, ultraviolet absorbers and anti-blocking agents.

[0078] Laminated Film

[0079] The laminated film has a laminated structure comprising more than two layers. Among these laminated layers, at least one outermost layer comprises the resin film involved in the present embodiment. The layer other than the layer comprising the resin film is made of, for example, a thermoplastic resin, an adhesive, an anchor coating agent, an adhesive resin or a metal such as aluminum. As examples of thermoplastic resins, polyesters such as polyolefin resins, polyethylene terephthalate, polyamides such as nylon 6, polyvinyl alcohol, polystyrene and acrylic resins such as polymethyl methacrylate can be cited. Thermoplastic resins can contain additives according to the purpose. As examples of additives, heat stabilizers, antioxidants, neutralizers, lubricants, weathering agents, ultraviolet light absorbers, anti-blocking agents, anti-static agents and anti-fogging agents can be cited.

[0080] The laminated film can be manufactured by a known method. Examples of the manufacturing method of the laminated film include dry lamination, sandwich lamination, extrusion lamination and coextrusion. When the laminated film is manufactured by dry lamination, sandwich lamination or extrusion lamination, for example, a known polyurethane adhesive, an organic titanium anchor coating agent, an isocyanate anchor coating agent or an adhesive resin can be used. As a manufacturing method using a coextrusion method, for example, inflation molding or T-die molding can be used. Any of an unstretched molding method and a stretch molding method can be used.

[0081] The resin film and laminated film involved in this embodiment are preferably used for food packaging. However, their use is not particularly limited. In addition, the film thickness of the resin film and laminated film is not particularly limited. The film thickness can be appropriately set according to its use.

[0082] The modifier involved in the present embodiment contains compound (A) and compound (B). Thus, it is possible to impart excellent anti-fogging properties to the polyolefin resin film. At the same time, it is possible to suppress extrusion variations during film manufacturing. As a result, a film with a stable film thickness can be obtained. Therefore, the manufacturability of the film can be improved. And it is possible to suppress undesirable conditions such as demoulding or strand disorder during the manufacture of the masterbatch. Therefore, manufacturability is improved. At the same time, it is possible to suppress adhesion caused by the modifier that seeps out during the storage of the masterbatch.

[0083] Example

[0084] The configuration and effects of the present embodiment will be described in more detail using Examples and Comparative Examples. In the following description, "parts" represent parts by mass.

[0085] The compound (A), compound (B), nonionic surfactant (C) and polyolefin resin used in the following examples are as follows.

[0086] Compound (A)

[0087] Compound (A) is a diester represented by the following formula (1). 1 ~R 3 The carbon number of each is shown in Table 1.

[0088] Compound (A)

[0089]

[0090] (Where R 1 and R 3 is a hydrocarbon group having 5 to 21 carbon atoms. 2 A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule.

[0091] Table 1

[0092]

[0093] R of A-2 to A-5 and A-7 1 and R 3 In the formula, saturated hydrocarbon groups and unsaturated hydrocarbon groups exist in combination. 1 and R 3It is a saturated hydrocarbon group.

[0094] Compound (B)

[0095] Compound (B) is a monoester represented by the following formula (2). 4 and R 5 The carbon number of each of the compounds is shown in Table 2.

[0096] Compound (B)

[0097]

[0098] (Where R 4 is a hydrocarbon group having 5 to 21 carbon atoms. 5 A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule.

[0099] Table 2

[0100]

[0101] R of B-2 to B-5 and B-7 4 In the formula, saturated hydrocarbon groups and unsaturated hydrocarbon groups exist in combination. 4 It is a saturated hydrocarbon group.

[0102] Nonionic surfactant (C)

[0103] C-1: Partial ester of glycerol and oleic acid

[0104] C-2: Partial ester of diglycerol and lauric acid

[0105] C-3: Partial ester of diglycerol and oleic acid

[0106] C-4: partial ester of tetraglycerol and oleic acid

[0107] Polyolefin resin

[0108] P-1: Ethylene 1-hexene copolymer (C6-LLDPE, density: 0.930 g / cm 3 , MFR: 1.0g / 10min, ethylene content 96%)

[0109] P-2: Ethylene-1-butene copolymer (C4-LLDPE, density: 0.920 g / cm 3 , MFR: 2.1g / 10min, ethylene content 95%)

[0110] P-3: Polyethylene (LDPE, density: 0.927 g / cm 3 , MFR: 4.0g / 10min)

[0111] P-4: Ethylene-propylene copolymer (co-PP, density: 0.900 g / cm 3 , MFR: 8.0g / 10min, ethylene content 3.5%)

[0112] P-5: Ethylene vinyl acetate copolymer (EVA, density: 0.930 g / cm 3 , MFR: 1.5g / 10min, ethylene content 90%)

[0113] Example 1

[0114] Modifier (K-1) was obtained by uniformly mixing 70 parts of compound A-1, 30 parts of compound B-1, and 200 parts of partial ester of glycerol and oleic acid (C-1).

[0115] Examples 2 to 25, Comparative Examples 1 to 6

[0116] In the same manner as in the modifying agent (K-1) of Example 1, modifying agents (K-2 to K-25, k-1 to k-6) of Examples 2 to 25 and Comparative Examples 1 to 6 having the compositions shown in Table 3 were obtained.

[0117] Table 3

[0118]

[0119] Embodiment 26

[0120] 15 parts of the modifier (K-1) were supplied in the form of liquid injection into 85 parts of ethylene-1-hexene copolymer (P-1) melted at 220°C using a twin-screw extruder. The contents were then melt-kneaded. The resulting mixture was pelletized to obtain a masterbatch (M-1).

[0121] Examples 27 to 50, Comparative Examples 7 to 12

[0122] In the same manner as the master batch (M-1) of Example 26, master batches (M-2 to M-25, m-1 to m-6) of Examples 27 to 50 and Comparative Examples 7 to 12 having the compositions shown in Table 4 below were obtained.

[0123] 《Evaluation of Masterbatch》

[0124] The master batches of the examples and comparative examples were evaluated by the following test methods. The evaluation results are shown in Table 4.

[0125] Manufacturability

[0126] The manufacturability was evaluated according to the following criteria based on the production conditions of the masterbatch.

[0127] A: No demoulding or strand disturbance occurs.

[0128] B: The strands were disturbed during their travel, but no demolding occurred.

[0129] C: Strand turbulence and demolding occur.

[0130] Adhesion

[0131] The masterbatch stored at 40°C for 30 days is supplied to a cubic transparent container (length × width × height = 16.2 cm × 6.3 cm × 5.4 cm) arranged on a horizontal platform. The surface of the contents is made flat. With one end of the container in contact with the platform, the other end is lifted to tilt the container. The height h (cm) of the other end from the platform when the masterbatch starts to slide is measured. The angle of repose θ is calculated by the following formula.

[0132] Angle of repose θ = (180 / π) × sin -1 (16.2 / h)

[0133] The blocking property of the masterbatch was evaluated based on the repose angle θ according to the following criteria.

[0134] A: 55°≥θ

[0135] B: 65°≥θ>55°

[0136] C: θ>65°

[0137] Table 4

[0138]

[0139] Resin

[0140]

[0141] The masterbatches of Examples 26 to 50 have excellent manufacturability and at the same time, the blocking property is suppressed to a low level. On the other hand, the masterbatches of Comparative Examples 7 to 10 are inferior in either manufacturability or blocking property.

[0142] Embodiment 51

[0143] 3.3 parts of the masterbatch (M-1) and 96.7 parts of the ethylene-1-hexene copolymer (P-1) were mixed by a drum. Next, the mixture was melted at 190°C using an inflation molding machine. The molten mixture was extruded while being cooled at 20°C. In this way, a polyolefin resin film (SF-1) having a thickness of 40 μm was produced.

[0144] Examples 52 to 75, Comparative Examples 13 to 18

[0145] Polyolefin resin films (SF-2 to SF-25, sf-1 to sf-6) of Examples 52 to 75 and Comparative Examples 13 to 18 having the compositions and film thicknesses shown in Table 5 below were produced in the same manner as the polyolefin resin film (SF-1) of Example 51.

[0146] 《Evaluation of membrane》

[0147] The antifogging property and the productivity of the polyolefin resin film were evaluated by the following test methods. The evaluation results are shown in Table 5.

[0148] Anti-fog

[0149] The film was stored at 20°C for 24 hours or at 35°C for 30 days. Thereafter, the film was covered at the opening of a 100 ml beaker containing 60 ml of 20°C water. Next, the beaker was left to stand at 5°C for 1 hour. Thereafter, the adhesion of water droplets to the film was observed. The anti-fogging properties were evaluated according to the following criteria. It should be noted that when the film is a laminated film, the laminated film is covered at the opening of the beaker in such a way that the first layer becomes the inner side.

[0150] A: No water droplets attached, transparent.

[0151] B: There are large water droplets attached, but it is transparent.

[0152] C: A large number of tiny water droplets are attached, and it is not transparent.

[0153] Film Manufacture

[0154] The manufacturability was evaluated according to the following criteria depending on the film production conditions.

[0155] A: No extrusion fluctuation occurs, and the film thickness variation is less than ±5 μm relative to the set thickness.

[0156] B: Extrusion fluctuation slightly occurred, and the film thickness variation was less than ±8 μm relative to the set thickness.

[0157] C: Streaks or uneven film thickness due to extrusion fluctuations occurred.

[0158] Table 5

[0159]

[0160] Resin

[0161]

[0162] The polyolefin-based resin films of Examples 51 to 75 exhibited excellent antifogging properties and manufacturability. On the other hand, the polyolefin-based resin films of Comparative Examples 13 and 15 to 18 were inferior in at least one of antifogging properties and manufacturability.

[0163] Embodiment 76

[0164] 10 parts of the masterbatch (M-1) and 90 parts of the ethylene·1-hexene copolymer (P-1) were mixed with a roller. The obtained mixture was used as the molding material of the first layer (polyolefin resin film). As the molding materials for the second layer (intermediate layer) and the third layer, ethylene·1-hexene copolymer (P-1) was used. These molding materials were melted at 190°C using an inflation molding machine. The molten molding materials were co-extruded while being cooled at 20°C. In this way, a laminated film (MF-1) with a thickness of 55 μm was manufactured, including a first layer with a film thickness of 15 μm, a second layer with a film thickness of 30 μm, and a third layer with a film thickness of 10 μm.

[0165] Examples 77 to 100, Comparative Examples 19 to 24

[0166] In the same manner as the laminated film (MF-1) of Example 76, laminated films (MF-2 to MF-25, mf-1 to mf-6) of Examples 77 to 100 and Comparative Examples 19 to 24 having the compositions and film thicknesses shown in Table 6 were produced.

[0167]

[0168] The antifogging property and the manufacturability of the laminated films (MF-1 to MF-25, mf-1 to mf-6) were evaluated by the above-mentioned test methods. The evaluation results are shown in Table 7.

[0169] Table 7

[0170]

[0171] The laminated films of Examples 76 to 100 exhibited excellent antifogging properties and film productivity. On the other hand, the laminated films of Comparative Examples 19 and 21 to 24 were inferior in at least one of the antifogging properties and film productivity.

[0172] Embodiment 101

[0173] 1.5 parts of modifier (K-1) and 98.5 parts of ethylene·1-hexene copolymer (P-1) were mixed with a roller. The obtained mixture was used as the molding material of the first layer (polyolefin resin film). As the molding materials of the second layer (intermediate layer) and the third layer, ethylene·1-hexene copolymer (P-1) was used. These molding materials were melted at 190°C using an inflation molding machine. The molten molding materials were co-extruded while being cooled at 20°C. In this way, a laminated film (F-1) with a thickness of 55 μm was manufactured, including a first layer with a film thickness of 15 μm, a second layer with a film thickness of 30 μm, and a third layer with a film thickness of 10 μm.

[0174] Examples 102 to 125, Comparative Examples 25 to 30

[0175] In the same manner as the laminated film (F-1) of Example 101, laminated films (F-2 to F-25, f-1 to f-6) of Examples 102 to 125 and Comparative Examples 25 to 30 having the compositions and film thicknesses shown in Table 8 were produced.

[0176]

[0177] The antifogging property and the manufacturability of the laminated films (F-1 to F-25, f-1 to f-6) were evaluated by the above-mentioned test methods. The evaluation results are shown in Table 9.

[0178] Table 9

[0179]

[0180] The laminated films of Examples 101 to 125 showed excellent anti-fogging properties and film manufacturability. It was found that the modifier involved in this embodiment can achieve excellent anti-fogging properties and film manufacturability even without going through a masterbatch. On the other hand, the laminated films of Comparative Examples 25 and 27 to 30 had poor anti-fogging properties and poor film manufacturability.

[0181] The above detailed description is provided for the purpose of illustration and description. Many modifications and changes can be made in accordance with the above teachings. It is not intended to concretize or limit the subject matter described herein to the precise form disclosed. Although the subject matter has been described in language specific to structural features and / or method behaviors, it should be understood that the subject matter defined in the appended claims is not necessarily limited to the above-mentioned specific features or behaviors. On the contrary, the above-mentioned specific features and behaviors are disclosed as example forms of implementing the appended claims.

Claims

1. A modifier for a polyolefin resin, comprising a compound A represented by the following formula (1) and a compound B represented by the following formula (2), In formula (1), R 1 and R 3 is a hydrocarbon group having 5 to 21 carbon atoms, R 2 A residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule, In formula (2), R 4 is a hydrocarbon group having 5 to 21 carbon atoms, R 5 It is a residue obtained by removing all hydroxyl groups from a (poly)oxyalkylene glycol having 2 to 100 carbon atoms, wherein the (poly)oxyalkylene glycol having 2 to 100 carbon atoms has a (poly)oxyalkylene group composed of oxyalkylene units having 2 to 4 carbon atoms in its molecule.

2. The modifier for polyolefin resin according to claim 1, wherein R 1 , R 3 and R 4 It is a hydrocarbon group having 7 to 17 carbon atoms.

3. The modifier for polyolefin resin according to claim 1, wherein R 2 and R 5 It is a residue obtained by removing all hydroxyl groups from a polyoxyalkylene glycol having 4 to 50 carbon atoms, wherein the polyoxyalkylene glycol having 4 to 50 carbon atoms has a polyoxyalkylene group containing an oxyalkylene unit having 2 carbon atoms in its molecule.

4. The modifier for polyolefin resin according to claim 1, wherein When the total amount of the compound A and the compound B is 100 parts by mass, 20 to 80 parts by mass of the compound A and 20 to 80 parts by mass of the compound B are contained.

5. The modifier for polyolefin resin according to claim 1, wherein It further contains a nonionic surfactant C.

6. The modifier for polyolefin resin according to claim 5, wherein The nonionic surfactant C is a partial ester of a 3-6-valent polyol and an aliphatic carboxylic acid having 6-22 carbon atoms.

7. The modifier for polyolefin resin according to claim 5, wherein The nonionic surfactant C is contained in an amount of 20 to 400 parts by mass, based on 100 parts by mass of the total of the compound A and the compound B. 8 . A polyolefin resin composition comprising a polyolefin resin and the polyolefin resin modifier according to claim 1 . 9 . A polyolefin-based resin film comprising the polyolefin-based resin composition according to claim 8 .

10. A laminated film comprising two or more laminated layers, At least one outermost layer among the two or more layers comprises the polyolefin-based resin film according to claim 9 .

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