POLYOLEFIN RESIN MODIFIER, POLYOLEFIN RESIN COMPOSITION, MODIFIED POLYOLEFIN RESIN FILM, AND LAMINATED FILM

Abstract

Polyolefin resin modifiers are provided that contain a nonionic surfactant, an organic sulfonate salt, and an inorganic salt. The organic sulfonate salt can be at least one selected from the group consisting of alkylsulfonic acid alkali metal salts whose alkyl group has 6 to 22 carbon atoms, alkylarylsulfonic acid alkali metal salts whose alkyl group has 6 to 22 carbon atoms, and sulfonic aliphatic ester alkali metal salts whose alkyl group has 6 to 22 carbon atoms. The inorganic salt can be at least one selected from the group consisting of sodium sulfate, potassium sulfate, calcium sulfate, lithium sulfate, sodium chloride, potassium chloride, lithium chloride, magnesium chloride, and calcium chloride.

Claims

1. A polyolefin resin composition comprising: a polyolefin resin; and a polyolefin resin modifier, wherein the polyolefin resin modifier contains a nonionic surfactant, an organic sulfonate salt, and an inorganic salt, the organic sulfonate salt is at least one selected from the group consisting of alkylsulfonic acid alkali metal salts whose alkyl group has 6 to 22 carbon atoms, alkylarylsulfonic acid alkali metal salts whose alkyl group has 6 to 22 carbon atoms, and sulfonic aliphatic carboxylic acid ester alkali metal salts whose alkyl group has 6 to 22 carbon atoms, and the inorganic salt is at least one selected from the group consisting of sodium sulfate, potassium sulfate, calcium sulfate, lithium sulfate, sodium chloride, potassium chloride, lithium chloride, magnesium chloride, and calcium chloride.

2. The polyolefin resin composition according to claim 1, wherein the polyolefin resin and the polyolefin resin modifier are contained in the polyolefin resin composition in amounts of 99.9% to 95.0% by mass and 0.1% to 5.0% by mass, respectively, so that the sum of the amounts of the polyolefin resin and the polyolefin resin modifier is equal to 100% by mass.

3. The polyolefin resin composition according to claim 1, wherein the inorganic salt is sodium sulfate and/or sodium chloride.

4. The polyolefin resin composition according to claim 1, wherein the nonionic surfactant, the organic sulfonate salt, and the inorganic salt are contained in the polyolefin resin modifier at a mass ratio of (the nonionic surfactant+the organic sulfonate salt)/the inorganic salt=99.9995/0.0005 to 75/25.

5. The polyolefin resin composition according to claim 1, wherein the organic sulfonate salt is at least one selected from the group consisting of alkylsulfonic acid alkali metal salts whose alkyl group has 6 to 22 carbon atoms.

6. The polyolefin resin composition according to claim 1, wherein the nonionic surfactant is at least one selected from the group consisting of partial esters of a tri- to hexa-hydric polyol with an aliphatic carboxylic acid having 6 to 22 carbon atoms, alkyldiethanolamides whose acyl group has 6 to 22 carbon atoms, ester compounds represented by Chemical Formula 1, ester compounds represented by Chemical Formula 2, and ether compounds represented by Chemical Formula 3, ##STR00003## wherein R.sup.1 is a hydrocarbon group having 5 to 21 carbon atoms, and R.sup.2 is a residue of a (poly)oxyalkylene glycol from which all hydroxyl groups have been eliminated, the (poly)oxyalkylene glycol having 2 to 200 carbon atoms having a (poly)oxyalkylene group constituted of oxyalkylene units having 2 to 4 carbon atoms in its molecule; ##STR00004## wherein R.sup.3 and R.sup.5 are each a hydrocarbon group having 5 to 21 carbon atoms, and R.sup.4 is a residue of a (poly)oxyalkylene glycol from which all hydroxyl groups have been eliminated, the (poly)oxyalkylene glycol having 2 to 200 carbon atoms having a (poly)oxyalkylene group constituted of oxyalkylene units having 2 to 4 carbon atoms in is molecule; and
R.sup.6—O—R.sup.7—OH  Chemical Formula 3: wherein R.sup.6 is a hydrocarbon group having 6 to 22 carbon atoms, and R.sup.7 is a residue of a (poly)oxyalkylene glycol from which all hydroxyl groups have been eliminated, the (poly)oxyalkylene glycol having 2 to 200 carbon atoms having a (poly)oxyalkylene group constituted of oxyalkylene units having 2 to 4 carbon atoms in is molecule.

7. The polyolefin resin composition according to claim 6, wherein the nonionic surfactant is at least one selected from the group consisting of partial esters of a tri- to hexa-hydric polyol with an aliphatic carboxylic acid having 8 to 18 carbon atoms, ester compounds represented by Chemical Formula 1 in which R.sup.1 is a hydrocarbon group having 7 to 17 carbon atoms, ester compounds represented by Chemical Formula 2 in which R.sup.3 and R.sup.5 are each a hydrocarbon group having 7 to 17 carbon atoms, and ether compounds represented by Chemical Formula 3 in which R.sup.6 is a hydrocarbon group having 8 to 18 carbon atoms.

8. A modified polyolefin resin film, which is formed of the polyolefin resin composition according to claim 1.

9. A laminated film, which is a two- or more layer laminated film, wherein at least one surface layer of the laminated film is formed of the polyolefin resin composition according to claim 1.

Description

EXAMPLES

[0042] Hereinafter, in order to more embodying the constitution and advantageous effects of the present invention, examples and the like will be cited, but the present invention is not any more limited to these examples. Here, in the following examples and comparative examples, parts means parts by mass, and % means % by mass.

[0043] Test Section 1 (Preparation of Polyolefin Resin Modifiers)

Example 1

[0044] 68.18 parts of a partial ester (A-1) of diglycerol with lauric acid as a nonionic surfactant, 29.22 parts of a sodium alkylsulfonate (S-1) whose alkyl group has 13 to 18 carbon atoms as an organic sulfonate salt, and 2.60 parts of sodium sulfate as an inorganic salt were homogeneously mixed to thereby prepare a polyolefin resin modifier (F-1) of Example 1.

Examples 2 to 43, and Comparative Examples 1 to 6

[0045] Polyolefin resin modifiers (F-2) to (F-43) and (f-1) to (f-6) of Examples 2 to 43 and Comparative Examples 1 to 6, respectively, were prepared as in the polyolefin resin modifier (F-1) of Example 1. The details of the prepared polyolefin resin modifiers of those examples and comparative examples are shown in Table 1 collectively with the details of the polyolefin resin modifier (F-1) of Example 1.

TABLE-US-00001 TABLE 1 Nonionic Organic Surfactant Sulfonate Salt Inorganic Salt Content Content Content Item Kind Kind (%) Kind (%) Kind (%) *1 Example 1 F-1 A-1 68.18 S-1 29.22 sodium sulfate 2.60 97.4/2.6 2 F-2 A-2 66.53 S-2 33.27 sodium sulfate 0.20 99.8/0.2 3 F-3 A-3 47.75 S-2 47.75 sodium chloride 4.50 95.5/4.5 4 F-4 A-4 83.33 S-2 16.67 sodium chloride 0.0005 99.9995/0.000  5 F-5 C-1 39.96 S-2 59.94 sodium sulfate 0.10 5 6 F-6 C-2 80.83 S-2 16.17 sodium chloride 3.00 99.9/0.1 7 F-7 C-3 90.43 S-2 3.77 sodium sulfate 5.80 97/3 8 F-8 C-4 52.00 S-2 48.00 sodium sulfate 0.0020 94.2/5.8 9 F-9 D-1 74.99 S-2 25.00 sodium sulfate 0.0180 99.998/0.002 10 F-10 D-2 79.32 S-2 14.93 sodium chloride 5.75 99.982/0.018 11 F-11 E-1 70.68 S-3 5.32 sodium sulfate 24.0 94.2541/5.746  12 F-12 E-2 87.57 S-4 9.73 sodium chloride 2.70  76/24 13 F-13 A-1 64.53 S-5 32.27 sodium sulfate 3.20 97.3/2.7 14 F-14 A-2 70.30 S-6 24.70 sodium chloride 5.00 96.8/3.2 15 F-15 A-5 94.97 S-2 5.00 sodium sulfate 0.0300 95/5 16 F-16 A-6 69.30 S-2 20.70 sodium sulfate 10.00 99.97/0.03 17 F-17 B-1 51.20 S-2 28.80 sodium chloride 20.00  90/10 18 F-18 B-2 70.00 S-2 30.00 sodium sulfate 0.0010  80/20 19 F-19 C-1 49.14 S-6 28.86 sodium chloride 22.00 99.999/0.001 20 F-20 C-2 83.32 S-6 16.66 sodium sulfate 0.0150  78/22 21 F-21 D-3 76.28 S-6 21.52 sodium chloride 2.20 99.985/0.015 22 F-22 D-4 65.90 S-7 29.61 sodium sulfate 4.50 97.8/2.2 23 F-23 E-3 49.15 S-7 49.15 sodium sulfate 1.70 95.5/4.5 24 F-24 E-4 91.68 S-6 4.83 sodium sulfate 3.50 98.3/1.7 25 F-25 B-3 81.00 S-6 16.20 potassium chloride 2.80 96.5/3.5 26 F-26 B-4 68.00 S-6 17.00 potassium chloride 15.00 97.2/2.8 27 F-27 A-1 72.90 S-6 24.30 potassium chloride 2.80  85/15 28 F-28 A-2 71.48 S-8 23.83 potassium chloride 4.70 97.2/2.8 29 F-29 C-1 77.28 S-6 14.72 potassium chloride 8.00 95.3/4.7 30 F-30 C-2 58.67 S-6 29.33 potassium chloride 12.00 92/8 31 F-31 D-1 64.78 S-6 14.22 potassium chloride 21.00  88/12 32 F-32 D-2 56.67 S-6 28.33 magnesium 15.00  79/21 33 F-33 D-1 49.10 S-6 49.10 chloride 1.80  85/15 34 F-34 D-2 91.65 S-6 5.85 calcium chloride 2.50 98.2/1.8 35 F-35 B-1 66.67 S-8 13.33 potassium chloride 20.00 97.5/2.5 36 F-36 B-2 83.26 S-6 7.24 potassium chloride 9.50  80/20 37 F-37 C-5 40.00 S-6 40.00 potassium chloride 20.00 90.5/9.5 38 F-38 D-5 87.30 S-6 2.70 potassium chloride 10.00  80/20 39 F-39 E-5 76.40 S-6 19.10 potassium chloride 4.50  90/10 40 F-40 A-7 79.71 S-6 15.59 potassium chloride 4.70 95.5/4.5 41 F-41 A-8 59.05 S-8 33.75 potassium chloride 7.20 95.3/4.7 42 F-42 B-5 86.53 S-6 13.46 potassium chloride 0.0050 92.8/7.2 43 F-43 B-6 88.23 S-6 11.76 potassium chloride 0.0050 99.995/0.005 potassium chloride 99.995/0.005 Comparative 1 f-1 B-2 92.2 — 0 sodium chloride 7.8 92.2/7.8 Example 2 f-2 A-8 85.95 S-6 9.55 sodium oleate 4.5 95.5/4.5 3 f-3 A-2 62.5 S-6 37.5 — 0 100/0  4 f-4 A-2 75 S-6 25 — 0 100/0  5 f-5 — 0 S-2 98 sodium chloride 0 98/0 6 f-6 A-8 40 S-6 20 sodium oleate 40  60/40 In Table 1, *1 is a mass ratio of (nonionic surfactant + organic sulfonate salt)/inorganic salt, A-1 represents a partial ester of diglycerol with lauric acid, A-2 represents a partial ester of diglycerol with stearic acid, A-3 represents a partial ester of glycerol with oleic acid, A-4 represents a partial ester of sorbitan with lauric acid, A-5 represents a partial ester of tetraglycerol with hexanoic acid, A-6 represents a partial ester of diglycerol with docosanoic acid, A-7 represents a partial ester of glycerol with acetic acid, A-8 represents a partial ester of decaglycerol with lauric acid, B-1 represents lauryldiethanolamide, B-2 represents stearyldiethanolamide, B-3 represents oleyldiethanolamide, B-4 represents octyldiethanolamide, B-5 represents docosyldiethanolamide, B-6 represents lauryldiethanolamine, C-1 represents an adduct of 9 mol of ethylene oxide to lauric acid, C-2 represents an adduct of 7 mol of ethylene oxide to oleic acid, C-3 represents an adduct of 13 mol of propylene oxide to stearic acid, C-4 represents an adduct of 50 mol of ethylene oxide to octanoic acid, C-5 represents an adduct of 300 mol of ethylene oxide to lauric acid, D-1 represents an ester of an ethylene oxide adduct (addition molar number: 9) of lauric acid with lauric acid, D-2 represents an ester of an ethylene oxide adduct (addition molar number: 7) of oleic acid with oleic acid, D-3 represents an ester of a propylene oxide adduct (addition molar number: 13) of stearic acid with stearic acid, D-4 represents an ester of an ethylene oxide adduct (addition molar number: 50) of octanoic acid with octanoic acid, D-5 represents an ester of an ethylene oxide adduct (addition molar number: 300) of lauric acid with lauric acid, E-1 represents an adduct of 10 mol of polyethylene oxide to lauryl alcohol, E-2 represents an adduct of 6 mol of polyethylene oxide to oleyl alcohol, E-3 represents an adduct of 15 mol of polypropylene oxide to stearyl alcohol, E-4 represents an adduct of 60 mol of polyethylene oxide to octyl alcohol, E-5 represents a random EO adduct of 75 mol of polyethylene oxide/75 mol of polypropylene oxide to lauryl alcohol, S-1 represents a sodium alkylsulfonate whose alkyl group has 13 to 18 carbon atoms, S-2 represents sodium pentadecylsulfonate, S-3 represents sodium hexylsulfonate, S-4 represents sodium behenylsulfonate, S-5 represents a sodium alkylbenzenesulfonate whose alkyl group has 10 to 16 carbon atoms, S-6 represents sodium dedecylbenzenesulfonate, S-7 represents lithium dedecylbenzenesulfonate, and S-8 represents sodium dioctyl sulfosuccinate.

[0046] Test Section 2 (Production 1 of Laminated Films)

Example 44

[0047] 87 parts of an ethylene-(1-hexene) copolymer (density: 0.930 g/cm.sup.3, MRF: 1.0 g/10 min, ethylene copolymerization ratio: 96%) (R-1) as an olefin resin, 10 parts of the polyolefin resin modifier (F-1) prepared in Test Section 1, and 3 parts of a silica (average particle diameter: 3 μm, amorphous) as an anti-blocking agent were homogeneously mixed to thereby fabricate a master batch having a concentration of the modifier of the present invention of 10% and a concentration of the silica of 3%, and thereafter, 20 parts of the master batch and 80 parts of the above ethylene-(1-hexene) copolymer (R-1) were mixed with a tumbler blender. By using the obtained mixture for an outer layer (A layer) on one side, and the above ethylene-(1-hexene) copolymer (R-1) for a middle layer (B layer) and an outer layer (C layer) on the other side, these were coextruded under cooling at 30° C. by a T die method to thereby produce a 3-layer laminated film of 60 μm in thickness (the ratio of thicknesses of the layers was A layer/B layer/C layer=1/4/1).

Examples 45 to 86 and Comparative Examples 7 to 12

[0048] Laminated films of Examples 45 to 86 and Comparative Examples 7 to 12 were produced as in the production of the laminated film of Example 44. The details of the produced laminated films of those examples and comparative examples are shown in Table 2 collectively with the details of the laminated film of Example 44.

TABLE-US-00002 TABLE 2 Polyolefin Resin Polyolefin Kind of Kind of used for A Layer Resin Modifier Polyolefin Polyolefin Content Content Resin used Resin used Item Kind (parts) Kind (parts) for B Layer for C Layer Example 44 R-1 98.00 F-1 2.0 R-1 R-1 45 R-2 98.20 F-2 1.8 R-2 R-2 46 R-3 98.50 F-3 1.5 R-3 R-3 47 R-4 97.60 F-4 2.4 R-4 R-4 48 R-2 98.50 F-5 1.5 R-2 R-2 49 R-2 97.60 F-6 2.4 R-2 R-2 50 R-2 97.90 F-7 2.1 R-2 R-2 51 R-2 98.10 F-8 1.9 R-2 R-2 52 R-2 99.80 F-9 0.2 R-2 R-2 53 R-2 98.18 F-10 1.8 R-2 R-2 54 R-2 98.30 F-11 1.7 R-2 R-2 55 R-2 99.50 F-12 0.5 R-2 R-2 56 R-1 97.00 F-13 3.0 R-1 R-1 57 R-2 97.30 F-14 2.7 R-2 R-2 58 R-3 98.00 F-15 2.0 R-3 R-3 59 R-4 95.20 F-16 4.8 R-4 R-4 60 R-2 98.60 F-17 1.4 R-2 R-2 61 R-2 98.30 F-18 1.7 R-2 R-2 62 R-2 97.20 F-19 2.8 R-2 R-2 63 R-2 95.20 F-20 4.8 R-2 R-2 64 R-2 96.80 F-21 3.2 R-2 R-2 65 R-2 97.10 F-22 2.9 R-2 R-2 66 R-2 98.40 F-23 1.6 R-2 R-2 67 R-2 98.00 F-24 2.0 R-2 R-2 68 R-1 98.80 F-25 1.2 R-1 R-1 69 R-2 96.50 F-26 3.5 R-2 R-2 70 R-3 98.00 F-27 2.0 R-3 R-3 71 R-4 96.00 F-28 4.0 R-4 R-4 72 R-2 95.50 F-29 4.5 R-2 R-2 73 R-2 97.00 F-30 3.0 R-2 R-2 74 R-2 97.80 F-31 2.2 R-2 R-2 75 R-2 97.90 F-32 2.1 R-2 R-2 76 R-2 98.20 F-33 1.8 R-2 R-2 77 R-2 98.50 F-34 1.5 R-2 R-2 78 R-1 97.00 F-35 3.0 R-1 R-1 79 R-2 97.50 F-36 2.5 R-2 R-2 80 R-3 98.30 F-37 1.7 R-3 R-3 81 R-4 97.60 F-38 2.4 R-4 R-4 82 R-1 94.00 F-39 6.0 R-1 R-1 83 R-2 97.60 F-40 5.8 R-2 R-2 84 R-3 98.28 F-41 5.9 R-3 R-3 85 R-4 97.20 F-42 5.2 R-4 R-4 86 R-2 97.20 F-43 3.4 R-2 R-2 Comparative 7 R-1 99.30 f-1 0.7 R-1 R-1 Example 8 R-2 97.80 f-2 2.2 R-2 R-2 9 R-3 99.20 f-3 0.8 R-3 R-3 10 R-4 98.80 f-4 1.2 R-4 R-4 11 R-2 98.63 f-5 1.4 R-2 R-2 12 R-2 89.00 f-6 11 R-2 R-2 In Table 2, R-1 represents an ethylene-(1-hexene) copolymer (density: 0.930 g/cm.sup.3, MRF: 1.0 g/10 min, ethylene copolymerization ratio: 96%), R-2 represents an ethylene-(1-butene) copolymer (density: 0.920 g/cm.sup.3, MRF: 2.1 g/10 min, ethylene copolymerization ratio: 95%), R-3 represents an ethylene-propylene copolymer (density: 0.90 g/cm.sup.3, MRF: 7.0 g/10 min, ethylene copolymerization ratio: 4%), R-4 represents an ethylene-(1-butene) copolymer (density: 0.93 g/cm.sup.3, MRF: 4.0 g/10 min, ethylene copolymerization ratio: 95%), and F-1 to F-43 and f-1 to f-6 each represent the polyolefin resin modifier prepared in Test Section 1 and shown in Table 1

[0049] Test Section 3 (Evaluation 1 of the Laminated Films)

[0050] Evaluation of the Antifogging Properties

[0051] The laminated films produced in Test Section 2 were humidity conditioned under the condition of 20° C. and a relative humidity of 65% for 24 hours, and thereafter adhered on a beaker having water at 20° C. put therein so that the A layer directed inward and left in an atmosphere of 5° C. for 0.5 hours; then, the degree of deposition of water droplets on the A layer was observed and the antifogging properties were evaluated based on the following criteria. Further, for the laminated films humidity conditioned under the condition of 40° C. and a relative humidity of 50% for 4 weeks, the antifogging properties were similarly evaluated as stability with time. The evaluation results are collectively shown in Table 3.

[0052] Evaluation Criteria of the Antifogging Properties

[0053] ∘∘: exhibiting no deposition of water droplets and being transparent; being remarkably excellent in the antifogging properties

[0054] ∘: exhibiting deposition of large water droplets, but being transparent; being excellent in the antifogging properties

[0055] x: exhibiting deposition of a large number of small water droplets, and being opaque; being inferior in the antifogging properties

[0056] Evaluation of the Transparency

[0057] The laminated films produced in Test Section 2 were humidity conditioned under the condition of 20° C. and a relative humidity of 65% for 24 hours, and thereafter, the haze thereof was measured by using a haze meter (trade name: NDH-5000, manufactured by Nippon Denshoku Industries Co., Ltd.), and the transparency was evaluated based on the following criteria. The evaluation results are collectively shown in Table 3.

[0058] Evaluation Criteria of the Transparency

[0059] ∘∘: being lower than 10% (being excellent in the transparency)

[0060] ∘: being 10% or higher and lower than 15% (being good in the transparency)

[0061] x: being 15% or higher (being inferior in the transparency)

[0062] Evaluation of the Antistaticity

[0063] The laminated films produced in Test Section 2 were humidity conditioned under the condition of 20° C. and a relative humidity of 65% for 24 hours, and thereafter, the surface specific resistance (Ω/□) thereof was measured under the same condition by using a surface resistance meter (trade name: Super Megohmmeter SM-8220, manufactured by HIOKI E.E. CORPORATION), and the antistaticity was evaluated based on the following criteria. The results are collectively shown in Table 3. Further, for the laminated films stored for 4 weeks under the condition of 40° C. and a relative humidity of 50%, the antistaticity was similarly evaluated as stability with time. The evaluation results are collectively shown in Table 3.

[0064] Evaluation Criteria of the Antistaticity

[0065] ∘∘: the surface specific resistance was lower than 1×10.sup.12Ω/□

[0066] ∘: the surface specific resistance was 1×10.sup.12Ω/□ or higher and lower than 1×10.sup.13Ω/□

[0067] x: the surface specific resistance was 1×10.sup.13Ω/□ or higher

[0068] Evaluation of the Film-Forming Stability

[0069] When the laminated films were formed in Test Section 2, the film-forming stability of the films was visually observed, and evaluated based on the following criteria. The evaluation results are collectively shown in Table 3.

[0070] Evaluation Criteria of the Film-Forming Stability

[0071] ∘: the formed film exhibited no extrusion fluctuation, and the film having a stable film thickness was obtained.

[0072] x: the formed film exhibited extrusion fluctuation, and no film having a stable film thickness was obtained.

TABLE-US-00003 TABLE 3 Antifogging Properties Antistaticity Film After 0.5 Stability After 24 Stability Forming Item hours With Time Transparency hours With Time Stability Example 44 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 45 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 46 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 47 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 48 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 49 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 50 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 51 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 52 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 53 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 54 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 55 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 56 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 57 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 58 ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 59 ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 60 ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 61 ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 62 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 63 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 64 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 65 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 66 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 67 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 68 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 69 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 70 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 71 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 72 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 73 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 74 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 75 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 76 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 77 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 78 ∘ ∘ ∘∘ ∘ ∘ ∘ 79 ∘ ∘ ∘∘ ∘ ∘ ∘ 80 ∘ ∘ ∘∘ ∘ ∘ ∘ 81 ∘ ∘ ∘∘ ∘ ∘ ∘ 82 ∘ ∘ ∘ ∘ ∘ ∘ 83 ∘ ∘ ∘ ∘ ∘ ∘ 84 ∘ ∘ ∘ ∘ ∘ ∘ 85 ∘ ∘ ∘ ∘ ∘ ∘ 86 ∘ ∘ ∘ ∘ ∘ ∘ Comparative 7 x x ∘∘ x x ∘ Example 8 x ∘ ∘∘ ∘ x ∘ 9 x ∘ ∘∘ ∘ ∘ ∘ 10 x ∘ ∘∘ ∘ ∘ ∘ 11 x x x ∘ ∘ ∘ 12 ∘ x ∘ x x x

[0073] Test Section 4 (Production of Modified Polyolefin Resin Films)

Example 87

[0074] By using the polyolefin resin (R-1), the polyolefin resin modifier (F-1) prepared in Test Section 1, and the silica, a master batch having a concentration of the polyolefin resin modifier of 10% and a concentration of the silica of 3% was fabricated as in Test Section 2, and thereafter mixed with the polyolefin resin (R-1) with a tumbler blender. By using the obtained mixture, a modified polyolefin resin film (N-1) of 60 μm in thickness was produced by an inflation method.

Examples 88 to 129 and Comparative Examples 13 to 18

[0075] Modified polyolefin resin films (N-2) to (N-43) and (n-1) to (n-6) of Examples 88 to 129 and Comparative Examples 13 to 18, respectively, were produced as in the production of the modified polyolefin resin film (N-1) of Example 87. The details of the modified polyolefin resin films of those examples and comparative examples are shown in Table 4 collectively with the details of the modified polyolefin resin film of Example 87.

TABLE-US-00004 TABLE 4 Kind of Polyolefin Resin Modified Polyolefin Resin Modifier Polyolefin Content Content Item Resin Film Kind (%) Kind (%) Example 87 N-1 R-1 98.00 F-1 2.0 88 N-2 R-2 98.20 F-2 1.8 89 N-3 R-3 98.50 F-3 1.5 90 N-4 R-4 97.60 F-4 2.4 91 N-5 R-2 98.50 F-5 1.5 92 N-6 R-2 97.60 F-6 2.4 93 N-7 R-2 97.90 F-7 2.1 94 N-8 R-2 98.10 F-8 1.9 95 N-9 R-2 99.80 F-9 0.2 96 N-10 R-2 98.18 F-10 1.8 97 N-11 R-2 98.30 F-11 1.7 98 N-12 R-2 99.50 F-12 0.5 99 N-13 R-1 97.00 F-13 3.0 100 N-14 R-2 97.30 F-14 2.7 101 N-15 R-3 98.00 F-15 2.0 102 N-16 R-4 95.20 F-16 4.8 103 N-17 R-2 98.60 F-17 1.4 104 N-18 R-2 98.30 F-18 1.7 105 N-19 R-2 97.20 F-19 2.8 106 N-20 R-2 95.20 F-20 4.8 107 N-21 R-2 96.80 F-21 3.2 108 N-22 R-2 97.10 F-22 2.9 109 N-23 R-2 98.40 F-23 1.6 110 N-24 R-2 98.00 F-24 2.0 111 N-25 R-1 98.80 F-25 1.2 112 N-26 R-2 96.50 F-26 3.5 113 N-27 R-3 98.00 F-27 2.0 114 N-28 R-4 96.00 F-28 4.0 115 N-29 R-2 95.50 F-29 4.5 116 N-30 R-2 97.00 F-30 3.0 117 N-31 R-2 97.80 F-31 2.2 118 N-32 R-2 97.90 F-32 2.1 119 N-33 R-2 98.20 F-33 1.8 120 N-34 R-2 98.50 F-34 1.5 121 N-35 R-1 97.00 F-35 3.0 122 N-36 R-2 97.50 F-36 2.5 123 N-37 R-3 98.30 F-37 1.7 124 N-38 R-4 97.60 F-38 2.4 125 N-39 R-1 94.00 F-39 6.0 126 N-40 R-2 97.60 F-40 5.8 127 N-41 R-3 98.28 F-41 5.9 128 N-42 R-4 97.20 F-42 5.2 129 N-43 R-2 97.20 F-43 3.4 Comparative 13 n-1 R-1 99.30 f-1 0.7 Example 14 n-2 R-2 97.80 f-2 2.2 15 n-3 R-3 99.20 f-3 0.8 16 n-4 R-4 98.80 f-4 1.2 17 n-5 R-2 98.63 f-5 1.4 18 n-6 R-2 70.00 f-5 30

[0076] Test Section 5 (Evaluation of the Modified Polyolefin Resin Films)

[0077] For the modified polyolefin resin films produced in Test Section 4, evaluations of the antifogging properties, the transparency, the antistaticity, and the film formability were carried out as in Test Section 3. The evaluation results are collectively shown in Table 5.

TABLE-US-00005 TABLE 5 Kind of Antifogging Modified Properties Antistaticity Film Polyolefin After 0.5 Stability After 24 Stability Forming Item Resin Film hours With Time Transparency hours With Time Stability Example 87 N-1 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 88 N-2 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 89 N-3 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 90 N-4 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 91 N-5 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 92 N-6 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 93 N-7 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 94 N-8 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 95 N-9 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 96 N-10 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 97 N-11 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 98 N-12 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 99 N-13 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 100 N-14 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 101 N-15 ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 102 N-16 ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 103 N-17 ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 104 N-18 ∘ ∘∘ ∘∘ ∘∘ ∘∘ ∘ 105 N-19 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 106 N-20 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 107 N-21 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 108 N-22 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 109 N-23 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 110 N-24 ∘∘ ∘∘ ∘∘ ∘∘ ∘ ∘ 111 N-25 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 112 N-26 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 113 N-27 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 114 N-28 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 115 N-29 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 116 N-30 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 117 N-31 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 118 N-32 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 119 N-33 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 120 N-34 ∘ ∘∘ ∘∘ ∘ ∘ ∘ 121 N-35 ∘ ∘ ∘∘ ∘ ∘ ∘ 122 N-36 ∘ ∘ ∘∘ ∘ ∘ ∘ 123 N-37 ∘ ∘ ∘∘ ∘ ∘ ∘ 124 N-38 ∘ ∘ ∘∘ ∘ ∘ ∘ 125 N-39 ∘ ∘ ∘ ∘ ∘ ∘ 126 N-40 ∘ ∘ ∘ ∘ ∘ ∘ 127 N-41 ∘ ∘ ∘ ∘ ∘ ∘ 128 N-42 ∘ ∘ ∘ ∘ ∘ ∘ 129 N-43 ∘ ∘ ∘ ∘ ∘ ∘ Comparative 13 n-1 x x ∘∘ x x ∘ Example 14 n-2 x ∘ ∘∘ ∘ x ∘ 15 n-3 x ∘ ∘∘ ∘ ∘ ∘ 16 n-4 x ∘ ∘∘ ∘ ∘ ∘ 17 n-5 x x x ∘ ∘ ∘ 18 n-6 ∘ x ∘ x x x

[0078] Test Section 6 (Production 2 of Laminated Films)

Example 130

[0079] A polyurethane adhesive (an adhesive (T-1) prepared by diluting a mixture of aromatic ether adhesives of Takelac A-969V/Takenate A-5=3/1 (mass ratio) by trade names manufactured by Mitsui Chemicals Inc. with ethyl acetate so that the solids concentration was equal to 20%) was applied onto a base film (biaxially stretched polyamide film, thickness: 15 μm) (K-1) so that the coating weight was equal to 4 g/m.sup.2 (solids), and dried at 80° C. for 90 seconds; thereafter, the resultant was laminated with the modified polyolefin resin film (N-1) produced in Test Section 4 by a nip roll, and was left at 40° C. for 24 hours to cure the adhesive to thereby obtain a laminated film.

Examples 131 to 172 and Comparative Examples 19 to 24

[0080] Laminated films of Examples 131 to 172 and Comparative Examples 19 to 24 were produced as in the production of the laminated film of Example 130. The details of the laminated films produced in the above are shown in Table 6 collectively with the details of Example 130.

TABLE-US-00006 TABLE 6 Kind of Modified Polyolefin Kind of Kind of Item Resin Film Base Film Adhesive Example 130 N-1 K-1 T-1 131 N-2 K-1 T-2 132 N-3 K-1 T-3 133 N-4 K-1 T-4 134 N-5 K-1 T-5 135 N-6 K-1 T-6 136 N-7 K-2 T-3 137 N-8 K-3 T-5 138 N-9 K-2 T-1 139 N-10 K-2 T-1 140 N-11 K-2 T-1 141 N-12 K-2 T-1 142 N-13 K-1 T-1 143 N-14 K-1 T-2 144 N-15 K-1 T-3 145 N-16 K-1 T-4 146 N-17 K-1 T-5 147 N-18 K-1 T-6 148 N-19 K-2 T-3 149 N-20 K-3 T-5 150 N-21 K-2 T-1 151 N-22 K-2 T-1 152 N-23 K-2 T-1 153 N-24 K-2 T-1 154 N-25 K-1 T-1 155 N-26 K-1 T-2 156 N-27 K-1 T-3 157 N-28 K-1 T-4 158 N-29 K-1 T-5 159 N-30 K-1 T-6 160 N-31 K-2 T-3 161 N-32 K-3 T-5 162 N-33 K-2 T-1 163 N-34 K-2 T-1 164 N-35 K-2 T-1 165 N-36 K-2 T-1 166 N-37 K-2 T-1 167 N-38 K-2 T-1 168 N-39 K-2 T-1 169 N-40 K-2 T-1 170 N-41 K-2 T-1 171 N-42 K-2 T-1 172 N-43 K-2 T-1 Comparative 19 n-1 K-2 T-1 Example 20 n-2 K-2 T-1 21 n-3 K-2 T-1 22 n-4 K-2 T-1 23 n-5 K-2 T-1 24 n-6 K-2 T-1 In Table 6, K-1 represents Emblem ON (trade name), manufactured by Unitika Ltd., thickness: 15 μm, K-2 represents E5100 (trade name), manufactured by Toyobo Co., Ltd., thickness: 12 μm, K-3 represents Pylen Film-OT P2108 (trade name), manufactured by Toyobo Co., Ltd., thickness: 30 μm, T-1 represents a polyurethane adhesive (an adhesive prepared by diluting a mixture of aromatic ether adhesives of Takelac A-969V/Takenate A-5 = 3/1 (mass ratio) by trade names manufactured by Mitsui Chemicals Inc. with ethyl acetate so that the solids concentration was equal to 20%), T-2 represents a polyurethane adhesive (an adhesive prepared by diluting a mixture of aromatic ester adhesives of Takelac A-515/Takenate A-3 = 3/1 (mass ratio) by trade names manufactured by Mitsui Chemicals Inc. with ethyl acetate so that the solids concentration was equal to 20%), T-3 represents a polyurethane adhesive (an adhesive prepared by diluting a mixture of aliphatic ester adhesives of Takelac A-385/Takenate A-50 = 3/1 (mass ratio) by trade names manufactured by Mitsui Chemicals Inc. with ethyl acetate so that the solids concentration was equal to 20%), T-4 represents a polyurethane adhesive (an adhesive prepared by diluting a mixture of aromatic ether adhesives of Takelac A-242B/Takenate A-242A = 3/1 (mass ratio) by trade names manufactured by Mitsui Chemicals Inc. with an ion-exchange water so that the solids concentration was equal to 20%), T-5 represents a polyurethane adhesive (an adhesive prepared by diluting a mixture of aliphatic ester adhesives of Takelac A-695/Takenate A-95 = 3/1 (mass ratio) by trade names manufactured by Mitsui Chemicals Inc. with an ion-exchange water so that the solids concentration was equal to 20%), and T-6 represents a polyurethane adhesive (an adhesive prepared by diluting an aromatic ether adhesive of Takelac A-260 by trade name manufactured by Mitsui Chemicals Inc. with an ion-exchange water so that the solids concentration was equal to 20%).

[0081] Test Section 7 (Evaluation 2 of the Laminated Films)

[0082] For the laminated films produced in Test Section 6, evaluations of the antifogging properties, the transparency, and the antistaticity were carried out as in Test Section 3. The evaluation results are collectively shown in Table 7.

TABLE-US-00007 TABLE 7 Antifogging Properties Antistaticity After Stability After Stability 0.5 With 24 With Item hours Time Transparency hours Time Example 130 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 131 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 132 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 133 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 134 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 135 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 136 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 137 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 138 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 139 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 140 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 141 ∘∘ ∘∘ ∘∘ ∘∘ ∘∘ 142 ∘∘ ∘∘ ∘∘ ∘∘ ∘ 143 ∘∘ ∘∘ ∘∘ ∘∘ ∘ 144 ∘ ∘∘ ∘∘ ∘∘ ∘∘ 145 ∘ ∘∘ ∘∘ ∘∘ ∘∘ 146 ∘ ∘∘ ∘∘ ∘∘ ∘∘ 147 ∘ ∘∘ ∘∘ ∘∘ ∘∘ 148 ∘∘ ∘∘ ∘∘ ∘∘ ∘ 149 ∘∘ ∘∘ ∘∘ ∘∘ ∘ 150 ∘∘ ∘∘ ∘∘ ∘∘ ∘ 151 ∘∘ ∘∘ ∘∘ ∘∘ ∘ 152 ∘∘ ∘∘ ∘∘ ∘∘ ∘ 153 ∘∘ ∘∘ ∘∘ ∘∘ ∘ 154 ∘ ∘∘ ∘∘ ∘ ∘ 155 ∘ ∘∘ ∘∘ ∘ ∘ 156 ∘ ∘∘ ∘∘ ∘ ∘ 157 ∘ ∘∘ ∘∘ ∘ ∘ 158 ∘ ∘∘ ∘∘ ∘ ∘ 159 ∘ ∘∘ ∘∘ ∘ ∘ 160 ∘ ∘∘ ∘∘ ∘ ∘ 161 ∘ ∘∘ ∘∘ ∘ ∘ 162 ∘ ∘∘ ∘∘ ∘ ∘ 163 ∘ ∘∘ ∘∘ ∘ ∘ 164 ∘ ∘ ∘∘ ∘ ∘ 165 ∘ ∘ ∘∘ ∘ ∘ 166 ∘ ∘ ∘∘ ∘ ∘ 167 ∘ ∘ ∘∘ ∘ ∘ 168 ∘ ∘ ∘ ∘ ∘ 169 ∘ ∘ ∘ ∘ ∘ 170 ∘ ∘ ∘ ∘ ∘ 171 ∘ ∘ ∘ ∘ ∘ 172 ∘ ∘ ∘ ∘ ∘ Comparative 19 x x ∘∘ x x Example 20 x ∘ ∘∘ ∘ x 21 x ∘ ∘∘ ∘ ∘ 22 x ∘ ∘∘ ∘ ∘ 23 x x x ∘ ∘ 24 ∘ x ∘ x x

[0083] As is clear from the evaluation results of the examples against the comparative examples in Tables 3, 5, and 7 corresponding to Tables 1, 2, 4, and 6, according to the present invention, the excellent antistaticity and antifogging properties having persistency can be imparted to a polyolefin resin, and moreover, such antistaticity and antifogging properties can be developed in a short time, without adversely affecting transparency and film formability intrinsic to the polyolefin resin.