KR20180030233A - Composition for thermoplastic polymer film coating, process for producing composition for coating thermoplastic polymer film, process for producing modified thermoplastic polymer film and modified thermoplastic polymer film - Google Patents

Abstract

It is possible to reduce the deterioration of property performance due to friction at the time of film formation and electric field, to exhibit excellent relics from the beginning of electric field, to maintain good relics over a long period even after electric field, There is provided a thermoplastic polymer film coated surface composition, a process for producing a modified thermoplastic polymer film using such a composition, and a modified thermoplastic polymer film obtained by this process. As a composition for coating a thermoplastic polymer film, a specific modified inorganic cationic colloidal sol obtained by hydrolyzing a specific inorganic cationic colloidal sol with a specific silanol-forming organosilane compound includes a polyether-modified silicone, a specific polyoxyalkylene derivative, And a polyalkylene glycol having a number-average molecular weight of 1,500 to 50,000 at a specific ratio.

Description

Composition for thermoplastic polymer film coating, process for producing composition for coating thermoplastic polymer film, process for producing modified thermoplastic polymer film and modified thermoplastic polymer film

The present invention relates to a method for producing a fermented soybean curd, which has less deterioration in the performance of oil due to friction at the time of film formation at a factory or at the time of electric field to an agricultural house, exhibits excellent legibility from the beginning of the electric field, A thermoplastic polymer film coated surface composition having very little film surface tackiness, a process for producing such a composition, a modified thermoplastic polymer film using such a composition, and a process for producing such a modified thermoplastic polymer film.

Conventionally, as a composition for coating a thermoplastic polymer film, there has been known a method of using alumina sol, an acidic silica sol, an organosilane derivative and a nonionic surfactant (see, for example, Patent Document 1), colloidal alumina, colloidal silica and polyethylene glycol (See, for example, Patent Document 2) have been proposed. However, these conventional thermoplastic polymer film coated surface compositions have problems such as deterioration of the performance of the film (flow-through performance) due to film formation at the factory or friction at the time of electric field to the agricultural house, and stickiness of the coated surface of the film have.

Patent Document 1: JP-A-62-241984 Patent Document 2: JP-A-2000-160146

The problem to be solved by the present invention is to reduce the deterioration of property performance caused by friction at the time of film formation or expansion, to exhibit excellent relics from the beginning of the battle, to maintain excellent relics over a long period even after the battle, A method for producing such a composition, a modified thermoplastic polymer film using such a composition, and a process for producing such a modified thermoplastic polymer film .

DISCLOSURE OF THE INVENTION The present inventors have conducted studies to solve the above problems and found that a modified inorganic cationic colloid sol modified with a specific condensation polymer of a silanol compound as a specific inorganic cationic colloid sol can be modified with a polyether- Derivatives and polyalkylene glycols having a number average molecular weight of 1,500 to 50,000 in a specific ratio are certainly suitable.

That is, the present invention relates to a process for producing a modified cationic cationic colloid sol comprising the steps of: mixing 10 parts by mass to 50 parts by mass of a polyether-modified silicone with 100 parts by mass of a modified inorganic cationic colloid sol in terms of solid content, 2 to 30 parts by mass of a polyoxyalkylene derivative And a polyalkylene glycol having a number average molecular weight of 1,500 to 50,000 at a ratio of 45 parts by mass to 75 parts by mass. The present invention also relates to a composition for coating a thermoplastic polymer film. The present invention also relates to a process for producing such a composition, a modified thermoplastic polymer film using such a composition, and a process for producing such a modified thermoplastic polymer film.

Modified inorganic cationic colloidal sol: The condensation polymer of the following silanol compound in the solid particle of the following inorganic cationic colloidal sol is a solid content of inorganic cationic colloidal sol / condensation polymer of silanol compound = 100/5 (mass ratio) to 100 / 15 (by mass ratio).

Inorganic cationic colloidal sol: 20% by mass to 90% by mass of a cationic alumina sol in terms of solid content, and 10% by mass to 80% by mass (in total of 100% by mass in terms of solid content) ≪ / RTI >

Silanol compound: a product obtained by hydrolyzing at least one silanol-forming organosilane compound selected from trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes.

Polyoxyalkylene derivative: a compound in which ethylene oxide is added in a proportion of 3 to 100 moles per one mole of the following starting compound, 3 to 100 moles of ethylene oxide and propylene oxide per mole of the following starting compound, At least one compound selected from a compound added in a form of a block in a total amount of 3 to 100 moles of ethylene oxide and propylene oxide per 1 mole of the following starting compound.

Starting compounds: aliphatic alcohols having 8 to 22 carbon atoms, fatty acids having 8 to 22 carbon atoms, alkylphenols having 8 to 22 carbon atoms in the alkyl group or monoalkylamines having 8 to 22 carbon atoms in the alkyl group.

First, a composition for coating a thermoplastic polymer film (hereinafter referred to as a composition of the present invention) according to the present invention will be described. The composition of the present invention comprises 10 parts by mass to 50 parts by mass of the polyether-modified silicone, 2 parts by mass to 30 parts by mass of the polyoxyalkylene derivative and 100 parts by mass of the polyoxyalkylene derivative per 100 parts by mass of the modified inorganic cationic colloid sol, And polyalkylene glycol having a number average molecular weight of 1,500 to 50,000 at a ratio of 45 to 75 parts by mass, but it is preferable that 20 parts by mass of polyether-modified silicone is added to 100 parts by mass of the modified inorganic cationic colloid sol in terms of solid matter To 40 parts by mass of the polyoxyalkylene derivative, 5 parts by mass to 20 parts by mass of the polyoxyalkylene derivative, and 50 parts by mass to 70 parts by mass of the polyalkylene glycol.

The modified inorganic cationic colloidal sol provided in the composition of the present invention is a modified inorganic cationic colloidal sol having a specific inorganic cationic colloidal sol and a condensed polymer of a specific silanol compound in the solid particle of the specific inorganic cationic colloidal sol is a solid component of an inorganic cationic colloidal sol / 5 (mass ratio) to 100/15 (mass ratio).

The inorganic cationic colloidal sol to be used as a raw material of the modified inorganic cationic colloidal sol is a mixture of 20% by mass to 90% by mass of the cationic alumina sol in terms of solid content and 10% by mass to 80% by mass of the cationic silica sol in terms of solid content By mass, in terms of solids content) of the cationic alumina sol in a solid content of 50% by mass to 80% by mass and the cationic silica sol in terms of solid content of 20% by mass to 50% By mass to 100% by mass in total).

The cationic alumina sol is so-called colloidal alumina, and the commercially available water dispersion can be used as it is. Examples of such commercial products include alumina sol 100, alumina sol 200 and alumina sol 520 (all trade names of Nissan Kagaku Co., Ltd.), cataract AS-1 and cataract AS-2 (all available from Nikkiso Co., Product name of a priest).

As the cationic silacazole sol water dispersion, those commercially available can be used as they are. Examples of such commercial products include Snowtex AK and Snowtex AK-L (all trade names of Nissan Kagaku Co., Ltd.), cataract (trade name of Nippon Shokubai Ikasei Co., Ltd.), Quartron PL-3-C Manufactured by Sokakagaku Kogyo Co., Ltd.) and the like.

The condensation polymer of the silanol compound attached to the surface of the solid particle (colloidal particle of alumina or silica) of the inorganic cationic colloid sol is obtained by hydrolyzing the silanol-forming organosilane compound and condensing the resulting silanol compound by condensation polymerization . Specifically, as described later, the silanol-forming organosilane compound is hydrolyzed in the presence of the inorganic cationic colloid sol, and then the resulting silanol compound is subjected to condensation polymerization to form a silanol- A modified inorganic cationic colloidal sol to which a condensation polymer of a novolak compound is adhered can be obtained.

The modified inorganic cationic colloidal sol provided in the composition of the present invention is attached in the form such that the condensation polymer of the silanol compound covers all or a part of the surface of the solid particle of the inorganic cationic colloidal sol, It is believed to be chemically bonded to the solid particles of the cationic colloidal sol. The modified cationic cationic colloidal sol may be prepared by dissolving the condensation polymer of the silanol compound in the solid particles of the inorganic cationic colloidal sol in such a ratio that the solid content of the inorganic cationic colloidal sol / condensation polymer of the silanol compound = 100/5 (by mass) to 100/15 (Mass ratio) to 100/12 (mass ratio) of the solid content of the inorganic cationic colloidal sol / condensed polymer of the silanol compound is preferably in the range of 100/7 (mass ratio) to 100/12 (mass ratio).

As the polyether-modified silicone provided in the composition of the present invention, those commercially available can be used as they are. Examples of such commercially available products include TSF4440, TSF4441, TSF4445, TSF4446, TSF4452 and TSF4460 (all trade names of Momentive Performance Products Japan), X22-4952, X22-4272, KF-6123, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF- (All products of Shin-Etsu Silicone Co., Ltd.), SH8700, SH8410, SH8400, L-7002, FZ-2104, FZ-77, L-7604, FZ-2203 and FZ- Among these, HLB is preferably 4 to 16, such as TSF4440, KF-354L, KF-945, SH8400, KF-6004 and the like.

The polyoxyalkylene derivative provided in the composition of the present invention is a compound obtained by adding ethylene oxide to the following starting compound and / or a compound obtained by adding ethylene oxide and propylene oxide, In one case, any of a block-shaped portion or a random-shaped portion may be used. The addition mole number may be in the range of 3 to 100 moles in total of ethylene oxide or ethylene oxide and propylene oxide per mole of the following starting compound, but it is preferably in the range of 5 to 50 moles Do.

Starting compounds: aliphatic alcohols having 8 to 22 carbon atoms, fatty acids having 8 to 22 carbon atoms, alkylphenols having 8 to 22 carbon atoms in the alkyl group, or monoalkylamines having 8 to 22 carbon atoms in the alkyl group.

Examples of the aliphatic alcohol having 8 to 22 carbon atoms as the starting compound include capryl alcohol, 2-ethylhexyl alcohol, pelargon alcohol, caprin alcohol, undecyl alcohol, secondary alcohol having 9 to 11 carbon atoms, lauryl alcohol, Decyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, ricillail alcohol, behenyl alcohol and the like. Examples of fatty acids having 8 to 22 carbon atoms include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linolic acid, eicosanoic acid, And the like. Examples of the alkylphenol having 8 to 22 carbon atoms in the alkyl group include octylpethol, nonylphenol, decylphenol, dodecylphenol, octadecylphenol and the like. Examples of the monoalkylamines having 8 to 22 carbon atoms in the alkyl group include caprylamines, nonylamines, decylamines, laurylamines, tridecylamines, myristylamines, stearylamines, oleylamines, . Among them, aliphatic alcohols having 8 to 22 carbon atoms and fatty acids having 8 to 22 carbon atoms are preferred as starting compounds.

Specifically, as the ethylene oxide adduct of an aliphatic alcohol having 8 to 22 carbon atoms, capryl alcohol ethylene oxide 5 mole adduct, 2-ethylhexyl alcohol ethylene oxide 100 mole adduct, nonyl alcohol ethylene oxide 5 mole adduct , Undecyl alcohol ethylene oxide 30 mole adduct, secondary alcohol ethylene oxide 9 mole adduct having 9 to 12 carbon atoms, lauryl alcohol ethylene oxide 10 mole adduct, palmityl alcohol ethylene oxide 50 mole adduct, Stearyl alcohol ethylene oxide 20 mole adduct, isostearyl alcohol ethylene oxide 20 mole adduct, oleyl alcohol ethylene oxide 14 mole adduct, behenyl alcohol ethylene oxide 24 mole adduct, and the like. Examples of adducts of fatty alcohol having 8 to 22 carbon atoms in which ethylene oxide and propylene oxide are used in combination are capryl alcohol ethylene oxide 10 mol propylene oxide 10 mol random adduct, 2-ethylhexyl alcohol propylene oxide 30 mol ethylene Oxide 30 mol adduct, decyl alcohol ethylene oxide 30 mol propylene oxide 20 mol random adduct, dodecyl alcohol ethylene oxide 9 mol propylene oxide 9 mol random adduct, tridecyl alcohol ethylene oxide 10 mol propylene oxide 10 Molar random adduct, myristyl alcohol propylene oxide 13 mole ethylene oxide 10 mole block adduct, tetradecyl alcohol propylene oxide 13 mole ethylene oxide 11 mole block adduct, pentadecyl alcohol propylene oxide 13 mole ethylene oxide 10-mol block adducts and the like.

Specific examples of the ethylene oxide adduct of fatty acids having 8 to 22 carbon atoms include adduct of caprylic acid ethylene oxide 10 mole, adduct of 12 mole of lauric acid ethylene oxide, adduct of 5 mole of palmitic acid ethylene oxide, Ethylene oxide 13-moles adduct, and oleic acid ethylene oxide 13-moles adduct. Examples of adducts of ethylene oxide and propylene oxide of fatty acids having 8 to 22 carbon atoms include caprylic acid ethylene oxide 10 mol propylene Propylene oxide 10 mol random adduct, lauric acid alcohol ethylene oxide 10 mol propylene oxide 10 mol random adduct, propylene oxide myristic adduct, caprylic acid 10 mol random adduct, caprinic acid alcohol ethylene oxide 40 mol propylene oxide 10 mol random adduct, lauric acid alcohol ethylene oxide 10 mol propylene oxide 10 mol random adduct, 13 mol ethylene oxide 10 mol block adduct, 13 mol of propylene oxide of pentadecanoic acid 10 mol of ethylene oxide block adduct, 24 mol of propylene oxide oleate, 24 mol of ethylene oxide, , Ethylene oxide behenate 10 propylene oxide 10 mol random adduct, and the like.

Specific examples of the ethylene oxide adduct of an alkylphenol having 8 to 22 carbon atoms in the alkyl group include octylphenol ethylene oxide 3 mole adduct, nonylphenol ethyleneoxide 10 mole adduct, decylphenol ethyleneoxide 12 mole adduct And dodecylphenol ethylene oxide 100 mole adduct. Examples of adducts of ethylene oxide and propylene oxide of alkylphenol having 8 to 22 carbon atoms in the alkyl group include octylphenol ethylene oxide 50 mole propylene oxide SEED 10 mol Random adduct, nonyl phenol propylene oxide 10 mol ethylene oxide 35 mol random adduct, decyl phenol propylene oxide 3 mol ethylene oxide 10 mol block block adduct, octadecyl phenol propylene oxide 10 mol ethylene oxide A seed 80 mole random adduct, and the like.

More specifically, examples of the ethylene oxide adduct of monoalkylamine having 8 to 22 carbon atoms in the alkyl group include caprylamine ethylene oxide 4 mole adduct, laurylamine ethylene oxide 10 mole adduct, myristylamine ethyleneoxide 20 mole adduct, stearylamine ethylene oxide 45 mole adduct, and the adducts of ethylene oxide and propylene oxide of a monoalkylamine having 8 to 22 carbon atoms in the alkyl group include caprylamine ethyleneoxide Seed 20 mol Propylene oxide 10 mol Random adduct, lauryl amine Ethylene oxide 10 mol Propylene oxide 10 mol Random adduct, palmityl amine Propylene oxide 10 mol Ethylene oxide 20 mol Block adduct, stearyl amine Propylene Oxide 20 mole ethylene oxide 60 mole adduct block, behenyl amine ethylene oxide 20 mole propylene oxide 5 mole block adduct, and the like.

Of these, polyoxyalkylene derivatives include ethylene oxide adducts of aliphatic alkoxides having 8 to 22 carbon atoms, adducts of ethylene oxide and propylene oxide of aliphatic alkoxycarbon having 8 to 22 carbon atoms, ethylene of a fatty acid having 8 to 22 carbon atoms Oxide adducts and adducts of ethylene oxide and propylene oxide of a fatty acid having 8 to 22 carbon atoms and further containing ethylene oxide or ethylene oxide and propylene oxide in a total amount of 5 to 50 moles By weight. Specific examples of such preferred polyoxyalkylene derivatives include ethylene oxide 10-mole adduct of decyl alcohol, 10-moles adduct of lauryl alcohol ethylene oxide, adduct of ethylene oxide 9-mole adduct of secondary alcohol of 9 to 12 carbon atoms, Stearyl alcohol ethylene oxide 20 mole adduct, oleyl alcohol ethylene oxide 14 mole adduct, dodecyl alcohol ethylene oxide 10 mole propylene oxide 10 mole random adduct, ethylene oxide of tridecyl alcohol 10 mole propylene oxide A seed 10 mole random adduct, 13 mole of propylene oxide of tetradecyl alcohol, 11 mole adduct of ethylene oxide, 12 mole adduct of ethylene oxide of lauric acid, 13 mole adduct of ethylene oxide of stearic acid, ethylene oxide of oleic acid Propylene oxide 9 mole random adduct of stearic acid, propylene oxide 24 mole of oleic acid, and ethylene oxide 24 mole olefin adduct of stearic acid.

Examples of the polyalkylene glycol having a number average molecular weight of 1,500 to 50,000 provided in the composition of the present invention include polyethyleneglycol having a number average molecular weight of 1,500 to 50,000, polypropylene glycol, ethylene oxide-propylene oxide random polymerized polymer, Propylene oxide block polymer, and the like. Among them, polyethylene glycol, propylene glycol, ethylene oxide-propylene oxide random polymerized polymer having a number average molecular weight of 3,000 to 40,000, ethylene oxide-propylene oxide Block polymerized polymers are preferable, and polyethylene glycol having a number average molecular weight of 6,000 to 30,000 is more preferable. The number average molecular weight can be calculated from the hydroxyl value, and the hydroxyl value can be obtained by the method described in JIS K0070.

Next, a method for producing a composition for coating a thermoplastic polymer film according to the present invention (hereinafter referred to as a method for producing a composition of the present invention) will be described. The method for producing the composition of the present invention is a manufacturing method comprising the following first and second steps.

Step 1: Hydrolysis of the following silanol-forming organosilane compound in an amount ranging from 5 parts by mass to 15 parts by mass per 100 parts by mass of the solid content of the inorganic cationic colloid sol in the presence of the following inorganic cationic colloid sol And condensation polymerization of the resulting silanol compound to obtain a modified inorganic cationic colloidal sol.

Inorganic cationic colloidal sol: 20% by mass to 90% by mass of a cationic alumina sol in terms of solid content, and 10% by mass to 80% by mass (in total of 100% by mass in terms of solid content) ≪ / RTI >

Silanol-forming organosilane compounds: at least one selected from the group consisting of trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes.

Second Step: The modified inorganic cationic colloid sol obtained in the first step is added in an amount of 10 parts by mass to 50 parts by mass of polyether-modified silicone per 100 parts by mass in terms of solid content, 2 parts by mass of the following polyoxyalkylene derivative To 30 parts by mass and a polyalkylene glycol having a number average molecular weight of 1,500 to 50,000 at a ratio of 45 parts by mass to 75 parts by mass to obtain a composition for coating a thermoplastic polymer film.

Polyoxyalkylene derivative: a compound in which ethylene oxide is added in an amount of 3 to 100 moles per one mole of the following starting compound, 3 to 100 moles of ethylene oxide and propylene oxide per mole of the following starting compound At least one compound selected from a compound added in random form and a compound in which a total of 3 to 100 mol of ethylene oxide and propylene oxide are added in block form per 1 mol of the following starting compound.

Starting compounds: aliphatic alcohols having 8 to 22 carbon atoms, fatty acids having 8 to 22 carbon atoms, alkylphenols having 8 to 22 carbon atoms in the alkyl group, or monoalkylamines having 8 to 22 carbon atoms in the alkyl group.

In the method for producing the composition of the present invention, the inorganic cationic colloid sol used in the first step is as described above. Examples of the silanol-forming organosilane compound used in the first step include 1) methyltrimethoxysilane, methyltriethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane ,? -chloropropyltripropoxysilane,? -mercaptopropyltriethoxysilane,? -glycidoxypropyltrimethoxysilane,? -methacryloxypropyltriethoxysilane,? -ureidopropyltrimethoxysilane , Trialkoxysilanes such as phenyltrimethoxysilane, 2) dialkoxysilanes such as dimethyldimethoxysilane,? -Chloropropylmethyldimethoxysilane and? -Glycidoxypropylmethyldimethoxysilane, 3) trimethylchlorosilane such as trimethylchloro And monoalkoxysilanes such as silane and trimethylmethoxysilane. Of these, γ-glycidoxypropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane and the like are preferable.

In the method for producing the composition of the present invention, the mass ratio of the solid component of the inorganic cationic colloidal sol to the silanol-forming organosilane compound used in the first step is preferably from 1: And the polyether-modified silicone, polyoxyalkylene derivative and polyalkylene glycol used in the second step are as described above including their ratios.

Next, the modified thermoplastic polymer film (hereinafter referred to as the film of the present invention) according to the present invention will be described. In the film of the present invention, the above-described composition of the present invention is adhered to the corona discharge treated surface of the thermoplastic polymer film in a solid content of 0.1 g / m 2 to 2.0 g / m 2.

Examples of the thermoplastic polymer film include: 1) a polyolefin resin; 2) a chlorinated resin such as polyvinyl chloride, a vinyl chloride-methyl methacrylate copolymer, and polyvinylidene chloride; 3) a polyester resin such as polyethylene terephthalate or polyethylene terephthalate And general thermoplastic resins used for agricultural films such as resins. Examples of the polyolefin-based resin include a homopolymer of an? -Olefin and a copolymer of a? -Olefin with a different monomer, and examples thereof include polyethylene, polypropylene, ethylene-butene copolymer, ethylene- Ethylene-α-olefin copolymers such as 1-pentene copolymer and ethylene-hexene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate copolymer, Ionomer-resin, and the like. These resins may contain an antioxidant, a lubricant, an ultraviolet absorber, an infrared absorber, a lubricant, an anti-blocking agent, a repellent agent, a warming agent, a pigment, and the like, which are conventionally used. The method of molding these resins into a film is not particularly limited, and examples thereof include an inflation molding method and a T-die molding method. The resin used in the molding may blend a plurality of kinds of resins. The film may be a single layer, a multilayer, or a film formed by combining according to the purpose.

The use of the film of the present invention is not particularly limited, but a remarkable effect is exhibited when it is used in an agricultural coating film.

Finally, a method for producing a modified thermoplastic polymer film according to the present invention (hereinafter referred to as a method for producing a film of the present invention) will be described. The method for producing a film of the present invention is a manufacturing method comprising the following first and second steps.

Step 1: A step of subjecting the thermoplastic polymer film to corona discharge treatment so that the wet tension on the corona discharge treated surface is 35 mN / m or more.

Step 2: The step of coating the thermoplastic polymer film obtained in the first step on the corona discharge treated surface so that the composition of the present invention as solid content is from 0.1 g / m 2 to 2.0 g / m 2.

In the method for producing a film of the present invention, the thermoplastic polymer film is as described above. The first step is a step of subjecting the thermoplastic polymer film to a corona discharge treatment to make the wet tension of the corona discharge treated surface 35 mN / m or more. However, it is easily effected to set the wet tension within the range of 35 mN / m to 70 mN / m . In the present invention, the wet tensile strength is a value measured according to the description of JIS-K6768.

The second step is a step of applying the composition of the present invention described above to the corona discharge treated surface of the thermoplastic polymer film obtained in the first step so as to have a solid content of 0.1 g / m 2 to 2.0 g / m 2. When the composition of the present invention is applied to a thermoplastic polymer film, known coating methods can be used. These include, for example, a spray coat method, an immersion coat method, a roll coat method, a doctor blade coat method, a wire bar coat method, and an air knife coat method.

As described above, according to the present invention described above, the deterioration of the performance of relics due to friction during film formation or electric field is small, the excellent relics are exhibited from the beginning of the battle, the excellent relics are maintained for a long period even after the battle, An effect of extremely low tackiness is realized on the coated film surface.

Hereinafter, embodiments will be described in order to more specifically describe the structure and effects of the present invention, but the present invention is not limited to these embodiments. Further, in the following Examples and Comparative Examples, parts means parts by mass, and% means% by mass.

Test Category 1 (Preparation of Composition for Coating of Thermoplastic Polymer Film)

Example  One

An inorganic cationic colloidal sol was prepared by mixing 68.1 parts of water, 341.5 parts (70 parts in terms of solid content) of a cationic alumina sol (X1-1) and 130.4 parts (30 parts in terms of solid content) of a cationic silica sol (X2-1) . 10 parts of the silanol-forming inorganic silane compound (Y-1) was mixed with the inorganic cationic colloidal sol to prepare a mixed solution having a solid concentration of 20%, and the mixture was stirred at 50 캜 for 5 hours to obtain a silanol-forming organosilane compound (Y- 1) was hydrolyzed, and the resulting silanol compound was subjected to condensation polymerization to obtain a modified inorganic cationic colloidal sol (A-1). The modified inorganic canyon colloidal sol (A-1) was attached to the condensation polymer of the silanol compound on the solid particle of the inorganic cationic colloidal sol. Subsequently, 9,400 parts of water, 30 parts of polyether-modified silicone (B-1), 10 parts of polyoxyalkylene derivative (C-1) and 100 parts of water were added to 100 parts in terms of solid content of the modified inorganic cationic colloid sol (A- 60 parts of polyalkylene glycol (D-1) were further added and stirred to obtain a thermoplastic polymer film coating composition having a solid content concentration of 2%.

Example  2 to Example  37 and Comparative Example  1 to Comparative Example  15

Modified inorganic cationic colloid sols (A-12) and (AR-1) to (AR-3) were prepared in the same manner as in Example 1, and the same procedures as in Examples 2 to 37 and Comparative Examples 1 to 3 15 compositions for thermoplastic polymeric film coatings were obtained. The contents of the modified inorganic cationic colloidal sol prepared in each of the above Examples are summarized in Table 1, and the contents of the composition for thermoplastic polymer film coating obtained in each of the above Examples are summarized in Tables 2 and 3.

Kinds

Modified inorganic cationic colloid sol Inorganic cationic colloidal sol Silanol-forming
Organosilane compound Cateine alumina sol Cationic silica sol Kinds
Ratio (minus)
Kinds Ratio (minus) Kinds Ratio (minus) A-1
A-2
A-3
A-4
A-5
A-6
A-7
A-8
A-9
A-10
A-11
A-12 X1-1
X1-1
X1-1
X1-2
X1-2
X1-3
X1-1
X1-2
X1-1
X1-1
X1-1
X1-1 70
80
50
70
60
80
90
20
70
80
70
80 X2-1
X2-2
X2-3
X2-1
X2-2
X2-1
X2-1
X2-3
X2-1
X2-2
X2-1
X2-2 30
20
50
30
40
20
10
80
30
20
30
20 Y-1
Y-2
Y-3
Y-1
Y-2
Y-1
Y-2
Y-2
Y-1
Y-2
Y-4
Y-5 10
8
12
9
11
10
10
7
5
15
10
8 AR-1
AR-2
AR-3 X1-1
X1-2
X1-3 0
100
50 X2-1
X2-2
X2-3 100
0
50 Y-1
Y-1
Y-2 10
10
0

In Table 1,

X1-1: alumina sol 520 manufactured by Nissan Chemical Industries, Ltd.

X1-2: alumina sol 200 manufactured by Nissan Chemical Industries, Ltd.

X1-3: Product name Cataloid AS-1 manufactured by Nikkiso Co., Ltd.

X2-1: Snowtex AK, a product of Nissan Kagaku Kogyo Co.,

X2-2: Product name Cataroide SN, manufactured by Nippon Shokubai Pharmaceutical Co.,

X2-3: Product name Qwertron PL-3-C from Fusokagaku Kogyo Co.

Y-1:? -Glycidoxypropyltrimethoxysilane

Y-2: γ-ureidopropyltrimethoxysilane

Y-3: Ethyltriethoxysilane

Y-4:? -Glycidoxypropylmethyldimethoxysilane

Y-5: Trimethylmethoxysilane

division
Composition for thermoplastic polymer film coating Modified inorganic cationic colloid sol Polyether modification
silicon Polyoxyalkylene
derivative Polyalkylene glycol Kinds Mass part Kinds Mass part Kinds Mass part Kinds Mass part Example 1
2
3
4

5

6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28

29

30
31
32
33
34
35
36
37 A-1
A-2
A-3
A-4

A-5

A-6
A-1
A-2
A-1
A-2
A-3
A-1
A-3
A-1
A-1
A-2
A-1
A-1
A-7
A-8
A-9
A-10
A-11
A-12
A-4
A-5
A-2
A-1

A-1

A-1
A-1
A-5
A-2
A-1
A-1
A-1
A-1 100
100
100
100

100

100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100

100

100
100
100
100
100
100
100
100 B-1
B-2
B-3
B-1
B-4
B-2
B-5
B-1
B-2
B-3
B-1
B-2
B-3
B-3
B-1
B-2
B-2
B-3
B-3
B-1
B-1
B-4
B-5
B-1
B-1
B-2
B-3
B-4
B-1
B-1
B-3
B-1
B-3
B-4
B-2
B-5
B-1
B-1
B-1
B-1
B-1 30
20
40
15
15
15
10
30
30
30
30
20
40
10
10
45
30
20
40
20
30
30
30
30
30
30
30
30
10
24
24
5
5
50
23
25
30
20
30
30
30 C-1
C-2
C-3
C-4

C-5

C-7
C-8
C-9
C-10
C-11
C-12
C-6
C-13
C-1
C-7
C-3
C-3
C-4
C-1
C-1
C-7
C-1
C-1
C-2
C-3
C-4
C-4
C-1

C-9

C-1
C-4
C-8
C-4
C-1
C-14
C-15
C-16 10
20
5
20

5

10
20
10
10
20
5
20
20
5
2
30
15
5
10
10
10
10
10
10
10
10
30
2

15

5
2
30
10
20
10
10
10 D-1
D-2
D-3
D-1

D-2

D-1
D-2
D-3
D-4
D-5
D-3
D-1
D-1
D-1
D-1
D-2
D-1
D-1
D-2
D-1
D-3
D-1
D-6
D-7
D-8
D-9
D-1
D-3

D-1

D-3
D-1
D-2
D-10
D-11
D-1
D-1
D-1 60
60
55
50

70

60
50
60
60
60
55
70
70
50
68
50
45
75
60
60
60
60
60
60
60
60
60
50

75

45
75
45
60
60
60
60
60

division
Composition for thermoplastic polymer film coating Modified inorganic cationic colloid sol Polyether modification
silicon Polyoxyalkylene
derivative Polyalkylene glycol Kinds Mass part Kinds Mass part Kinds Mass part Kinds Mass part Comparative Example 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 A-1
A-1
A-2
A-2
A-1
A-1
AR-1
AR-2
AR-3
A-1
A-3
A-5
A-1
A-2
A-4 100
100
100
100
100
100
100
100
100
100
100
100
100
100
100 B-1
B-2
B-2
B-3
B-3
B-1
B-1
B-3
B-1
BR-1
BR-2
B-3
B-1
B-1
B-3 5
35
40
20
40
15
30
30
30
30
30
30
20
40
20 C-1
C-2
C-3
C-4
C-5
C-9
C-1
C-8
C-2
C-1
C-3
CR-1
CR-2
C-1
C-2 30
2
One
35
20
5
10
10
10
10
10
10
20
5
20 D-1
D-1
D-2
D-1
D-1
D-2
D-1
D-3
D-3
D-1
D-3
D-1
D-2
DR-1
DR-2 65
45
59
45
40
80
60
60
60
60
60
60
60
55
60

In Table 2 and Table 3,

A-1 to A-12, AR-1 to AR-3: Modified inorganic cationic colloid sols shown in Table 1

B-1: polyether-modified silicone (trade name: TSF4440, HLB = 14, manufactured by Momentive Performance Materials Japan)

B-2: Polyether-modified silicone (trade name KF-354L, HLB = 16 from Shin-Etsu Silicone Co., Ltd.)

B-3: Polyether-modified silicone (trade name KF-945, HLB = 4, manufactured by Shin-Etsu Silicone Co., Ltd.)

B-4: Polyether-modified silicone (trade name SH8400, HLB = 8, manufactured by Doray Dow Corning)

B-5: Polyether-modified silicone (trade name KF-6004, HLB = 9, manufactured by Shin-Etsu Silicone Co., Ltd.)

BR-1: Polydimethyl silicone (trade name KF-96, manufactured by Shin-Etsu Silicone Co., Ltd.)

BR-2: long-chain alkyl-modified silicone (trade name KF-412, manufactured by Shin-Etsu Silicone Co., Ltd.)

C-1: EO (ethylene oxide, hereinafter the same) of an aliphatic mixed alcohol having 12 to 13 carbon atoms PO (propylene oxide, hereinafter the same) 10 mol Random adduct

C-2: EO 10 mole adduct of lauryl alcohol

C-3: EO 9 mol adduct of an aliphatic mixed secondary alcohol having 9 to 11 carbon atoms

C-4: EO 14 mole adduct of oleyl alcohol

C-5: EO 20 mole adduct of stearyl alcohol

C-6: PO 13 mole of an aliphatic mixed alcohol having 14 to 15 carbon atoms EO 11 mole block adduct

C-7: EO 10 mole adduct of caprylic acid

C-8: EO 12 mole adduct of lauric acid

C-9: EO 13 mole adduct of stearic acid

C-10: EO 24 mole adduct of behenyl alcohol

C-11: EO 9 mole PO 9 mole random adduct of lauryl alcohol

C-12: PO 24 mole of oleic acid EO 24 mole block adduct

C-13: EO 13 mole adduct of oleic acid

C-14: caprylamine ethylene oxide 4 mole adduct

C-15: nonylphenol ethylene oxide 10 mole adduct

C-16: 2-ethylhexyl alcohol 100 mol adduct of ethylene oxide

CR-1: methanol

CR-2: Ethylene glycol

D-1: Polyethylene glycol (trade name PEG-20000, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 20,000)

D-2: Polyethylene glycol (trade name PEG-10000, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 11,000)

D-3: Polyethylene glycol (trade name PEG-13000, manufactured by Sanyo Chemical Industries, Ltd., number-average molecular weight: 13,000)

D-4: Polyethylene glycol (trade name PEG-6000P, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 8,600)

D-5: Polyethylene glycol (number average molecular weight: 28,000)

D-6: Ethylene oxide-propylene oxide random polymerized polymer (ethylene oxide / propylene oxide = 4/1 (molar ratio), number average molecular weight 10,000)

D-7: Ethylene oxide-propylene oxide block polymerization Polymer (ethylene oxide / propylene oxide / ethylene oxide = 141/44/141 (molar ratio), Pluronic F108NF manufactured by BASF Co., Molecular weight 14,600)

D-8: Ethylene oxide-propylene oxide random polymerized polymer (ethylene oxide / propylene oxide = 50/50 (molar ratio), number average molecular weight 3,500)

D-9: Polyethylene glycol (number average molecular weight: 40000)

D-10: Ethylene oxide-propylene oxide block polymerization polymer (ethylene oxide / propylene oxide = 25/75 (molar ratio), number average molecular weight 1,700)

D-11: Polyethylene glycol (number average molecular weight: 50,000)

DR-1: polyethylene glycol (trade name PEG-400, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 400)

DR-2: Polyethylene glycol (trade name: Alox R-150, manufactured by Meisei Chemical Industry Co., Ltd., number average molecular weight: 150,000)

Test Category 2 (Preparation of modified thermoplastic polymer film)

An ethylene / 1-butene copolymer (ethylene copolymerization ratio 96%, density 0.930 g / cm 3, MFR 1.0 g / 10 min) was provided in an inflation molding machine equipped with a die having a diameter of 75 mm and a lip gap of 3 mm, And BUR = 1.8, to prepare an olefin polymer film having a thickness of 150 mu m. Then, the olefin polymer film was subjected to corona treatment discharge, and the wet tensile strength on the corona discharge treated surface was set to 42 mN / m. Then, on the corona discharge treated surface, the thermoplastic polymer film coating composition prepared in Test Category 1 was dissolved in the solid To 0.3 g / m 2 by a gravure coating method, and the mixture was allowed to stand for 1 minute in a hot-air drying furnace adjusted to a temperature of 70 ° C to obtain modified thermoplastic polymer films of each example.

Test Category 3 (Evaluation of Modified Thermoplastic Polymer Film)

Relic  evaluation

Each of the modified thermoplastic polymer films prepared in the above Test Category 2 was put into a test house having a slope of 15 degrees adjusted to an inner temperature of 30 DEG C at an outer temperature of 10 DEG C, ) And long-term (after 30 days), the water drop prevention effect, that is, the oil resistance was evaluated by the following criteria. The results are summarized in Tables 4 and 5.

Estimation criteria of relics

5: No adhesion of water droplets

4: The adhesion area of water drops is less than 10%

3: the adhesion area of water drops is 10% or more to less than 50%

2: the adhesion area of water drops is 50% or more and less than 80%

1: the adhesion area of water drops is 80% or more

Abrasive  evaluation

A vinyl tape was attached to the friction surface of the arm of a friction tester (Kyodo type dyeing fastness tester, manufactured by Dai-igaku Kasei Seisakusho Co., Ltd.), and a load of 300 g was applied. The coated surface of each modified thermoplastic polymer film prepared in the above Test Category 2 100 cm < 2 >, subjected to 10 reciprocating rubbing, then subjected to water vapor on the rubbed portion, and the degree of peeling of the coating film was observed by the fogging portion formed by the adhesion of the water droplets, and the peeling strength . The results are summarized in Tables 4 and 5.

Evaluation criteria of scratch resistance

5: No peeling of film

4: Peeling area of the film is less than 10%

3: Peeling area of coating film is 10% or more and less than 50%

2: peeling area of coating film is 50% or more and less than 80%

1: Peeling area of coating film is 80% or more

Evaluation of stickiness

Two specimens of 20 cm x 20 cm square were cut out from each modified thermoplastic polymer film prepared in the above Test Category 2, and the applied surfaces of the specimens were overlapped and held at 50 캜 for 24 hours at a load of 1 kg / Thereafter, the overlapped film was cut into a square of 10 mm x 10 mm to prepare a test piece. The peeling force between the two films, that is, the stickiness was evaluated on the following criteria. The results are summarized in Tables 4 and 5.

Evaluation criteria of stickiness

5: Peel force less than 50mN / 10mm

4: peel force of 50 mN / 10 mm or more to less than 100 mN / 10 mm

3: Peel force of 50 mN / 10 mm or more to 150 mN / 10 mm or less

2: peeling force of 150 mN / 10 mm or more to less than 200 mN / 10 mm

1: Peel force of 200 mN / 10 mm or more

Liquid-stable  evaluation

The thermoplastic polymer film coating composition prepared in the above Test Category 1 was stored in a sealed container at room temperature at 20 DEG C to separate the solution, and the stability of the solution was evaluated according to the following criteria . The results are summarized in Tables 4 and 5.

Criteria for evaluation of liquid stability

5: No separation for more than 24 hours

4: No separation from more than 12 hours to less than 24 hours

3: no more than 6 hours to less than 12 hours separation

2: no more than 2 hours to less than 6 hours

1: Separation to less than 2 hours

Application  evaluation

The condition of the coated surface of each modified thermoplastic polymer film prepared in Test Category 2 was observed and the coating properties were evaluated according to the following criteria. The results are summarized in Tables 4 and 5.

Evaluation criterion of applicability

5: No staining, no staining

4: Some spots occur

3: All the stains occur

2: Some of them have a problem

1: The whole thing is 함

division
evaluation Drip castle Abrasion resistance
Stickiness
Liquid stability
Application property
Early long time Example 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37 5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
4
5
4
5
5
4
5
4
5
5
5
5
5
4
5
4
5
4
5
5
5 5
5
5
5
5
5
5
5
5
5
5
5
5
4
5
5
5
5
5
4
4
5
5
5
5
5
5
4
5
4
5
5
5
5
4
5
5 5
5
5
5
5
5
5
5
5
5
5
4
4
5
5
5
5
5
5
5
5
5
4
5
5
5
4
5
4
5
5
5
4
5
5
4
5 5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
4
5
5
5
5
5
5
5
5
5
5
4
5
5
5
5
4
4
5
5
4
4 5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
4
5
5
5
5
5
5
5
5
5
5
4
5
4
5
5
5
5
5
4 5
5
5
5
5
5
5
5
5
5
5
5
5
5
4
5
5
5
5
5
5
5
5
5
4
4
5
4
5
5
4
5
5
4
4
5
5

division
evaluation Drip castle Abrasion resistance
Stickiness
Liquid stability
Application property
Early long time Comparative Example 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 5
5
4
5
One
5
2
4
5
4
4
4
4
4
2 5
2
5
5
5
4
2
One
One
4
4
4
4
4
One One
5
5
4
5
5
2
One
One
One
One
4
4
2
4 4
5
5
2
5
5
5
5
5
4
4
4
One
One
4 5
5
5
5
5
One
5
5
4
2
2
One
4
4
One 5
5
One
5
5
5
5
5
5
One
One
2
2
4
One

As can be seen from the results of Tables 4 and 5 corresponding to Tables 2 and 3, when the composition of the present invention is applied, deterioration of the performance of the magnetic recording medium due to friction during film formation or electric field is small, It is possible to maintain the excellent relics over a long period of time even after the battle, and to have a very low tackiness on the coated surface.

Claims (13)

The following modified inorganic cationic colloidal sol is used in an amount of 10 to 50 parts by mass, preferably 2 to 30 parts by mass, and the following polyoxyalkylene derivative in 100 parts by mass in terms of solid content, And a polyalkylene glycol having a number average molecular weight of 1,500 to 50,000 in an amount of 45 to 75 parts by weight based on the total weight of the thermoplastic polymer film.
Modified inorganic cationic colloidal sol: The condensation polymer of the following silanol compound in solid particles of the following inorganic cationic colloidal sol is a solid content of inorganic cationic colloidal sol / condensation polymer of silanol compound = 100/5 (mass ratio) to 100 / 15 (by mass ratio).
Inorganic cationic colloid sol: 20% by mass to 90% by mass of the cationic alumina sol in terms of solid matter, and 10% by mass to 80% by mass (in terms of solid content, 100% by mass in total) By weight of a cationic colloidal sol.
Silanol compound: a product obtained by hydrolyzing at least one silanol-forming organosilane compound selected from trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes.
Polyoxyalkylene derivative: a compound in which ethylene oxide is added in a proportion of 3 to 100 moles per one mole of the following starting compound, 3 to 100 moles of ethylene oxide and propylene oxide per mole of the following starting compound, At least one compound selected from a compound added in a form of a block in a total amount of 3 to 100 moles of ethylene oxide and propylene oxide per 1 mole of the following starting compound.
Starting compounds: aliphatic alcohols having 8 to 22 carbon atoms, fatty acids having 8 to 22 carbon atoms, alkylphenols having 8 to 22 carbon atoms in the alkyl group, or monoalkylamines having 8 to 22 carbon atoms in the alkyl group. The composition for coating a thermoplastic polymer film according to claim 1, wherein the polyether-modified silicone has an HLB of 4 to 16. 3. The method according to claim 1 or 2, wherein the silanol compound is selected from? -Glycidoxypropyltrimethoxysilane,? -Ureidopropyltrimethoxysilane, methyltriethoxysilane and ethyltriethoxysilane Wherein the at least one silanol-forming organosilane compound is hydrolyzed. 4. The process according to any one of claims 1 to 3, wherein the polyoxyalkylene derivative is a compound in which ethylene oxide is added in an amount of 5 to 50 mol per 1 mol of the following starting compound, A compound in which a seed and propylene oxide are added at random in a ratio of 5 to 50 moles in total, and a compound in which a total of 5 to 50 moles of ethylene oxide and propylene oxide are added in a block form per 1 mole of the following starting compound Wherein the thermoplastic polymer film is at least one selected from the group consisting of a thermoplastic resin and a thermoplastic resin.
Starting compound: aliphatic alcohol having 8 to 22 carbon atoms or fatty acid having 8 to 22 carbon atoms 5. The polymer composition according to any one of claims 1 to 4, wherein the polyalkylene glycol is selected from the group consisting of polyethylene glycol having a number average molecular weight of 3,000 to 40,000, polypropylene glycol, ethylene oxide-propylene oxide random polymerized polymer, and ethylene oxide Wherein the thermoplastic polymer film is at least one selected from the group consisting of a propylene oxide block copolymer and a seed-propylene oxide block polymer. The composition for coating a thermoplastic polymer film according to any one of claims 1 to 4, wherein the polyalkylene glycol is polyethylene glycol having a number average molecular weight of 6,000 to 30,000. 7. The cemented carbide zeolite according to any one of claims 1 to 6, wherein the inorganic cationic colloidal sol contains 50% by mass to 80% by mass of the cationic alumina sol in terms of solid matter, and 20% by mass to 50% By mass to 100% by mass in total in terms of solid content) of the thermoplastic polymer film. [Claim 7] The method according to any one of claims 1 to 7, wherein the modified inorganic cationic colloid sol is a condensation polymer of a silanol compound on a solid particle of an inorganic cationic colloidal sol, Is in a ratio of 100/7 (mass ratio) to 100/12 (mass ratio). The composition for coating a thermoplastic polymer film according to claim 1, 9. The polyurethane foam according to any one of claims 1 to 8, wherein the modified inorganic cationic colloidal sol contains 20 to 40 parts by mass of polyether-modified silicone and 5 to 40 parts by mass of a polyoxyalkylene derivative in 100 parts by mass in terms of solid content, By mass to 20 parts by mass of the polyalkylene glycol and 50 to 70 parts by mass of the polyalkylene glycol. A method for producing a composition for coating a thermoplastic polymer film, which comprises the following first step and a second step.
Step 1: Hydrolysis of the following silanol-forming organosilane compound in an amount ranging from 5 parts by mass to 15 parts by mass per 100 parts by mass of the solid content of the inorganic cationic colloid sol in the presence of the following inorganic cationic colloid sol And condensation polymerization of the resulting silanol compound to obtain a modified inorganic cationic colloidal sol.
Inorganic cationic colloidal sol: 20% by mass to 90% by mass of a cationic alumina sol in terms of solid content, and 10% by mass to 80% by mass (in total of 100% by mass in terms of solid content) The inorganic cationic colloidal sol.
Silanol-forming organosilane compounds: at least one selected from the group consisting of trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes.
Second Step: The modified inorganic cationic colloid sol obtained in the first step is added in an amount of 10 parts by mass to 50 parts by mass of polyether-modified silicone per 100 parts by mass in terms of solid content, 2 parts by mass of the following polyoxyalkylene derivative To 30 parts by mass and a polyalkylene glycol having a number average molecular weight of 1,500 to 50,000 at a ratio of 45 parts by mass to 75 parts by mass to obtain a composition for coating a thermoplastic polymer film.
Polyoxyalkylene derivative: a compound in which ethylene oxide is added in a proportion of 3 molar equivalents per 100 mol of the following starting compound, 3 mol to 100 mol of ethylene oxide and propylene oxide per 1 mol of the following starting compound, At least one compound selected from a compound added in a form of a block in a total amount of 3 to 100 moles of ethylene oxide and propylene oxide per 1 mole of the following starting compound.
Starting compounds: aliphatic alcohols having 8 to 22 carbon atoms, fatty acids having 8 to 22 carbon atoms, alkylphenols having 8 to 22 carbon atoms in the alkyl group, or monoalkylamines having 8 to 22 carbon atoms in the alkyl group. The thermoplastic polymer film according to any one of claims 1 to 9, wherein a composition for coating a thermoplastic polymer film is adhered in an amount of 0.1 g / m 2 to 2.0 g / m 2 as a solid content on a corona discharge treated surface of the thermoplastic polymer film film. 12. The modified thermoplastic polymer film according to claim 11, which is an agricultural coating film. A method for producing a modified thermoplastic polymer film, comprising the following first step and a second step.
Step 1: A step of subjecting the thermoplastic polymer film to corona discharge treatment so that the wet tension on the corona discharge treated surface is 35 mN / m or more.
Step 2: The thermoplastic polymer film coating composition according to any one of claims 1 to 10 is applied to the corona discharge treated surface of the thermoplastic polymer film obtained in the first step in an amount of 0.1 g / m 2 to 2.0 g / M < 2 >.