WO2017029867A1

WO2017029867A1 - Thermoplastic polymer film coating composition, method for preparing thermoplastic polymer film coating composition, modified thermoplastic polymer film, and method for preparing modified thermoplastic polymer film

Info

Publication number: WO2017029867A1
Application number: PCT/JP2016/067751
Authority: WO
Inventors: 享弘山田; 和史潮谷; 麻美常松
Original assignee: 竹本油脂株式会社
Priority date: 2015-08-17
Filing date: 2016-06-15
Publication date: 2017-02-23
Also published as: JP5963923B1; CN107922754B; JP2017039785A; KR20180030233A; KR101904129B1; CN107922754A

Abstract

Provided are: a thermoplastic polymer film coating composition which has only minimal deterioration of drop-flowing properties caused by friction during film formation or spreading, exhibits excellent drop-flowing properties from the start of spreading, maintains excellent drop-flowing properties over a long period of time even after spreading, and furthermore, has an extremely non-sticky film surface coated with a drop-flowing agent; a method for preparing a modified thermoplastic polymer film using such a composition; and a modified thermoplastic polymer film obtained by such a preparation method. This thermoplastic polymer film coating composition is a compound in which a polyether-modified silicone, a specific polyoxyalkylene derivative, and a polyalkyleneglycol having a number-average molecular weight of 1500-50000 are contained at a specific ratio in a specific modified inorganic cation colloidal sol obtained by hydrolyzing a specific inorganic cation colloidal sol with a specific silanol-forming organic silane compound.

Description

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

The present invention has little drop in droplet performance due to friction at the time of film formation in a factory or when it is extended to an agricultural house, exhibits excellent droplet properties from the initial stage of spreading, and has an excellent flow over a long period after spreading. A composition for coating a thermoplastic polymer film that maintains the droplet properties and has very little stickiness on the coated film surface, a method for producing such a composition, a modified thermoplastic polymer film using such a composition, and such a modified polymer film. The present invention relates to a method for producing a thermoplastic polymer film.

Conventionally, as a composition for coating a thermoplastic polymer film, an alumina sol, an acidic silica sol, an organic silane derivative and a nonionic surfactant (for example, see Patent Document 1), colloidal alumina, colloidal silica, and polyethylene glycol are used. (For example, see Patent Document 2) and the like have been proposed. However, in these conventional thermoplastic polymer film coating compositions, the film drip performance deteriorates due to friction during film formation at a factory or when it is applied to an agricultural house. There are problems such as stickiness.

JP 62-241984 JP 2000-160146 A

The problem to be solved by the present invention is that there is little drop in the droplet performance due to friction during film formation or stretching, and exhibits excellent droplet property from the initial stage of spreading, and excellent droplet property over a long period after stretching. In addition, a composition for coating a thermoplastic polymer film with very little stickiness on the surface of the film coated with a droplet agent, a method for producing such a composition, a modified thermoplastic polymer film using such a composition, and It exists in the place which provides the manufacturing method of this modified thermoplastic polymer film.

As a result of researches to solve the above-mentioned problems, the present inventors have obtained a modified inorganic cation colloid sol obtained by modifying a specific inorganic cation colloid sol with a condensation polymer of a specific silanol compound, a polyether-modified silicone, It has been found that a composition for coating a thermoplastic polymer film comprising a specific polyoxyalkylene derivative and a polyalkylene glycol having a number average molecular weight of 1500 to 50,000 in a specific ratio is correctly suitable.

That is, the present invention relates to the following modified inorganic cation colloid sol in terms of solid content of 100 parts by mass, 10 to 50 parts by mass of polyether-modified silicone, 2 to 30 parts by mass and the number average of the following polyoxyalkylene derivatives. The present invention relates to a thermoplastic polymer film coating composition comprising polyalkylene glycol having a molecular weight of 1500 to 50000 in a proportion of 45 to 75 parts by mass. The present invention also relates to a method for producing such a composition, a modified thermoplastic polymer film using such a composition, and a method for producing such a modified thermoplastic polymer film.

Modified inorganic cation colloid sol: Condensation polymer of the following silanol compound on solid content particles of the inorganic cation colloid sol described below, solid content of inorganic cation colloid sol / condensation polymer of silanol compound = 100/5 to 100/15 Modified inorganic cation colloid sol adhering at a ratio of (mass ratio).

Inorganic cation colloid sol: Inorganic cation colloid comprising cation alumina sol in a proportion of 20 to 90% by mass in terms of solid content and cationic silica sol in a proportion of 10 to 80% by mass in terms of solid content (total 100% by mass in terms of solid content) Sol.

Silanol compound: Hydrolyzed at least one silanol-forming organic silane compound selected from trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes

Polyoxyalkylene derivative: a compound in which ethylene oxide is added in a ratio of 3 to 100 mol per 1 mol of the following starting compound, and random in a ratio of 3 to 100 mol in total of ethylene oxide and propylene oxide per 1 mol of the following starting compound And at least one compound selected from the following compounds having a total of 3 to 100 moles of ethylene oxide and propylene oxide added in a block form per mole of the following starting compound

Starting compound: aliphatic alcohol having 8 to 22 carbon atoms, fatty acid having 8 to 22 carbon atoms, alkylphenol having 8 to 22 carbon atoms in alkyl group, or monoalkylamine having 8 to 22 carbon atoms in alkyl group

First, the thermoplastic polymer film coating composition according to the present invention (hereinafter referred to as the composition of the present invention) will be described. The composition of the present invention comprises 10 to 50 parts by mass of a polyether-modified silicone, 2 to 30 parts by mass of the polyoxyalkylene derivative, and 100 parts by mass of the modified inorganic cation colloid sol described above in terms of solid content. A polyalkylene glycol having a number average molecular weight of 1500 to 50000 is contained in a proportion of 45 to 75 parts by mass. The modified inorganic cation colloid sol is added to 100 parts by mass in terms of solid content with a polyether-modified silicone. It is preferable to contain 20 to 40 parts by mass, 5 to 20 parts by mass of the polyoxyalkylene derivative and 50 to 70 parts by mass of polyalkylene glycol.

The modified inorganic cation colloid sol to be used in the composition of the present invention comprises a specific silanol compound condensation polymer on solid particles of a specific inorganic cation colloid sol, a solid content of inorganic cation colloid sol / silanol compound condensation polymer. = 100/5 to 100/15 (mass ratio).

The inorganic cation colloid sol used as a raw material for the modified inorganic cation colloid sol is 20 to 90% by mass in terms of solid content of cation alumina sol and 10 to 80% by mass in terms of solid content of cation silica sol (total 100 in terms of solid content). The cation alumina sol is 50 to 80% by mass in terms of solid content and the cation silica sol is 20 to 50% by mass in terms of solid content (total 100% by mass in terms of solid content). What is contained in the ratio is preferably.

The cationic alumina sol is so-called colloidal alumina, and a commercially available aqueous dispersion can be used as it is. Examples of such commercially available products include alumina sol 100, alumina sol 200, alumina sol 520 (all are trade names manufactured by Nissan Chemical Co., Ltd.), cataloid AS-1, and cataloid AS-2 (all are manufactured by JGC Catalysts & Chemicals, Inc.). Product name).

As the cationic silica sol, a commercially available aqueous dispersion can be used as it is. Examples of such commercially available products include SNOWTEX AK, SNOWTEX AK-L (all of which are trade names manufactured by Nissan Chemical Co., Ltd.), Cataloid SN (trade name of JGC Catalysts & Chemicals Co., Ltd.), Quattron PL-3- C (trade name manufactured by Fuso Chemical Industry Co., Ltd.) and the like.

Silanol compound condensation polymer adhering to the surface of solid particles (alumina or silica colloidal particles) of such inorganic cation colloid sol hydrolyzes silanol-forming organosilane compounds, and the resulting silanol compound is condensation polymerized. Can be obtained. As will be described in detail later, the silanol-forming organic silane compound is hydrolyzed in the presence of the inorganic cation colloid sol, and the resulting silanol compound is subsequently subjected to condensation polymerization to form solid particles of the inorganic cation colloid sol. A modified inorganic cation colloidal sol having a silanol compound condensation polymer adhered thereto can be obtained.

The modified inorganic cation colloid sol used in the composition of the present invention is attached in such a form that the condensation polymer of the silanol compound covers all or part of the surface of the solid particles of the inorganic cation colloid sol, A part of this is presumed to be chemically bonded to the solid particles of the inorganic cation colloid sol. In this modified inorganic cation colloid sol, the solid polymer particles of the inorganic cation colloid sol have a silanol compound condensation polymer, the solid content of the inorganic cation colloid sol / condensation polymer of the silanol compound = 100/5 to 100/15 (mass). Ratio), but the solid content of inorganic cation colloidosol / condensation polymer of silanol compound = 100/7 to 100/12 (mass ratio). It is preferable to do this.

As the polyether-modified silicone used in the composition of the present invention, commercially available products can be used as they are. Examples of such commercially available products include TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, and TSF4460 (all of which are trade names of Momentive Performance Materials Japan), X22-4952, X-22-4272, and KF. -6123, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-644, KF-6204 X-22-4515, KF-6004 (all are trade names manufactured by Shin-Etsu Silicone), SH8700, SH8410, SH8400, L-7002, FZ-2104, FZ-77, L-7604, FZ-2203, FZ-2208 (all the above Dow Corning Toray Co., Ltd. under the trade name), but and the like, and among them, TSF4440, KF-354L, KF-945, SH8400, KF-6004, etc., HLB is preferably from 4 to 16.

The polyoxyalkylene derivative used for the composition of the present invention is a compound in which ethylene oxide is added to the following starting compound and / or a compound in which ethylene oxide and propylene oxide are added, and ethylene oxide and propylene oxide are added. In this case, either a block-like addition or a random-like addition structure may be used. The number of moles added is 3 to 100 moles of ethylene oxide or ethylene oxide and propylene oxide in total with respect to 1 mole of the following starting compound, but preferably 5 to 50 moles.

Examples of the aliphatic alcohol having 8 to 22 carbon atoms of 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, tridecyl alcohol, Examples include myristyl alcohol, pentadecyl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, lysylyl alcohol, and behenyl alcohol. Examples of the fatty acid 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, linoleic acid, eicosanoic acid, and behenic acid. . Further, examples of the alkylphenol having 8 to 22 carbon atoms in the alkyl group include octylphenol, nonylphenol, decylphenol, dodecylphenol, octadecylphenol and the like. Furthermore, examples of the monoalkylamine having 8 to 22 carbon atoms in the alkyl group include caprylamine, nonylamine, decylamine, laurylamine, tridecylamine, myristylamine, stearylamine, oleylamine, and behenylamine. Among these, starting alcohols are preferably aliphatic alcohols having 8 to 22 carbon atoms and fatty acids having 8 to 22 carbon atoms.

Specifically, ethylene oxide adducts of aliphatic alcohols having 8 to 22 carbon atoms include capryl alcohol ethylene oxide 5 mol adduct, 2-ethylhexyl alcohol ethylene oxide 100 mol adduct, nonyl alcohol ethylene oxide 5 mol adduct, undecyl alcohol ethylene oxide 30. Mole adduct, 9 mol adduct of secondary alcohol ethylene oxide having 9 to 12 carbon atoms, 10 mol adduct of lauryl alcohol ethylene oxide, 50 mol adduct of palmityl alcohol ethylene oxide, 20 mol adduct of stearyl alcohol ethylene oxide, 20 mol of isostearyl alcohol ethylene oxide Adduct, oleyl alcohol ethylene oxide 14 mol adduct, behenyl alcohol ethylene oxide 24 mol adduct, and the like. Examples of adducts of ethylene oxide and propylene oxide of aliphatic alcohols having a prime number of 8 to 22 include 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 mol random adduct, myristyl alcohol propylene oxide 13 mol ethylene oxide 10 mol block addition Body, tetradecyl alcohol propylene oxide 13 mol ethylene oxide 1 Mole block adduct, pentadecyl alcohol propylene oxide 13 moles of ethylene oxide 10 mole block adduct, and the like.

Specific examples of ethylene oxide adducts of fatty acids having 8 to 22 carbon atoms include caprylic acid ethylene oxide 10 mol adduct, lauric acid ethylene oxide 12 mol adduct, palmitic acid ethylene oxide 5 mol adduct, stearic acid ethylene oxide 13 mol adduct, Examples include 13 mole adducts of oleic acid ethylene oxide. Examples of adducts of fatty acid having 8 to 22 carbon atoms with ethylene oxide and propylene oxide include 10 mol of caprylic acid ethylene oxide, 10 mol of propylene oxide, and 40 mol of capric acid alcohol ethylene oxide. Propylene oxide 10 mol random adduct, Lauric acid alcohol ethylene oxide 10 mol Propylene oxide 10 mol random adduct, Myristate propylene oxide 13 mol ethylene Kishido 10 mole block adduct, pentadecanoate propylene oxide 13 moles of ethylene oxide 10 mole block adduct, propylene oxide 24 moles of ethylene oxide 24 mole block adduct of oleic acid, behenic acid ethylene 10 propylene oxide 10 mole random adduct, and the like.

More specifically, ethylene oxide adducts of alkylphenols having 8 to 22 carbon atoms in the alkyl group include octylphenol ethylene oxide 3 mol adduct, nonylphenol ethylene oxide 10 mol adduct, decylphenol ethylene oxide 12 mol adduct, dodecylphenol ethylene oxide 100 mol adduct. The adducts of alkylphenols having 8 to 22 alkyl groups with an alkyl group of ethylene oxide and propylene oxide include octylphenol ethylene oxide 50 mol propylene oxide 10 mol random adduct, nonylphenol propylene oxide 10 mol ethylene oxide 35 mol random addition. Decylphenol propylene oxide 3 mol ethylene oxide 10 mol block block adduct, oct Decyl phenol propylene oxide 10 moles of ethylene oxide 80 mol random adduct, and the like.

Further, specific examples of the ethylene oxide adduct of monoalkylamine having 8 to 22 carbon atoms in the alkyl group include caprylamine ethylene oxide 4 mol adduct, laurylamine ethylene oxide 10 mol adduct, myristylamine ethylene oxide 20 mol adduct, stearyl. Examples include adducts of 45 mol of amine ethylene oxide, and adducts of ethylene oxide and propylene oxide of monoalkylamine having 8 to 22 carbon atoms in the alkyl group include caprylamine ethylene oxide 20 mol propylene oxide 10 mol random adduct, laurylamine Ethylene oxide 10 mol propylene oxide 10 mol random adduct, palmitylamine propylene oxide 10 mol ethylene oxide 20 mol block adduct, stearylamine propylene N'okishido 20 moles of ethylene oxide 60 mole block adduct, behenyl amine ethylene oxide 20 moles of propylene oxide 5 mol block adduct, and the like.

Among them, polyoxyalkylene derivatives include ethylene oxide adducts of aliphatic alcohols having 8 to 22 carbon atoms, adducts of ethylene oxide and propylene oxide of aliphatic alcohols having 8 to 22 carbon atoms, ethylene oxides of fatty acids having 8 to 22 carbon atoms. Adducts and adducts of fatty acid having 8 to 22 carbon atoms with ethylene oxide and propylene oxide, and ethylene oxide or ethylene oxide and propylene oxide are added at a ratio of 5 to 50 moles per mole of starting compound Is preferred. Specifically, preferred polyoxyalkylene derivatives include 10 mol adduct of decyl alcohol, 10 mol adduct of lauryl alcohol ethylene oxide, 9 mol adduct of secondary alcohol having 9 to 12 carbon atoms, stearyl alcohol ethylene oxide 20 Mole adduct, oleyl alcohol ethylene oxide 14 mol adduct, dodecyl alcohol ethylene oxide 10 mol propylene oxide 10 mol random adduct, tridecyl alcohol ethylene oxide 10 mol propylene oxide 10 mol random adduct, tetradecyl alcohol propylene oxide 13 mol ethylene oxide 11 Mole block adduct, 12 mol adduct of lauric acid ethylene oxide, 13 mol of stearic acid ethylene oxide Adducts, ethylene oxide 13 mol adduct of oleic acid, 9 moles of ethylene oxide propylene oxide 9 mole random adduct of stearic acid, propylene oxide 24 moles of ethylene oxide 24 mole block adduct of oleic acid.

Examples of the polyalkylene glycol having a number average molecular weight of 1500 to 50000 to be used in the composition of the present invention include polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random polymerization polymer, and ethylene oxide-propylene oxide block polymerization polymer having a number average molecular weight of 1500 to 50000. Among them, polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random polymerized polymer, ethylene oxide-propylene oxide block polymerized polymer having a number average molecular weight of 3,000 to 40,000 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 determined by the method described in JIS K0070.

Next, a method for producing a thermoplastic polymer film coating composition according to the present invention (hereinafter referred to as a method for producing the composition of the present invention) will be described. The manufacturing method of the composition of this invention is a manufacturing method which passes through the following 1st process and 2nd process.

First step: In the presence of the following inorganic cation colloid sol, the following silanol-forming organosilane compound in an amount of 5 to 15 parts by mass per 100 parts by mass of the solid content of the inorganic cation colloid sol is hydrolyzed. Further, a process of obtaining a modified inorganic cation colloid sol by condensation polymerization of the produced silanol compound Inorganic cation colloid sol: 20 to 90% by mass of cation alumina sol in terms of solid content and 10 to 80% by mass of cation silica sol in terms of solid content % Inorganic cation colloidal sol containing in a proportion of 100% by mass in terms of solid content

Silanol-forming organosilane compound: at least one selected from trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes

Second step: 10 to 50 parts by mass of polyether-modified silicone, 2 to 30 parts by mass of the following polyoxyalkylene derivative, and 100 parts by mass of the modified inorganic cation colloid sol obtained in step 1 in terms of solid content A step of blending polyalkylene glycol having a number average molecular weight of 1500 to 50000 in a proportion of 45 to 75 parts by mass to obtain a composition for coating a thermoplastic polymer film

In the method for producing the composition of the present invention, the inorganic cation colloid sol used in the first step is as described above. Silanol-forming organosilane compounds used in the first step include 1) methyltrimethoxysilane, methyltriethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ-chloropropyltripropoxysilane, γ-mercaptopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, trialkoxysilanes such as phenyltrimethoxysilane, 2) dimethyldimethoxy Dialkoxysilanes such as silane, γ-chloropropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane; 3) compounds such as trimethylchlorosilane and trimethylmethoxysilane; Alkoxysilanes, and the like. Of these, γ-glycidoxypropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane are preferable.

In the method for producing the composition of the present invention, the mass ratio of the solid content of the inorganic cation colloid sol and the silanol-forming organic silane compound used in the first step is determined by the condensation of the solid content of the inorganic cation colloid sol and the silanol compound. The polyether-modified silicone, polyoxyalkylene derivative and polyalkylene glycol used in the second step are the same as described above, including the proportions thereof.

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

The thermoplastic polymer film includes 1) polyolefin resin, 2) chlorinated resin such as polyvinyl chloride, vinyl chloride-methyl methacrylate copolymer, polyvinylidene chloride, and 3) polyester such as polyethylene terephthalate and polyethylene terephthalate. Examples of the resin include thermoplastic resins generally used as agricultural films. Examples of the polyolefin-based resin include homopolymerization of α-olefin, and a copolymer with a heterogeneous monomer having α-olefin as a main component. For example, polyethylene, polypropylene, ethylene-butene copolymer, ethylene-4 -Ethylene-α-olefin copolymers such as methyl-1-pentene copolymer and ethylene-hexene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate Examples thereof include copolymers and ionomer resins. These resins can contain an antioxidant, a weathering agent, an ultraviolet absorber, an infrared absorber, a lubricant, an antiblocking agent, an antifogging agent, a heat retention agent, a pigment, and the like as required. There is no restriction | limiting in particular as a method of shape | molding these resin into a film, For example, the inflation molding method, T-die molding method, etc. are mentioned. The resin used for molding may be a blend of a plurality of types of resins. Further, the film may be a single layer or a multilayer, and a film formed by combining in accordance with the purpose can be used.

The use of the film of the present invention is not particularly limited, but the effect is remarkable when it is used for a coating film for agriculture.

Finally, a method for producing a modified thermoplastic polymer film according to the present invention (hereinafter referred to as the film production method of the present invention) will be described. The manufacturing method of the film of this invention is a manufacturing method which passes through the following 1st process and the following 2nd process.

First step: A step of corona discharge treatment on the thermoplastic polymer film to increase the wetting tension of the corona discharge treatment surface to 35 mN / m or more.

Second step: A step of applying the above-described composition of the present invention to a solid content of 0.1 to 2.0 g / m ^{2 on} the corona discharge-treated surface of the thermoplastic polymer film obtained in the first step.

In the film production method of the present invention, the thermoplastic polymer film is as described above. The first step is a step in which the thermoplastic polymer film is subjected to corona discharge treatment so that the wetting tension of the corona discharge treatment surface is 35 mN / m or more, but the wetting tension is within the range of 35 to 70 mN / m. It is preferable that the effect is easily manifested. In the present invention, the wetting tension is a value measured according to the description of JIS-K6768.

In the second step, the composition of the present invention is applied to the corona discharge-treated surface of the thermoplastic polymer film obtained in the first step so that the solid content is 0.1 to 2.0 g / m ^2. It is a process to do. In order to apply the composition of the present invention to the thermoplastic polymer film, a known coating method can be used. Examples thereof include a spray coating method, a dip coating method, a roll coating method, a doctor blade coating method, a wire bar coating method, and an air knife coating method.

According to the present invention described above, there is little drop in droplet performance due to friction during film formation or stretching, and excellent droplet characteristics are exhibited from the initial stage of stretching, and excellent droplet dropping properties are maintained for a long time after stretching. In addition, there is an effect that the film surface coated with the droplet agent has very little stickiness.

Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.

Test Category 1 (Preparation of a composition for coating a thermoplastic polymer film)
Example 1
Inorganic cationic colloid by mixing 68.1 parts of water, 341.5 parts of cationic alumina sol (X1-1) (70 parts in terms of solid content) and 130.4 parts (30 parts in terms of solid content) of cationic silica sol (X2-1) A sol was prepared. This inorganic cation colloidal sol is mixed with 10 parts of a silanol-forming organosilane compound (Y-1) to prepare a mixed solution having a solid content of 20%, and stirred at 50 ° C. 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 cation colloid sol (A-1). In this modified inorganic cation colloid sol (A-1), a condensation polymerization product of a silanol compound was adhered to the solid particles of the inorganic cation colloid sol. Subsequently, 9400 parts of water, 30 parts of polyether-modified silicone (B-1), 10 parts of polyoxyalkylene derivative (C-1) are added to 100 parts in terms of solid content of the modified inorganic cation colloid sol (A-1). And 60 parts of polyalkylene glycol (D-1) were added and stirred to obtain a composition for coating a thermoplastic polymer film having a solid content concentration of 2%.

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

In Table 1,
X1-1: Trade name Alumina Sol 520 manufactured by Nissan Chemical Industries, Ltd.
X1-2: Product name Alumina Sol 200 manufactured by Nissan Chemical Industries, Ltd.
X1-3: Trade name Cataloid AS-1 manufactured by JGC Catalysts & Chemicals
X2-1: Product name Snowtex AK manufactured by Nissan Chemical Industries, Ltd.
X2-2: Product name Cataloid SN manufactured by JGC Catalysts & Chemicals
X2-3: Trade name Quarton PL-3-C manufactured by Fuso Chemical Industry Co., Ltd.
Y-1: γ-glycidoxypropyltrimethoxysilane Y-2: γ-ureidopropyltrimethoxysilane Y-3: ethyltriethoxysilane Y-4: γ-glycidoxypropylmethyldimethoxysilane Y-5: trimethyl Methoxysilane

In Table 2 and Table 3,
A-1 to A-12, AR-1 to AR-3: Modified inorganic cation colloid sol described in Table 1 B-1: Polyether-modified silicone (trade name TSF4440 manufactured by Momentive Performance Materials Japan) , HLB = 14)
B-2: Polyether-modified silicone (trade names KF-354L, HLB = 16 manufactured by Shin-Etsu Silicone)
B-3: Polyether-modified silicone (trade name KF-945 manufactured by Shin-Etsu Silicone, HLB = 4)
B-4: Polyether-modified silicone (trade names SH8400, HLB = 8 manufactured by Toray Dow Corning)
B-5: Polyether-modified silicone (trade name KF-6004 manufactured by Shin-Etsu Silicone, HLB = 9)
BR-1: Polydimethylsilicone (trade name KF-96 manufactured by Shin-Etsu Silicone)
BR-2: Long chain alkyl-modified silicone (trade name KF-412 manufactured by Shin-Etsu Silicone)

C-1: EO (ethylene oxide, same hereinafter) 10 mol PO (propylene oxide, same hereinafter) 10 mol random adduct of aliphatic mixed alcohol having 12 to 13 carbon atoms C-2: EO 10 mol adduct of lauryl alcohol C- 3: EO 9 mol adduct of aliphatic mixed secondary alcohol having 9 to 11 carbon atoms C-4: EO 14 mol adduct of oleyl alcohol C-5: EO 20 mol adduct of stearyl alcohol C-6: 14 to 15 carbon atoms PO-13 mole EO11 mole block adduct of aliphatic mixed alcohol of C-7: EO10 mole adduct of caprylic acid C-8: EO12 mole adduct of lauric acid C-9: EO13 mole adduct of stearic acid C-10: EO24 mol adduct of behenyl alcohol C-11: EO9 mol PO9 mollander of lauryl alcohol C-12: oleic acid PO 24 mol EO 24 mol block adduct C-13: oleic acid EO 13 mol adduct C-14: caprylamine ethylene oxide 4 mol adduct C-15: nonylphenol ethylene oxide 10 mol adduct C -16: 2-ethylhexyl alcohol ethylene oxide 100 mol adduct 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 20000)
D-2: Polyethylene glycol (trade name PEG-10000 manufactured by Sanyo Chemical Industries, number average molecular weight 11000)
D-3: Polyethylene glycol (trade name PEG-13000 manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 13000)
D-4: Polyethylene glycol (trade name PEG-6000P manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 8600)
D-5: Polyethylene glycol (number average molecular weight 28000)
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), trade name Pluronic F108NF, number average molecular weight 14600, manufactured by BASF))
D-8: ethylene oxide-propylene oxide random polymer (ethylene oxide / propylene oxide = 50/50 (molar ratio), number average molecular weight 3500)
D-9: Polyethylene glycol (number average molecular weight 40000)
D-10: ethylene oxide-propylene oxide block polymer (ethylene oxide / propylene oxide = 25/75 (molar ratio), number average molecular weight 1700)
D-11: Polyethylene glycol (number average molecular weight 50000)
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 Alcox R-150 manufactured by Meisei Chemical Industry Co., Ltd., number average molecular weight 150,000)

Test Category 2 (Manufacture of modified thermoplastic polymer film)
The ethylene / 1-butene copolymer (ethylene copolymer ratio 96%, density 0.930 g / cm ³ , MFR 1.0 g / 10 min) was subjected to an inflation molding machine equipped with a die having a diameter of 75 mm and a lip gap of 3 mm, Inflation molding was carried out under the conditions of a resin extrusion temperature of 200 ° C. and BUR = 1.8 to produce an olefin polymer film having a thickness of 150 μm. Next, the olefin polymer film is subjected to corona treatment discharge, the wet tension of the corona discharge treatment surface is set to 42 mN / m, and then the thermoplastic polymer film coating composition prepared in Test Category 1 on the corona discharge treatment surface. Was applied by a gravure coating method so as to have a solid content of 0.3 g / m ^2, and was allowed to stay in a warm air drying oven adjusted to 70 ° C. for 1 minute to obtain a modified thermoplastic polymer film of each example. .

Test category 3 (evaluation of modified thermoplastic polymer film)
・ Evaluation of drip properties The modified thermoplastic polymer film of each example manufactured in Test Category 2 was changed to a test house having an inclined surface of 15 degrees adjusted to an internal temperature of the house of 30 ° C. and an external temperature of the house of 10 ° C. 1 m ² nets, by observing the water droplets adhesion state to the initial (after 1 day) and long term (30 days), the water droplet prevention effect i.e. dripping property was evaluated according to the following criteria. The results are summarized in Table 4 and Table 5.

Evaluation criteria for flowability 5: No water droplet adhesion 4: Water droplet adhesion area of less than 10% 3: Water droplet adhesion area of 10% to less than 50% 2: Water droplet adhesion area of 50% to less than 80% 1: Water drop adhesion area is 80% or more

・ Evaluation of scratch resistance Each of the products manufactured in Test Category 2 by applying a 300 g load on the friction surface of the arm of a friction tester (Gakushin dyeing fastness tester manufactured by Daiei Kagaku Seisakusho Co., Ltd.) and applying a load of 300 g. After 10 reciprocating rubs on the coated surface 100 cm ² of the modified thermoplastic polymer film of the example, steam is applied to the rubbed part, and the degree of peeling of the coating film is observed by the cloudy part formed by water droplets attached, The peel resistance, that is, scratch resistance, of the coating film was evaluated according to the following criteria. The results are summarized in Table 4 and Table 5.

Evaluation criteria for scratch resistance 5: No peeling of the coating film 4: The peeling area of the coating film is less than 10% 3: The peeling area of the coating film is 10% to less than 50% 2: The peeling area of the coating film is 50% or more ~ Less than 80% 1: Stripped area of the coating is 80% or more

・ Evaluation of stickiness Two 20 cm × 20 cm square sample pieces were cut out from the modified thermoplastic polymer film of each example produced in Test Category 2, the application surfaces of the sample pieces were overlapped, and a load of 1 kg / m ² was applied. Evenly held at 50 ° C. for 24 hours, the stacked film is cut into 10 mm × 10 mm squares to form test pieces, and the peel strength between the two films, that is, the stickiness of the test pieces, based on the following criteria: evaluated. The results are summarized in Table 4 and Table 5.

Stickiness Evaluation Criteria 5: Peeling force is less than 50 mN / 10 mm 4: Peeling force is 50 mN / 10 mm or more to less than 100 mN / 10 mm 3: Peeling force is 100 mN / 10 mm or more to less than 150 cmN / 10 mm 2: Peeling force is 150 mN / 10 mm or more to Less than 200 mN / 10 mm 1: Peeling force is 200 mN / 10 mm or more

-Evaluation of liquid stability The state of separation when the thermoplastic polymer film coating composition of each example prepared in Test Category 1 was stored at room temperature 20 ° C in a sealed container was observed and separated. The liquid stability was evaluated according to the following criteria according to the time taken to complete. The results are summarized in Table 4 and Table 5.

Evaluation criteria of liquid stability 5: No separation for 24 hours or more 4: No separation for 12 hours or more to less than 24 hours 3: No separation for 6 hours or more to less than 12 hours 2: No separation for 2 hours or more to less than 6 hours 1: 2 hours Less than

-Evaluation of applicability The state of the application surface of the modified thermoplastic polymer film of each example produced in Test Category 2 was observed, and applicability was evaluated according to the following criteria. The results are summarized in Table 4 and Table 5.

Evaluation criteria for applicability 5: No unevenness or repellency occurred 4: Partial unevenness occurred 3: Unevenness occurred throughout the entire surface 2: Partial repellent occurred 1: Entire Repelling has occurred

As is apparent from the results of Tables 4 and 5 corresponding to Tables 2 and 3, when the composition of the present invention was applied, the drop performance of the droplets due to friction during film formation and stretching was small, and the film was stretched. It can be seen that it exhibits excellent dripping properties from the beginning, maintains excellent dripping properties for a long time after spreading, and has very little stickiness on the coated surface.

Claims

The following modified inorganic cation colloidal sol is 10 to 50 parts by mass of polyether-modified silicone, 2 to 30 parts by mass of the following polyoxyalkylene derivative, and a number average molecular weight of 1500 to 50000 with respect to 100 parts by mass in terms of solid content. A thermoplastic polymer film coating composition comprising polyalkylene glycol in a proportion of 45 to 75 parts by mass.
Modified inorganic cation colloid sol: Condensation polymer of the following silanol compound on solid content particles of the inorganic cation colloid sol described below, solid content of inorganic cation colloid sol / condensation polymer of silanol compound = 100/5 to 100/15 Modified inorganic cation colloid sol adhering at a ratio of (mass ratio) Inorganic cation colloid sol: 20 to 90 mass% in terms of solid content of cation alumina sol and 10 to 80 mass% in terms of solid content of cation silica sol (solid content) Inorganic cationic colloidal sol containing a total of 100% by mass) Silanol compound: Hydrolyzes at least one silanol-forming organosilane compound selected from trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes Processed Polyoxyalkylene derivative: A compound in which ethylene oxide is added in a proportion of 3 to 100 mol per mol of starting compound, a compound in which ethylene oxide and propylene oxide are added in a random manner in a proportion of 3 to 100 mol in total per mol of the following starting compound, and At least one selected from compounds in which ethylene oxide and propylene oxide are added in a block form in a proportion of 3 to 100 moles per mole of the starting compound below. Starting compound: aliphatic alcohol having 8 to 22 carbon atoms, carbon number 8-22 fatty acids, alkylphenols having 8-22 carbon atoms or monoalkylamines having 8-22 carbon atoms.
The composition for coating a thermoplastic polymer film according to claim 1, wherein the polyether-modified silicone has an HLB of 4 to 16.
The silanol compound is obtained by hydrolyzing at least one silanol-forming organic silane compound selected from γ-glycidoxypropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, methyltriethoxysilane, and ethyltriethoxysilane. The thermoplastic polymer film coating composition according to claim 1 or 2.
Polyoxyalkylene derivatives are compounds in which 5 to 50 moles of ethylene oxide are added per mole of the following starting compounds, and random in a ratio of 5 to 50 moles of ethylene oxide and propylene oxide per mole of the following starting compounds. The compound added in the form of a block and at least one selected from a compound in which ethylene oxide and propylene oxide are added in a block form in a ratio of 5 to 50 mol in total per mole of the following starting compound: The composition for thermoplastic polymer film coating according to any one of the above.
Starting compound: aliphatic alcohol having 8 to 22 carbon atoms or fatty acid having 8 to 22 carbon atoms
The polyalkylene glycol is at least one selected from polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random polymerized polymer and ethylene oxide-propylene oxide block polymerized polymer each having a number average molecular weight of 3000-40000. The thermoplastic polymer film coating composition according to any one of the preceding items.
The thermoplastic polymer film coating composition according to any one of claims 1 to 4, wherein the polyalkylene glycol is polyethylene glycol having a number average molecular weight of 6000 to 30,000.
The inorganic cationic colloidal sol contains a cationic alumina sol in a proportion of 50 to 80% by mass in terms of solid content and a cationic silica sol in a proportion of 20 to 50% by mass in terms of solid content (a total of 100% by mass in terms of solid content). Item 7. The thermoplastic polymer film coating composition according to any one of Items 1 to 6.
The modified inorganic cation colloid sol has a solid content particle of the inorganic cation colloid sol and a condensation polymer of silanol compound, the solid content of the inorganic cation colloid sol / condensation polymer of the silanol compound = 100/7 to 100/12 (mass ratio). The thermoplastic polymer film coating composition according to any one of claims 1 to 7, which is attached at a ratio of
Ratio of 20 to 40 parts by mass of polyether-modified silicone, 5 to 20 parts by mass of polyoxyalkylene derivative, and 50 to 70 parts by mass of polyalkylene glycol based on 100 parts by mass of the modified inorganic cation colloid sol The composition for coating a thermoplastic polymer film according to any one of claims 1 to 8, comprising
The manufacturing method of the composition for thermoplastic polymer film coating characterized by passing through the following 1st process and the following 2nd process.
First step: In the presence of the following inorganic cation colloid sol, the following silanol-forming organosilane compound in an amount of 5 to 15 parts by mass per 100 parts by mass of the solid content of the inorganic cation colloid sol is hydrolyzed. Further, a process of obtaining a modified inorganic cation colloid sol by condensation polymerization of the produced silanol compound Inorganic cation colloid sol: 20 to 90% by mass of cation alumina sol in terms of solid content and 10 to 80% by mass of cation silica sol in terms of solid content % (Total 100 mass% in terms of solid content) Inorganic cation colloidal sol Silanol-forming organosilane compound: at least one selected from trialkoxysilanes, dialkoxysilanes and monoalkoxysilanes Step 2: Solid content of the modified inorganic cation colloid sol obtained in Step 1 A ratio of 10 to 50 parts by mass of the polyether-modified silicone, 2 to 30 parts by mass of the following polyoxyalkylene derivative, and 45 to 75 parts by mass of a polyalkylene glycol having a number average molecular weight of 1500 to 50000 with respect to 100 parts by mass. To obtain a composition for coating a thermoplastic polymer film by polyoxyalkylene derivative: a compound to which 3 to 100 moles of ethylene oxide is added per mole of the following starting compound, per mole of the following starting compound A compound in which ethylene oxide and propylene oxide are randomly added at a ratio of 3 to 100 moles, and ethylene oxide and propylene oxide are added in a block form at a ratio of 3 to 100 moles per mole of the following starting compound. At least one selected from Compound: Aliphatic alcohol having 8 to 22 carbon atoms, fatty acid having 8 to 22 carbon atoms, alkylphenol having 8 to 22 carbon atoms in alkyl group, or monoalkylamine having 8 to 22 carbon atoms in alkyl group
The thermoplastic polymer film coating composition according to any one of claims 1 to 9 adheres to the corona discharge-treated surface of the thermoplastic polymer film in an amount of 0.1 to 2.0 g / m 2 as a solid content. A modified thermoplastic polymer film characterized in that:
The modified thermoplastic polymer film according to claim 11, which is a coated film for agriculture.
The manufacturing method of the modified thermoplastic polymer film characterized by passing through the following 1st process and the following 2nd process.
1st process: The process which corona discharge-processes to a thermoplastic polymer film, and sets the wetting tension of a corona discharge process surface to 35 mN / m or more 2nd process: The corona discharge of the thermoplastic polymer film obtained at the 1st process A step of applying the thermoplastic polymer film coating composition according to any one of claims 1 to 10 to a treated surface so that the solid content is 0.1 to 2.0 g / m 2.