CN107922754B - Composition for coating thermoplastic polymer film, method for producing the composition, modified thermoplastic polymer film, and method for producing the modified thermoplastic polymer film - Google Patents
Composition for coating thermoplastic polymer film, method for producing the composition, modified thermoplastic polymer film, and method for producing the modified thermoplastic polymer film Download PDFInfo
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
The invention provides a composition for coating a thermoplastic polymer film, a method for producing a modified thermoplastic polymer film using the composition, and a modified thermoplastic polymer film obtained by the production method, wherein the composition is less in drop performance reduction due to friction during film formation or spreading, exhibits excellent drop performance from the initial stage of spreading, maintains excellent drop performance for a long period of time even after spreading, and is less sticky on the film surface coated with drop agent. A composition for coating a thermoplastic polymer film, which comprises a specific modified inorganic cationic colloidal sol obtained by hydrolyzing a specific inorganic cationic colloidal sol with a specific silanol-forming organic silane compound, wherein the specific modified inorganic cationic colloidal sol contains a polyether-modified silicone, a specific polyoxyalkylene derivative and a polyalkylene glycol having a number average molecular weight of 1500-50000 at a specific ratio.
Description
Technical field
The present invention relates to a kind of thermal plastic high polymer film coating composition, the composition manufacturing method, used this
The modified thermoplastic polymeric membrane of composition and the manufacturing method of the modified thermoplastic polymeric membrane, because making in the factory
The reduction of drip performance caused by friction when film or spreading into agricultural booth is few, plays from the initial stage sprawled excellent
Anti-drop property even if maintaining excellent anti-drop property for a long time after sprawling, and then is coated with obtained film surface also few stickness.
Background technique
In the past, as thermal plastic high polymer film coating composition, propose using alumina sol, acidic silicasol,
The composition (for example, with reference to patent document 1) of organic silane derivative and nonionic surfactant, using colloidal alumina,
The motions such as the composition (for example, with reference to patent document 2) of cabosil and polyethylene glycol.But these existing thermoplasticity
In polymeric membrane coating composition have due to being film-made in the factory when or friction when spreading into agricultural booth and make film
The problems such as drip performance reduces or further makes the coated face stickness of film.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 62-241984 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2000-160146 bulletin
Summary of the invention
Problems to be solved by the invention
Project to be solved by this invention is to provide a kind of thermal plastic high polymer film coating composition, the composition
The manufacturer of manufacturing method, the modified thermoplastic polymeric membrane for having used the composition and the modified thermoplastic polymeric membrane
The reduction of method, the drip performance caused by friction when because being film-made or when sprawling is few, plays from the initial stage sprawled excellent
Anti-drop property even if maintaining excellent anti-drop property for a long time after sprawling, and then is coated with the film surface of drip agent also few stickness.
The means to solve the problem
The present inventor is studied in order to solve the above problems, as a result, it has been found that, following thermal plastic high polymer film coatings
Strictly suitable with composition, which is relative to the specific silanol chemical combination of utilization
Modified inorganic cationic colloidal colloidal sol made of the condensation polymer of object is modified specific inorganic cationic colloidal colloidal sol,
It is at a specific ratio 1500~50000 containing polyether modified silicone, specific polyoxyalkylene derivative and number-average molecular weight
Made of ployalkylene glycol.
That is, the present invention relates to a kind of thermal plastic high polymer film coating compositions, which is characterized in that it is relative to solid
Body ingredient is scaled following modified inorganic cationic colloidal colloidal sols of 100 mass parts, is contained with the ratio of 10~50 mass parts poly-
Ether modified silicone contains following polyoxyalkylene derivatives and with the ratio of 2~30 mass parts with the ratio of 45~75 mass parts
Made of the ployalkylene glycol that example is 1500~50000 containing number-average molecular weight.The invention further relates to the manufacturers of the composition
The manufacturing method of method, the modified thermoplastic polymeric membrane for having used the composition and the modified thermoplastic polymeric membrane.
Modified inorganic cationic colloidal colloidal sol: the condensation polymer of following silanol compounds is made to be attached to following inorganic sun
Modified inorganic cationic colloidal colloidal sol made of on the solid component particle of Ionic colloid colloidal sol, the ratio of attachment be inorganic sun from
Solid component/silanol compound condensation polymer=100/5~100/15 (mass ratio) of sub- colloid solution.
Inorganic cationic colloidal colloidal sol: the cationic oxidation containing the ratio for being scaled 20~90 mass % with solid component
Aluminum sol and the ratio that 10~80 mass % (100 mass % are added up to solid component conversion) is scaled with solid component
Cationic colloidal silica made of inorganic cationic colloidal colloidal sol.
Silanol compound: in trialkoxysilanes, dialkoxy silicane class and monoalkoxysilane class
Compound made of at least one silanol formative organic silane compound is hydrolyzed.
Polyoxyalkylene derivative: selected from least one of following compounds: relative to every 1 mole of following initial compounds
Compound made of addition is carried out with the ratio that ethylene oxide is 3~100 moles；Relative to every 1 mole of following initial compounds
Compound made of random addition is carried out with the ratio that ethylene oxide and propylene oxide add up to 3~100 moles；And relative to
Every 1 mole of following initial compounds with ethylene oxide and propylene oxide add up to 3~100 moles ratio carry out block addition and
At compound.
Initial compounds: aliphatic alcohol that carbon atom number is 8~22, the fatty acid that carbon atom number is 8~22, alkyl carbon
The monoalkylamine that the carbon atom number of alkyl phenol or alkyl that atomicity is 8~22 is 8~22.
Thermal plastic high polymer film coating composition (composition hereinafter referred to as of the invention) of the invention is carried out first
Explanation.Composition of the invention is relative to the above-mentioned modified inorganic cationic colloidal for being scaled 100 mass parts with solid component
Colloidal sol is contained polyether modified silicone with the ratio of 10~50 mass parts, is contained above-mentioned polyoxy with the ratio of 2~30 mass parts
Change ene derivative and with the ratio of 45~75 mass parts contain number-average molecular weight be 1500~50000 ployalkylene glycol and
At, preferably relative to the modified inorganic cationic colloidal colloidal sol for being scaled 100 mass parts with solid component, with 20~40 matter
The ratio of amount part contains polyether modified silicone, contain above-mentioned polyoxyalkylene derivative with the ratio of 5~20 mass parts and with
The ratio of 50~70 mass parts contains made of ployalkylene glycol.
The modified inorganic cationic colloidal colloidal sol being provided in composition of the invention is to make specific silanol chemical combination
Made of the condensation polymer of object is attached on the solid component particle of specific inorganic cationic colloidal colloidal sol, the ratio of attachment
For solid component/silanol compound condensation polymer=100/5~100/15 (quality of inorganic cationic colloidal colloidal sol
Than).
The inorganic cationic colloidal colloidal sol of raw material as above-mentioned modified inorganic cationic colloidal colloidal sol is containing with solid
Ingredient is scaled the cationic oxidation Aluminum sol of the ratio of 20~90 mass % and is scaled 10~80 matter with solid component
Made of the cationic colloidal silica of the ratio of amount % (adding up to 100 mass % with solid component conversion), preferably containing with solid
Body ingredient is scaled the cationic oxidation Aluminum sol of the ratio of 50~80 mass % and is scaled 20~50 matter with solid component
Made of the cationic colloidal silica of the ratio of amount % (adding up to 100 mass % with solid component conversion).
Cationic oxidation Aluminum sol is so-called colloidal alumina, can directly be used with the commercially available object of aqueous dispersion
Product.As such commercially available product, for example, alumina sol 100, alumina sol 200, alumina sol 520 (with
On be the manufacture of Nissan Chemical society trade name), Cataloid AS-1, Cataloid AS-2 (be above day to wave catalyst
The trade name manufactured at society) etc..
Cationic colloidal silica can also be used directly with the commercially available article of aqueous dispersion.As such commercially available product,
For example, Snowtex AK, Snowtex AK-L (being above the trade name of Nissan Chemical society manufacture), Cataloid
SN (trade name for waving the manufacture of catalyst chemical conversion society day), Quartron PL-3-C (trade name of Japan's chemical industry corporation manufacture) etc..
It is attached to the solid component particle (colloidal solid of aluminium oxide, silica) of the inorganic cationic colloidal colloidal sol
The condensation polymer of the silanol compound on surface can be by hydrolyzing silanol formative organic silane compound and to institute
The silanol compound of generation carries out condensation polymerization and obtains.About details, as described below, in above-mentioned inorganic cation
Silanol formative organic silane compound is hydrolyzed in the presence of colloid solution, then the silanol compound of generation is carried out
Condensation polymerization, thus, it is possible to obtain the condensation polymer of silanol compound be attached to the solid of inorganic cationic colloidal colloidal sol at
Divide modified inorganic cationic colloidal colloidal sol made of on particle.
In the modified inorganic cationic colloidal colloidal sol being supplied in composition of the invention, the contracting of silanol compound
Close the surface of solid component particle of the polymer to cover inorganic cationic colloidal colloidal sol it is all or part of in the form of adhere to,
The solid component particle of part of it and inorganic cationic colloidal colloidal sol is chemically bonded by inference.The modified inorganic cationic colloidal
In colloidal sol, the condensation polymer of silanol compound is with solid component/silanol compound of inorganic cationic colloidal colloidal sol
The ratio of condensation polymer=100/5~100/15 (mass ratio) is attached to the solid component of inorganic cationic colloidal colloidal sol
On grain, preferably with solid component/silanol compound condensation polymer=100/7~100/ of inorganic cationic colloidal colloidal sol
The ratio of 12 (mass ratioes) is attached on the particle.
As the polyether modified silicone being supplied in composition of the invention, commercially available product can be directly used.As this
The commercially available product of sample, for example, TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (more than
Be Japan Momentive Performance Materials society manufacture trade name), X22-4952, X-22-4272,
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 (being above the trade name of silicone society, SHIN-ETSU HANTOTAI manufacture),
SH8700, SH8410, SH8400, L-7002, FZ-2104, FZ-77, L-7604, FZ-2203, FZ-2208 (are above
The trade name of Toray Dow Corning society manufacture) etc., wherein it is preferred that TSF4440, KF-354L, KF-945, SH8400, KF-
The polyether modified silicone that 6004 equal HLB are 4~16.
Being fed into the polyoxyalkylene derivative in composition of the invention is the addition oxygen on following initial compounds
Change compound made of compound made of ethylene, and/or addition ethylene oxide and propylene oxide, in addition ethylene oxide and oxygen
It can be any structure in block addition or random addition in the case where changing propylene.In addition, about addition molal quantity, phase
For following 1 mole of initial compounds, ethylene oxide or ethylene oxide and propylene oxide add up to 3~100 moles ratio,
Preferably 5~50 moles of ratio.
Initial compounds: aliphatic alcohol that carbon atom number is 8~22, the fatty acid that carbon atom number is 8~22, alkyl carbon
The monoalkylamine that the carbon atom number of alkyl phenol or alkyl that atomicity is 8~22 is 8~22.
As the carbon atom number in initial compounds be 8~22 aliphatic alcohol, can enumerate octanol, 2-Ethylhexyl Alcohol,
Nonyl alcohol, decyl alcohol, undecyl alcohol, the secondary alcohol that carbon atom number is 9~11, laruyl alcohol, tridecyl alcohol, myristyl alcohol, pentadecane
Base alcohol, cetyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, ricinoleyl alcohol, docosyl alcohol etc..In addition, as carbon atom number be 8~
22 fatty acid can enumerate octanoic acid, n-nonanoic acid, capric acid, lauric acid, tetradecylic acid, palmitoleic acid, stearic acid, isostearic acid, oil
Acid, linoleic acid, arachic acid, behenic acid etc..In turn, the alkyl phenol for being 8~22 as the carbon atom number of alkyl, can enumerate pungent
Base phenol, nonyl phenol, decyl phenol, dodecylphenol, octadecyl phenol etc..In turn, the list for being 8~22 as the carbon atom number of alkyl
Alkylamine can enumerate octylame, nonyl amine, decyl amine, lauryl amine, tridecyl amine, nutmeg amine, stearylamine, oleyl amine, docosane
Base amine etc..Wherein, as initial compounds, preferably carbon atom number be 8~22 aliphatic alcohol, carbon atom number be 8~22 rouge
Fat acid.
Specifically, the ethylene oxide adduct for the aliphatic alcohol for being 8~22 as carbon atom number, can enumerate octanol
5 moles of additions of ethylene oxide of 5 moles of addition products of ethylene oxide, 100 moles of addition products of ethylene oxide of 2-Ethylhexyl Alcohol, nonyl alcohol
9 moles of additions of ethylene oxide of object, 30 moles of addition products of ethylene oxide of undecyl alcohol, the secondary alcohol that carbon atom number is 9~12
Object, 10 moles of addition products of ethylene oxide of laruyl alcohol, 50 moles of addition products of ethylene oxide of palmityl alcohol, stearyl alcohol ethylene oxide
20 moles of addition products, 20 moles of addition products of ethylene oxide of isooctadecanol, oleyl alcohol ethylene oxide 14 moles of addition products, docosyl alcohols
24 moles of addition products of ethylene oxide etc., the aliphatic alcohol for being 8~22 as carbon atom number shares ethylene oxide and oxidation third
The addition product of alkene can enumerate the random addition product of 10 moles of 10 mole propylene oxide of ethylene oxide of octanol, 2-Ethylhexyl Alcohol
Ethylene oxide 30 mole propylene oxide, 20 moles of random additions of 30 mole ethylene oxide of propylene oxide, 30 moles of addition products, decyl alcohol
Object, the random addition product of 9 moles of 9 mole propylene oxide of ethylene oxide of dodecyl alcohol, tridecyl alcohol ethylene oxide 10 rub
Your 10 moles of propylene oxide random addition products, myristyl alcohol 13 mole ethylene oxide of propylene oxide, 10 moles of block addition products,
13 mole ethylene oxide of propylene oxide, 11 moles of block addition products of myristyl alcohol, the propylene oxide 13 of pentadecyl alcohol rub
Your 10 moles of block addition products of ethylene oxide etc..
In addition, specifically, the ethylene oxide adduct for the fatty acid for being 8~22 as carbon atom number, can enumerate pungent
10 moles of addition products of ethylene oxide of acid, 12 moles of addition products of lauric ethylene oxide, 5 moles of ethylene oxide of palmitinic acid plus
At object, 13 moles of addition products of stearic ethylene oxide, 13 moles of addition products of ethylene oxide of oleic acid etc., it is as carbon atom number
The ethylene oxide of 8~22 fatty acid and the addition product of propylene oxide can enumerate 10 moles third of ethylene oxide of octanoic acid
10 moles of alkene random addition products, the random addition product of 10 moles of 40 mole propylene oxide of ethylene oxide of capric acid alcohol, laurel acid alcohol
10 moles of 13 mole ethylene oxide of propylene oxide of the random addition product of 10 moles of 10 mole propylene oxide of ethylene oxide, tetradecylic acid
Block addition product, 13 mole ethylene oxide of propylene oxide, 10 moles of block addition products of pentadecanoic acid, oleic acid propylene oxide 24
24 moles of block addition products of mole ethylene oxide, random addition product of 10 moles of 10 propylene oxide of ethylene oxide of behenic acid etc..
More specifically, the ethylene oxide adduct for the alkyl phenol for being 8~22 as the carbon atom number of alkyl, can enumerate
3 moles of addition products of ethylene oxide of octyl phenol, 10 moles of addition products of ethylene oxide of nonyl phenol, decyl phenol ethylene oxide 12 rub
Your addition product, 100 moles of addition products of ethylene oxide of dodecylphenol etc., the alkyl that the carbon atom number as alkyl is 8~22
The ethylene oxide of phenol and the addition product of propylene oxide can enumerate ethylene oxide 50 mole propylene oxide, 10 moles of nothings of octyl phenol
Advise addition product, the random addition product of 35 moles of 10 mole ethylene oxide of propylene oxide of nonyl phenol, 3 moles of propylene oxide of decyl phenol
10 moles of block block addition products of ethylene oxide, octadecyl phenol 80 moles of 10 mole ethylene oxide of propylene oxide it is random plus
At object etc..
More specifically, the ethylene oxide adduct for the monoalkylamine for being 8~22 as the carbon atom number of alkyl, Ke Yiju
The ethylene oxide 20 of 4 moles of addition products of the ethylene oxide of octylame, 10 moles of addition products of ethylene oxide of lauryl amine, nutmeg amine out
Mole addition product, 45 moles of addition products of ethylene oxide of stearylamine etc., the monoalkylamine that the carbon atom number as alkyl is 8~22
Ethylene oxide and propylene oxide addition product, can enumerate octylame 10 moles of 20 mole propylene oxide of ethylene oxide it is random plus
At 10 mole oxygen of propylene oxide of object, the random addition product of 10 moles of 10 mole propylene oxide of ethylene oxide of lauryl amine, palmitamide
Change 20 mole ethylene oxide of propylene oxide 60 moles of block addition products, 22 of 20 moles of block addition products of ethylene, stearylamine
20 5 moles of block addition products of mole propylene oxide of ethylene oxide of alkylamine etc..
Wherein, as polyoxyalkylene derivative, preferably carbon atom number be 8~22 aliphatic alcohol ethylene oxide addition
The rouge that the ethylene oxide and the addition product of propylene oxide, carbon atom number for the aliphatic alcohol that object, carbon atom number are 8~22 are 8~22
The ethylene oxide for the fatty acid that the ethylene oxide adduct and carbon atom number of fat acid are 8~22 and the addition product of propylene oxide,
And relative to 1 mole of initial compounds, with ethylene oxide or ethylene oxide and propylene oxide add up to 5~50 moles of ratio into
Row addition.Specifically, 10 moles of additions of ethylene oxide of decyl alcohol can be enumerated as the preferred polyoxyalkylene derivative
Object, 10 moles of addition products of ethylene oxide of laruyl alcohol, the secondary alcohol that carbon atom number is 9~12 9 moles of addition products of ethylene oxide, hard
20 moles of addition products of ethylene oxide of lipidol, 14 moles of addition products of ethylene oxide of oleyl alcohol, dodecyl alcohol ethylene oxide 10
10 moles of mole propylene oxide random addition products, tridecyl alcohol 10 moles of 10 mole propylene oxide of ethylene oxide it is random plus
It rubs at 13 mole ethylene oxide of propylene oxide, 11 moles of block addition products, the lauric ethylene oxide 12 of object, myristyl alcohol
That addition product, 13 moles of addition products of stearic ethylene oxide, 13 moles of addition products of ethylene oxide of oleic acid, stearic oxidation
Propylene oxide 24 mole ethylene oxide, 24 moles of block addition products of the random addition product of 9 moles of 9 mole propylene oxide of ethylene, oleic acid
Deng.
The ployalkylene glycol for being 1500~50000 as the number-average molecular weight being fed into composition of the invention, can
To enumerate the polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide atactic polymerization that number-average molecular weight is 1500~50000
Object, ethylene oxide-propylene oxide block polymer etc., wherein preferred number average molecular weight be 3000~40000 polyethylene glycol,
Polypropylene glycol, ethylene oxide-propylene oxide atactic polymer, ethylene oxide-propylene oxide block polymer, more preferably number are divided equally
The polyethylene glycol that son amount is 6000~30000.Number-average molecular weight can be calculated by hydroxyl value, and hydroxyl value can utilize to be remembered in JIS K0070
The method of load is found out.
Then to the manufacturing method (group hereinafter referred to as of the invention of thermal plastic high polymer film coating composition of the invention
Close the manufacturing method of object) it is illustrated.The manufacturing method of composition of the invention is following 1st processes of experience and the 2nd process
Manufacturing method.
1st process: in the presence of following inorganic cationic colloidal colloidal sols, to following silanol formative organic-silylations
It closes object to be hydrolyzed, further makes silanol compound condensation polymerization generated, obtain modified inorganic cationic colloidal
The process of colloidal sol, in hydrolysis process, the solid component of the inorganic cationic colloidal colloidal sol relative to every 100 mass parts,
The amount of the silanol formative organic silane compound is 5~15 mass parts ratios.
Inorganic cationic colloidal colloidal sol: the cationic oxidation containing the ratio for being scaled 20~90 mass % with solid component
Aluminum sol and the ratio that 10~80 mass % (100 mass % are added up to solid component conversion) is scaled with solid component
Cationic colloidal silica made of inorganic cationic colloidal colloidal sol.
Silanol formative organic silane compound: selected from trialkoxysilanes, dialkoxy silicane class and single alcoxyl
At least one of base silane class.
2nd process: relative to the modified inorganic cation obtained by process 1 for being scaled 100 mass parts with solid component
Colloid solution, with the ratio mixture polyether modified silicone of 10~50 mass parts, with the following polyoxies of ratio mixture of 2~30 mass parts
The ployalkylene glycol changed ene derivative and be 1500~50000 with the ratio mixture number-average molecular weight of 45~75 mass parts, obtains
To the process of thermal plastic high polymer film coating composition.
Polyoxyalkylene derivative: selected from least one of following compounds: relative to every 1 mole of following initial compounds
Compound made of addition is carried out with the ratio that ethylene oxide is 3~100 moles；Relative to every 1 mole of following initial compounds
Compound made of random addition is carried out with the ratio that ethylene oxide and propylene oxide add up to 3~100 moles；And relative to
Every 1 mole of following initial compounds with ethylene oxide and propylene oxide add up to 3~100 moles ratio carry out block addition and
At compound.
Initial compounds: aliphatic alcohol that carbon atom number is 8~22, the fatty acid that carbon atom number is 8~22, alkyl carbon
The monoalkylamine that the carbon atom number of alkyl phenol or alkyl that atomicity is 8~22 is 8~22.
In the manufacturing method of composition of the invention, the inorganic cationic colloidal colloidal sol used in the 1st process is as above
It is described.It as silanol formative organic silane compound used in the 1st process, can enumerate: 1) methyl trimethoxy oxygroup silicon
Alkane, methyltriethoxysilane, vinyl trichlorosilane, vinyltriethoxysilane, vinyl three (methoxy ethoxy)
Silane, γ-chloropropyl tripropoxy silane, γ-Mercaptopropyltriethoxysilane, γ-glycidoxypropyl group trimethoxy
Silane, γ-methacryloxypropyl, γ-urea propyl trimethoxy silicane, phenyltrimethoxysila,e
Etc. trialkoxysilanes, 2) dimethyldimethoxysil,ne, gamma-chloropropylmethyldimethoxysilane, γ-glycidoxy
The single alcoxyl of the dialkoxy silicanes such as hydroxypropyl methyl dimethoxysilane class, 3) trim,ethylchlorosilane, trimethylmethoxysilane etc.
Base silane class etc..Wherein preferred γ-glycidoxypropyltrime,hoxysilane, γ-urea propyl trimethoxy silicane, methyl three
Ethoxysilane, ethyl triethoxysilane.
In the manufacturing method of composition of the invention, the solid of inorganic cationic colloidal colloidal sol used in the 1st process
The mass ratio of ingredient and silanol formative organic silane compound with about inorganic cationic colloidal colloidal sol solid component with
The above situation of the mass ratio of the condensation polymer of silanol compound is identical, in addition, the polyethers used in the 2nd process changes
Property silicone, polyoxyalkylene derivative and ployalkylene glycol, also include they ratio it is as described above.
Then modified thermoplastic polymeric membrane (film hereinafter referred to as of the invention) of the invention is illustrated.Of the invention
Film is to adhere to be calculated as 0.1~2.0g/m with solid component in the Corona discharge Treatment face of thermal plastic high polymer film2Above-mentioned hair
Made of bright composition.
As thermal plastic high polymer film, 1) polyolefin-based resins, 2) polyvinyl chloride, vinyl chloride-metering system can be enumerated
The chlorine such as sour methyl terpolymer, polyvinylidene chloride system resin, 3) polyethylene terephthalate gather to naphthalenedicarboxylic acid ethylene glycol
Whole thermoplastic resins that polyester based resins such as ester etc. are used as plastic film for agricultural use.As polyolefin-based resins, α-alkene can be enumerated
The homopolymer of hydrocarbon, using alpha-olefin as the copolymer with heterobifunctional monomer of principal component, for example, polyethylene, polypropylene, second
The ethene-alpha-olefin copolymers, second such as alkene-butylene copolymer, ethylene-4- methyl-1-pentene copolymer, ethylene-hexene co-polymers
Alkene-vinyl acetate copolymer, ethylene methyl methacrylate copolymer, ethane-acetic acid ethyenyl ester-methyl methacrylate
Copolymer, ionomer resin etc..These resins can according to need containing usually used antioxidant, weather resisting agent, ultraviolet light
Absorbent, infrared absorbent, lubricant, anti-blocking agent, antifoggant, heat preserving agent, pigment etc..It is resin-molded into as by these
The method of film is not particularly limited, for example, film blowing, T mold forming method etc..The resin used when molding can be with
For the blend of two or more resins.In addition, film can be single layer or multilayer, group can be carried out according to purpose use
It closes and forms obtained film.
The effect that the purposes of film of the invention is not particularly limited, but is embodied for agricultural mulch films
Significantly.
Finally to the manufacturing method (manufacturer of film hereinafter referred to as of the invention of modified thermoplastic polymeric membrane of the invention
Method) it is illustrated.The manufacturing method of film of the invention is to undergo the manufacturing method of following 1st processes and following 2nd processes.
1st process: Corona discharge Treatment is carried out to thermal plastic high polymer film, makes the wetting tension in Corona discharge Treatment face
The process of 35mN/m or more.
2nd process: for the Corona discharge Treatment face of the thermal plastic high polymer film obtained by the 1st process, according to solid
Ingredient is calculated as 0.1~2.0g/m2The process for being coated with the composition of aforementioned present invention.
It is as described above about thermal plastic high polymer film in the manufacturing method of film of the invention.1st process is to thermoplasticity
Polymeric membrane carries out Corona discharge Treatment, makes the process of the wetting tension 35mN/m or more in Corona discharge Treatment face, but soak
When tension is in the range of 35~70mN/m, it is easy to show effect, is preferred.In the present invention, wetting tension is basis
The value that the record measurement of JIS-K6768 obtains.
In addition, the 2nd process is the Corona discharge Treatment face of the thermal plastic high polymer film for being obtained by the 1st process, according to
0.1~2.0g/m is calculated as with solid component2The process for being coated with the composition of aforementioned present invention.It is coated with by composition of the invention
When to thermal plastic high polymer film, well known rubbing method can be used.Wherein, for example, spray coating method, Dipcoat method, roller coating
Method, scraper for coating method, wire rod rubbing method, air knife coating method etc..
The effect of invention
Present invention mentioned above has following effects: the drop of the drip performance caused by friction when because being film-made or when sprawling
It is low few, excellent anti-drop property is played from the initial stage sprawled, even if maintaining excellent anti-drop property for a long time after sprawling, in turn
It is coated with the film surface of drip agent also few stickness.
Specific embodiment
Embodiment
Hereinafter, having enumerated embodiment etc., but the present invention is not limited to this to keep composition and effect of the invention more specific
A little embodiments.It should be noted that part refers to mass parts in embodiment below and comparative example, in addition % refers to quality %.
Test classification 1 (manufacture of thermal plastic high polymer film coating composition)
Embodiment 1
By 68.1 parts of water, 341.5 parts of cationic oxidation Aluminum sol (X1-1) (solid component converts 70 parts) and cationic silicon
130.4 parts of colloidal sol (X2-1) (solid component converts 30 parts) mixing, prepares inorganic cationic colloidal colloidal sol.In the inorganic cation
10 parts of mixed silanes alcohol formative organic silane compound (Y-1) in colloid solution, prepare solid component concentration be 20% it is mixed
Liquid is closed, is stirred 5 hours at 50 DEG C, silanol formative organic silane compound (Y-1) is hydrolyzed, institute is further made
The silanol compound of generation carries out condensation polymerization, has obtained modified inorganic cationic colloidal colloidal sol (A-1).Modified inorganic sun
Ionic colloid colloidal sol (A-1) is that the condensation polymer of silanol compound is made to be attached to consolidating for above-mentioned inorganic cationic colloidal colloidal sol
Made of on body ingredient granules.Next, in the modified inorganic cationic colloidal colloidal sol (A-1) in terms of solid component conversion
9400 parts of water, 30 parts of polyether modified silicone (B-1), 10 parts of polyoxyalkylene derivative (C-1) and poly- alkylene two are added in 100 parts
60 parts of alcohol (D-1) is simultaneously stirred, and has obtained the thermal plastic high polymer film coating composition that solid component concentration is 2%.
Embodiment 2~37 and comparative example 1~15
Modified inorganic cationic colloidal colloidal sol (A-2)~(A-12) and (AR-1) are prepared as with the case where embodiment 1
~(AR-3) has further obtained the thermal plastic high polymer film coating composition of embodiment 2~37 and comparative example 1~15.It will
Table 1 is listed in by the content aggregation of the modified inorganic cationic colloidal colloidal sol of above each example preparation, and will be obtained by above each example
The content aggregation of thermal plastic high polymer film coating composition is listed in table 2 and table 3.
[table 1]
In table 1,
X1-1: the trade name Alumina Sol 520 of Nissan Chemical Industries society manufacture
X1-2: the trade name Alumina Sol 200 of Nissan Chemical Industries society manufacture
X1-3: the trade name CataloidAS-1 of catalyst chemical conversion society manufacture is waved day
X2-1: the trade name Snowtex AK of Nissan Chemical Industries society manufacture
X2-2: the trade name CataloidSN of catalyst chemical conversion society manufacture is waved day
X2-3: the trade name Quartron PL-3-C of Japan's chemical industry corporation manufacture
Y-1: γ-glycidoxypropyltrime,hoxysilane
Y-2: γ-urea propyl trimethoxy silicane
Y-3: ethyl triethoxysilane
Y-4: γ-epoxy propoxy propyl methyl dimethoxysilane
Y-5: trimethylmethoxysilane
[table 2]
[table 3]
In table 2 and table 3,
A-1~A-12, AR-1~AR-3: modified inorganic cationic colloidal colloidal sol recorded in table 1
B-1: the polyether modified silicone (trade name of Japan Momentive Performance Materials society manufacture
TSF4440, HLB=14)
B-2: polyether modified silicone (trade name KF-354L, HLB=16 of silicone society, SHIN-ETSU HANTOTAI manufacture)
B-3: polyether modified silicone (trade name KF-945, HLB=4 of silicone society, SHIN-ETSU HANTOTAI manufacture)
B-4: polyether modified silicone (trade name SH8400, HLB=8 of Toray Dow Corning society manufacture)
B-5: polyether modified silicone (trade name KF-6004, HLB=9 of silicone society, SHIN-ETSU HANTOTAI manufacture)
BR-1: polydimethylsiloxane (the trade name KF-96 of silicone society, SHIN-ETSU HANTOTAI manufacture)
BR-2: long chain alkyl modified silicone (the trade name KF-412 of silicone society, SHIN-ETSU HANTOTAI manufacture)
C-1: the 10 moles of PO (oxygen of EO (ethylene oxide, same as below) for the aliphatic mixed alcohol that carbon atom number is 12~13
Change propylene, same as below) 10 moles of random addition products
C-2: EO10 moles of addition product of lauryl alcohol
C-3: the aliphatic that carbon atom number is 9~11 mixes EO9 moles of addition product of secondary alcohol
C-4: EO14 moles of addition product of oleyl alcohol
C-5: EO20 moles of addition product of stearyl alcohol
C-6: the PO13 moles of EO11 moles of block addition product for the aliphatic mixed alcohol that carbon atom number is 14~15
C-7: EO10 moles of sad addition product
C-8: lauric EO12 moles of addition product
C-9: stearic EO13 moles of addition product
C-10: EO24 moles of addition product of docosyl alcohol
C-11: EO9 moles of PO9 moles of random addition product of laruyl alcohol
C-12: PO24 moles of EO24 moles of block addition product of oleic acid
C-13: EO13 moles of addition product of oleic acid
C-14: 4 moles of addition products of ethylene oxide of octylame
C-15: 10 moles of addition products of ethylene oxide of nonyl phenol
100 moles of addition products of ethylene oxide of C-16:2- ethyl hexanol
CR-1: methanol
CR-2: ethylene glycol
D-1: polyethylene glycol (the trade name PEG-20000 of chemical conversion industry society, Sanyo manufacture, number-average molecular weight 20000)
D-2: polyethylene glycol (the trade name PEG-10000 of chemical conversion industry society, Sanyo manufacture, number-average molecular weight 11000)
D-3: polyethylene glycol (the trade name PEG-13000 of chemical conversion industry society, Sanyo manufacture, number-average molecular weight 13000)
D-4: polyethylene glycol (the trade name PEG-6000P of chemical conversion industry society, Sanyo manufacture, number-average molecular weight 8600)
D-5: polyethylene glycol (number-average molecular weight 28000)
D-6: ethylene oxide-propylene oxide atactic polymer (divide equally by ethylene oxide/propylene oxide=4/1 (molar ratio), number
Son amount is 10000)
D-7: ethylene oxide-propylene oxide block polymer (ethylene oxide/propylene oxide/ethylene oxide=141/44/
141 (molar ratios), trade name Pluronic F108NF of BASF society manufacture, number-average molecular weight 14600)
D-8: (ethylene oxide/propylene oxide=50/50 (molar ratio), number are equal for ethylene oxide-propylene oxide atactic polymer
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 (the trade name PEG-400 of chemical conversion industry society, Sanyo manufacture, number-average molecular weight 400)
DR-2: polyethylene glycol (bright trade name Alkox R-150 at chemical industry corporation manufacture, number-average molecular weight
150000)
Test classification 2 (manufacture of modified thermoplastic polymeric membrane)
By ethylene butene-1 copolymer (ethylene copolymer ratio 96%, density 0.930g/cm3, MFR1.0g/10 minutes)
It is supplied in the inflation forming machine for being equipped with the die head of diameter 75mm, die lip gap 3mm, in 200 DEG C of resin extruded temperature and BUR
Inflation molding is carried out under conditions of=1.8, produces the olefin polymer films with a thickness of 150 μm.Next, to the olefinic polymerization
Object film implements sided corona treatment electric discharge, after making the wetting tension 42mN/m in Corona discharge Treatment face, will be tried using gravure coating method
It tests the thermal plastic high polymer film coating composition prepared in classification 1 and is calculated as 0.3g/m according to solid component2It is applied to the electricity
Corona process face stops 1 minute in the hot-air drying stove that temperature is adjusted to 70 DEG C, and the modified thermoplastic for having obtained each example is high
Molecular film.
Test classification 3 (evaluation of modified thermoplastic polymeric membrane)
The evaluation of anti-drop property
The modified thermoplastic polymeric membrane of each example manufactured in test classification 2 is being adjusted in greenhouse warm 30 DEG C, greenhouse
1m is unfolded on the detection greenhouse with 15 degree of inclined surface of 10 DEG C of outer temperature2, observe water (after 1 day) and for a long time (after 30 days) in the early stage
Attachment is dripped, with following benchmark evaluation preventing water drops effect, i.e. anti-drop properties.Result is summarized and is listed in table 4 and table 5.
The evaluation criteria of anti-drop property
5: no water droplet attachment
4: water droplet bond area is less than 10%
3: water droplet bond area be 10% or more~less than 50%
2: water droplet bond area be 50% or more~less than 80%
1: water droplet bond area is 80% or more
The evaluation of marresistance
In the arm of frictional testing machine (vibration shape colorfastness testing machine of the smart mechanism Zuo Suo society manufacture of Daiei science)
Vinyl tape is pasted on rubbing surface, applies the load of 300g, the modified thermoplastic of each example manufactured in test classification 2
The coated face 100cm of polymeric membrane2After upper reciprocating friction 10 times, the part after making friction is contacted with hot vapour, by by water droplet
Attachment and the blurred portions that generate observe the extent of exfoliation of film, with the peel resistant strength of following benchmark evaluation films, i.e. resistance to
It is scratch resistance.Result is summarized and is listed in table 4 and table 5.
The evaluation criteria of marresistance
5: the peeling without film
4: the peeling area of film is less than 10%
3: the peeling area of film be 10% or more~less than 50%
2: the peeling area of film be 50% or more~less than 80%
1: the peeling area of film is 80% or more
The evaluation of stickness
It is cut into 2 20cm × 20cm's from the modified thermoplastic polymeric membrane of each example produced in test classification 2
The coated face of the coupons is overlapped each other, equably applies 1kg/m by square sample piece2Load, 50 DEG C keep 24
After hour, the film of overlap condition is cut into the square of 10mm × 10mm as test film, for the test film, with following
Peeling force, i.e. stickness between two film of benchmark evaluation.Result is summarized and is listed in table 4 and table 5.
Stickness evaluation criteria
5: peeling force is less than 50mN/10mm
4: peeling force be 50mN/10mm or more~be less than 100mN/10mm
3: peeling force be 100mN/10mm or more~be less than 150cmN/10mm
2: peeling force be 150mN/10mm or more~be less than 200mN/10mm
1: peeling force is 200mN/10mm or more
The evaluation of liquid stability
By the thermal plastic high polymer film coating composition of each example prepared in test classification 1 in room temperature in closed container
20 DEG C of standings save, and observe separate condition at this time, pass through the Time evaluation liquid stability until separation with following benchmark.
Result is summarized and is listed in table 4 and table 5.
The evaluation criteria of liquid stability
5: at 24 hours or more without separation
4: at 12 hours or more~less than 24 hours without separation
3: at 6 hours or more~less than 12 hours without separation
2: at 2 hours or more~less than 6 hours without separation
1: being separated less than 2 hours
The evaluation of coating
The state of the coated face of the modified thermoplastic polymeric membrane of each example manufactured in test classification 2 is observed,
With following benchmark evaluation coatings.Result is summarized and is listed in table 4 and table 5.
The evaluation criteria of coating
5: uneven, shrinkage cavity not occurring
4: occurring in a part uneven
3: whole that unevenness occurs
2: shrinkage cavity occurs in a part
1: whole that shrinkage cavity occurs
[table 4]
[table 5]
By the result of table 4 and table 5 corresponding to table 2 and table 3 it is found that when being coated with composition of the invention, when because of film
Or the reduction of drip performance caused by friction when sprawling is few, and excellent anti-drop property is played from the initial stage sprawled, even if
Also excellent anti-drop property is maintained after sprawling for a long time, and then coated face also few stickness.
Claims (12)
1. a kind of thermal plastic high polymer film coating composition, which is characterized in that it is to be scaled 100 relative to solid component
Following modified inorganic cationic colloidal colloidal sols of mass parts, with the ratio of 10~50 mass parts contain polyether modified silicone, with 2~
The ratio of 30 mass parts is contained following polyoxyalkylene derivatives and is contained following poly- alkane with the ratio of 45~75 mass parts
Made of supportting glycol,
Modified inorganic cationic colloidal colloidal sol: the condensation polymer of following silanol compounds is made to be attached to following inorganic cations
Modified inorganic cationic colloidal colloidal sol made of on the solid component particle of colloid solution, the ratio of attachment are inorganic cation glue
Solid component/silanol compound condensation polymer=100/5~100/15 of body colloidal sol, the ratio are mass ratio；
Inorganic cationic colloidal colloidal sol: the cationic oxidation aluminium containing the ratio for being scaled 20~90 mass % with solid component is molten
Glue and be scaled with solid component 10~80 mass % ratio cationic colloidal silica made of inorganic cationic colloidal it is molten
Glue, the ratio add up to 100 mass % with solid component conversion；
Silanol compound: to selected from least one of trialkoxysilanes silanol formative organic silane compound into
Compound made of row hydrolysis process；
Polyoxyalkylene derivative: selected from least one of following compounds: relative to every 1 mole of following initial compounds with oxygen
Change the ratio that ethylene is 9~24 moles and carries out compound made of addition；Relative to every 1 mole of following initial compounds to aoxidize
The ratio that ethylene and propylene oxide add up to 9~24 moles carries out compound made of random addition；And relative to every 1 mole
Following initial compounds carry out chemical combination made of block addition with the ratio that ethylene oxide and propylene oxide add up to 9~24 moles
Object；
Initial compounds: the fatty acid polyglycol alkylene glycol that the aliphatic alcohol or carbon atom number that carbon atom number is 8~22 are 8~22:
It is 10000~20000 polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide atactic polymer selected from number-average molecular weight
At least one of with ethylene oxide-propylene oxide block polymer.
2. thermal plastic high polymer film coating composition as described in claim 1, wherein the HLB of polyether modified silicone be 4~
16。
3. thermal plastic high polymer film coating composition as claimed in claim 1 or 2, wherein silanol compound is to choosing
From γ-glycidoxypropyltrime,hoxysilane, γ-urea propyl trimethoxy silicane, methyltriethoxysilane and ethyl
Compound made of at least one of triethoxysilane silanol formative organic silane compound is hydrolyzed.
4. thermal plastic high polymer film coating composition as claimed in claim 1 or 2, wherein ployalkylene glycol is poly- second two
Alcohol.
5. thermal plastic high polymer film coating composition as claimed in claim 1 or 2, wherein inorganic cationic colloidal colloidal sol
It cationic oxidation Aluminum sol containing the ratio for being scaled 50~80 mass % with solid component and is scaled with solid component
The cationic colloidal silica of the ratio of 20~50 mass %, the ratio add up to 100 mass % with solid component conversion.
6. thermal plastic high polymer film coating composition as claimed in claim 1 or 2, wherein modified inorganic cationic colloidal
Colloidal sol is to be attached to the condensation polymer of silanol compound on the solid component particle of inorganic cationic colloidal colloidal sol to form
, the ratio of attachment be inorganic cationic colloidal colloidal sol solid component/silanol compound condensation polymer=100/7~
100/12, which is mass ratio.
7. thermal plastic high polymer film coating composition as claimed in claim 1 or 2, is converted relative to solid component
For the modified inorganic cationic colloidal colloidal sol of 100 mass parts, polyether modified silicone is contained, with 5 with the ratio of 20~40 mass parts
The ratio of~20 mass parts, which contains polyoxyalkylene derivative and contains ployalkylene glycol with the ratio of 50~70 mass parts, to be formed
's.
8. a kind of manufacturing method of thermal plastic high polymer film coating composition, which is characterized in that its undergo following 1st processes and
Following 2nd processes,
1st process: in the presence of following inorganic cationic colloidal colloidal sols, to following silanol formative organic silane compounds
It is hydrolyzed, further makes silanol compound condensation polymerization generated, obtain modified inorganic cationic colloidal colloidal sol
Process, in hydrolysis process, the solid component of the inorganic cationic colloidal colloidal sol relative to every 100 mass parts is described
The amount of silanol formative organic silane compound is the ratio of 5~15 mass parts；
Inorganic cationic colloidal colloidal sol: the cationic oxidation aluminium containing the ratio for being scaled 20~90 mass % with solid component is molten
Glue and be scaled with solid component 10~80 mass % ratio cationic colloidal silica made of inorganic cationic colloidal it is molten
Glue, the ratio add up to 100 mass % with solid component conversion；
Silanol formative organic silane compound: selected from least one of trialkoxysilanes；
2nd process: relative to the modified inorganic cationic colloidal obtained by process 1 for being scaled 100 mass parts with solid component
Colloidal sol, with the ratio mixture polyether modified silicone of 10~50 mass parts, with the following polyoxyalkylenes of ratio mixture of 2~30 mass parts
Derivative and the ployalkylene glycol following with the ratio mixture of 45~75 mass parts, obtain the coating of thermal plastic high polymer film and use
The process of composition；
Polyoxyalkylene derivative: selected from least one of following compounds: relative to every 1 mole of following initial compounds with oxygen
Change the ratio that ethylene is 9~24 moles and carries out compound made of addition；Relative to every 1 mole of following initial compounds to aoxidize
The ratio that ethylene and propylene oxide add up to 9~24 moles carries out compound made of random addition；And relative to every 1 mole
Following initial compounds carry out chemical combination made of block addition with the ratio that ethylene oxide and propylene oxide add up to 9~24 moles
Object；
Initial compounds: the fatty acid polyglycol alkylene glycol that the aliphatic alcohol or carbon atom number that carbon atom number is 8~22 are 8~22:
It is 10000~20000 polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide atactic polymer selected from number-average molecular weight
At least one of with ethylene oxide-propylene oxide block polymer.
9. the manufacturing method of thermal plastic high polymer film coating composition as claimed in claim 8, which is characterized in that the silicon
Alkanol formative organic silane compound is to selected from γ-glycidoxypropyltrime,hoxysilane, γ-urea propyl trimethoxy
At least one of base silane, methyltriethoxysilane and ethyl triethoxysilane.
10. a kind of modified thermoplastic polymeric membrane, which is characterized in that adhere in the Corona discharge Treatment face of thermal plastic high polymer film
0.1~2.0g/m is calculated as with solid component2Thermal plastic high polymer film according to any one of claims 1 to 7 coating use group
Close object.
11. modified thermoplastic polymeric membrane as claimed in claim 10, is agricultural mulch films.
12. a kind of manufacturing method of modified thermoplastic polymeric membrane, which is characterized in that it undergoes following 1st processes and the following 2nd
Process,
1st process: Corona discharge Treatment is carried out to thermal plastic high polymer film, makes the wetting tension in Corona discharge Treatment face
The process of 35mN/m or more；
2nd process: for the Corona discharge Treatment face of the thermal plastic high polymer film obtained by the 1st process, according to solid component
It is calculated as 0.1~2.0g/m2It is coated with the work of thermal plastic high polymer film coating composition according to any one of claims 1 to 7
Sequence.
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| PCT/JP2016/067751 WO2017029867A1 (en) | 2015-08-17 | 2016-06-15 | 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 |
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|---|---|---|---|---|
| JPS62241984A (en) * | 1986-04-14 | 1987-10-22 | Takemoto Oil & Fat Co Ltd | Method of surface modification |
| JPH0782398A (en) * | 1993-09-17 | 1995-03-28 | Sumitomo Chem Co Ltd | Antifogging agent composition with improved applicability and agricultural film |
| JP2003049003A (en) * | 2001-02-05 | 2003-02-21 | Sekisui Chem Co Ltd | Thermoplastic resin film, coating antifogging agent and agricultural film |
| CN102719123A (en) * | 2012-07-05 | 2012-10-10 | 上海多纶化工有限公司 | External application anti-drop antifogging agent composition of agricultural film |
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| JP2000160146A (en) * | 1998-12-01 | 2000-06-13 | Sekisui Chem Co Ltd | Anti-fogging agent and agricultural film |
| JP4944311B2 (en) * | 2001-04-27 | 2012-05-30 | 積水化学工業株式会社 | Coating anti-fogging agent and agricultural film |
| JP2011179007A (en) * | 2011-04-18 | 2011-09-15 | Fumakilla Ltd | Anti-fogging agent and treatment method therewith |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62241984A (en) * | 1986-04-14 | 1987-10-22 | Takemoto Oil & Fat Co Ltd | Method of surface modification |
| JPH0782398A (en) * | 1993-09-17 | 1995-03-28 | Sumitomo Chem Co Ltd | Antifogging agent composition with improved applicability and agricultural film |
| JP2003049003A (en) * | 2001-02-05 | 2003-02-21 | Sekisui Chem Co Ltd | Thermoplastic resin film, coating antifogging agent and agricultural film |
| CN102719123A (en) * | 2012-07-05 | 2012-10-10 | 上海多纶化工有限公司 | External application anti-drop antifogging agent composition of agricultural film |
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