CN114058098A - Membrane, method for the production thereof and use thereof - Google Patents
Membrane, method for the production thereof and use thereof Download PDFInfo
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- CN114058098A CN114058098A CN202010766854.6A CN202010766854A CN114058098A CN 114058098 A CN114058098 A CN 114058098A CN 202010766854 A CN202010766854 A CN 202010766854A CN 114058098 A CN114058098 A CN 114058098A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
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Abstract
The invention discloses a membrane, a manufacturing method and application thereof. The film is a film containing a non-fluororesin and a fluororesin, wherein the content of the fluororesin is 0.1-20.0 mass% relative to the total mass of the non-fluororesin, and the fluorine atom content of the fluororesin is 50 mass% or less.
Description
Technical Field
The present invention relates to a membrane, a method for the production thereof, and the use thereof.
Background
Films used as release films, films for building structures, agricultural films, films for protecting wind-power-generating blades, decorative films, packaging films, protective films for automobile finishes, films for communication towers, films for aircraft, and the like are commonly used as cover films for various purposes, and these cover films are widely used to provide surface protection. In the agricultural field, agricultural covering materials are used for the purpose of soil heat preservation and water retention, prevention of outflow of nutrients in soil, maintenance of granular structure of soil, and the like. Agricultural covering materials include agricultural films such as agricultural greenhouses for plant cultivation and transparent synthetic resin films for ceilings and side walls, and are one type of product used for measures such as protection of plant water loss in agricultural production. With the progress of science and technology, the requirements on agricultural films are higher and higher
Currently, agricultural films such as polyethylene films made of polyethylene, polyvinyl chloride films made of polyvinyl chloride, and the like are commonly used. For example, patent document 1 proposes an agricultural film formed from a resin composition containing polyvinyl chloride as a main component.
Further, fluororesin films are excellent in weather resistance, stain resistance and the like, and can maintain weather resistance, transparency, stain resistance and the like for a long period of time, and therefore, they are used as roof materials, spreading films, wall decoration materials, surface laminate films of various substrates and the like for membrane structures (greenhouses for agriculture, sports facilities, tents and the like). For example, patent document 2 proposes a fluorinated film suitable for external use, particularly for greenhouse films in the agricultural field, which is a single-layer polymer film comprising a polyvinylidene fluoride (PVDF) matrix. Further, patent document 3 proposes an agricultural multilayer film having a three-layer structure, in which the intermediate layer is made of low density polyethylene (LLDPE), and the outer layer may be made of a material containing High Density Polyethylene (HDPE) and polyvinylidene fluoride (PVDF).
However, there remains a need in the art for such films to have improved chemical and weather resistance. Accordingly, it is desirable to provide a film having further improved weather resistance and chemical resistance, and a method for producing and use thereof.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. Hei 6-166762
Patent document 2: chinese patent application CN105814122A
Patent document 3: japanese patent laid-open No. 2000-324959
Disclosure of Invention
It is an object of the present invention to provide a film having further improved weather resistance and chemical resistance.
It is another object of the present invention to provide a method for producing the film.
It is also an object of the present invention to provide the use of the film.
Accordingly, one aspect of the present invention relates to a film comprising a non-fluororesin and a fluororesin, the content of the fluororesin being 0.1 to 20.0 mass% with respect to the total mass of the non-fluororesin, and the fluorine atom content of the fluororesin being 50 mass% or less.
Another aspect of the present invention relates to a method for producing the film, including melt-kneading a raw material including the non-fluororesin and the fluororesin to produce a film, wherein a content of the fluororesin is 0.1 to 20.0 mass% with respect to a total mass of the non-fluororesin, and a content of a fluorine atom in the fluororesin is 50 mass% or less.
Still another aspect of the present invention relates to the use of the film as a mold release film, a film for building structures, a film for agricultural use, a film for protecting wind-power-generating blades, a decorative film, a packaging film, a protective film for automobile finish, a film for communication towers, or a film for aircraft.
Detailed Description
The film of the present invention is a film comprising a non-fluororesin and a fluororesin, wherein the content of the fluororesin is 0.1 to 20.0 mass% with respect to the total mass of the non-fluororesin, and the fluorine atom content of the fluororesin is 50 mass% or less. The inventors of the present invention have intensively studied and found that a film having excellent film properties can be obtained by using a non-fluororesin and a fluororesin having a specific fluorine atom content and melt-kneading the components in such a manner that the content of the fluororesin is in a specific range with respect to the total mass of the non-fluororesin, the fluororesin has good dispersibility in the non-fluororesin, can be uniformly dispersed in the non-fluororesin after melting, and can protect other components such as a lubricant and a light stabilizer in the film, thereby further extending the weather resistance and chemical properties.
In one embodiment of the present invention, a film can be produced by melt-kneading raw materials including the non-fluororesin and the fluororesin.
In one embodiment of the present invention, the raw material contains a non-fluororesin and a fluororesin. In the production of the raw material, a film is produced by feeding a non-fluororesin, a fluororesin, and other components such as a plasticizer, a lubricant, and a light stabilizer as needed into an extruder and melt-kneading them.
< non-fluororesin >
Examples of the non-fluororesin in the raw material include polyethylene, polyvinyl chloride, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyvinyl alcohol, polystyrene, polyurethane, polyester, polycarbonate, (meth) acrylic resin, vinyl chloride resin, vinyl ester resin and the like. Among these, polyethylene, polyvinyl chloride, and polypropylene are preferable, and polyethylene and polyvinyl chloride are more preferable, from the viewpoint of the balance between weather resistance and cost. These resins may be used in combination of 2 or more.
When the polyester resin is contained as a non-fluororesin, the polyester resin has a structure in which a unit based on a polycarboxylic acid compound and a unit based on a polyol compound are bonded to each other via an ester bond. The polyester resin may also contain a hydroxycarboxylic acid-based unit or the like as a unit other than the carboxylic acid unit and the alcohol unit.
The polyester resin can be, for example, a polymer having a unit derived from an aromatic polycarboxylic acid compound having 8 to 15 carbon atoms and a unit derived from a polyhydric alcohol compound having 2 to 10 carbon atoms.
The hydroxyl value of the polyester resin is preferably 20 to 100mg KOH/g, more preferably 30 to 80mg KOH/g. The acid value of the polyester resin is preferably 1 to 80mg KOH/g, more preferably 3 to 50mg KOH/g.
From the viewpoint of melt viscosity, the Mn and Mw of the polyester resin are preferably 5000 or less and Mw is 6000 to 20000, and more preferably 5000 or less and Mw is 6000 to 10000.
Specific examples of the polyester polymer include "CryLCOAT (registered trademark) 4642-3", "CryLCOAT (registered trademark) 4890-0", manufactured by Nippon Cyanite industries, Ltd. "GV-250", "GV-740" and "GV-175", manufactured by Nippon Youbijia Ltd.
The (meth) acrylic resin preferably contains a unit based on one or more selected from acrylic acid and methacrylic acid, and a unit based on one or more selected from acrylic acid esters and methacrylic acid esters.
Specific examples of the acrylic resin include "ファインディック (registered trademark) A-249", "ファインディック (registered trademark) A-251", "ファインディック (registered trademark) A-266", available from DIC corporation, "アルマテックス (registered trademark) PD 6200", "アルマテックス (registered trademark) PD 7310", available from Sanyo chemical corporation, "サンペックス PA-55", available from Sanyo chemical corporation.
The polyurethane is a mixture of a polyol (acrylic polyol, polyester polyol, polyether polyol, propylene glycol, etc.) and an isocyanate compound, or a resin obtained by reacting the mixture, and is preferably a mixture of a powdery polyol (acrylic polyol, polyester polyol, polyether polyol) and a powdery isocyanate.
The non-fluororesin is preferably a solid non-fluororesin having a softening point of 100 to 150 ℃ at room temperature, a glass transition temperature Tg of 30 to 60 ℃ and a melting point of 200 ℃ or less.
< fluororesin >
The fluororesin used in the raw material may comprise a fluoropolymer containing a fluoroolefin-based unit. The fluoroolefin is an olefin in which 1 or more hydrogen atoms are replaced by fluorine atoms. The carbon number of the fluoroolefin is preferably 2 to 8, more preferably 2 to 6. The number of fluorine atoms in the fluoroolefin is preferably 2 or more, more preferably 3 to 4. When the number of fluorine atoms is 2 or more, the cured film is excellent in weather resistance. In the fluoroolefin, 1 or more of the hydrogen atoms not substituted by fluorine atoms may be substituted by chlorine atoms
As a specific example of the fluoroolefin, CF is exemplified2＝CF2、CF2＝CFCl、CF2＝CHF、CH2＝CF2、CF2＝CFCF3、CF2＝CHCF3、CF3CH＝CHF、CF3CF＝CH2From the viewpoint of polymerizability, CF is preferred2＝CFCl、CF3CHF or CF3CF＝CH2. The fluoroolefin may be used in combination of 2 or more.
The fluorine-containing polymer may contain only the fluoroolefin-based unit, may contain a unit based on a fluorine-containing monomer other than the fluoroolefin, and may contain a unit based on a non-fluorine-containing monomer.
The fluoropolymer containing only a fluoroolefin-based unit may, for example, be a homopolymer of a fluoroolefin or a copolymer of two or more fluoroolefins, and specifically may, for example, be polychlorotrifluoroethylene, a copolymer of tetrafluoroethylene and hexafluoropropylene, or polyvinylidene fluoride.
As the fluorine-containing polymer comprising a unit based on a fluorine-containing monomer other than the fluoroolefin, a fluoroolefin is exemplified-perfluoro (alkyl vinyl ether) copolymer, preferably fluoroolefin-perfluoro (C)1-10Alkyl vinyl ether) copolymer, more preferably fluoroolefin-perfluoro (C)1-6Alkyl vinyl ether) copolymer, specifically, tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer may be mentioned, and tetrafluoroethylene-perfluoro (C) is preferred1-10Alkyl vinyl ether) copolymer, more preferably tetrafluoroethylene-perfluoro (C)1-6Alkyl vinyl ether) copolymer.
As the fluorine-containing monomer, a fluoroolefin is more preferable than the above-mentioned fluorine-containing monomers other than the fluoroolefin. The fluoropolymer preferably contains only a fluoroolefin as the fluoromonomer, as compared to a fluoroolefin and a fluoromonomer other than the fluoroolefin.
The content of the fluoroolefin-based unit in the entire units contained in the fluoropolymer is preferably 5 to 100 mol%, more preferably 20 to 70 mol%, and particularly preferably 40 to 60 mol%.
When the fluoropolymer contains a unit based on a non-fluorine monomer, the unit preferably contains a unit based on a monomer having a crosslinkable group. By using the monomer having a crosslinkable group, the compatibility of the fluororesin with the plasticizer and the like in the film component can be improved, the component such as the plasticizer can be retained in the film, embrittlement of the film with time due to elution of the component can be prevented, the film does not become brittle even after long-term use, and excellent film performance is maintained. In this case, if a curing agent is contained as a raw material, the crosslinkable group serves as a crosslinking point, and the crosslinking reaction of the fluoropolymer bond proceeds through the curing agent, thereby improving the physical properties of the cured film. The crosslinkable group may, for example, be a hydroxyl group, a carboxyl group, an amino group, an alkoxysilyl group or an epoxy group, and from the viewpoint of water resistance, chemical resistance, impact resistance and the like of the cured film, a hydroxyl group or a carboxyl group is preferred, and a hydroxyl group is more preferred.
Examples of the monomer having a crosslinkable group include carboxylic acids polymerizable with vinyl alcohol or fluoroolefin, and vinyl ethers, vinyl esters, allyl ethers, allyl esters, acrylic esters, and methacrylic esters having a crosslinkable group, and specifically, may include CH2＝CHCOOH、CH(CH3)＝CHCOOH、CH2＝C(CH3) COOH, formulaCH2＝CH(CH2)n2A compound represented by COOH (wherein n2 represents an integer of 1 to 10), and CH2＝CHO-CH2-Ring C6H10-CH2OH、CH2＝CHCH2O-CH2-Ring C6H10-CH2OH、CH2＝CHOCH2CH2OH、CH2＝CHCH2OCH2CH2OH、CH2＝CHOCH2CH2CH2CH2OH、CH2＝CHCH2OCH2CH2CH2CH2OH、CH2＝CHCOOCH2CH2OH、CH2＝C(CH3)COOCH2CH2And (5) OH. In addition, "-Ring C6H10- "denotes cyclohexylidene," -ring C6H10The bonding site of the- "is usually 1, 4-. The monomer having a crosslinkable group may be used in combination of 2 or more.
The content of the unit based on the monomer having a crosslinkable group in all units contained in the fluoropolymer may be 0.5 to 100 mol%, preferably 10 to 55 mol%, more preferably 15 to 50 mol%, or may be 0.5 to 35 mol%, preferably 3 to 30 mol%, more preferably 5 to 25 mol%, particularly preferably 5 to 20 mol%, from the viewpoint of excellent physical properties of the cured film.
The fluoropolymer may also contain units based on monomers that do not contain fluorine atoms and do not have crosslinkable groups. The above-mentioned unit may, for example, be an olefin, a vinyl ether, a vinyl ester, an allyl ether, an allyl ester, an acrylic ester, a methacrylic ester or the like, preferably a vinyl ether, a vinyl ester, an allyl ether, an allyl ester, an acrylic ester, a methacrylic ester, more preferably a vinyl ether or a vinyl ester. Specific examples thereof may include ethylene, propylene, ethyl vinyl ether, 2-ethylhexyl vinyl ether, vinyl acetate, vinyl benzoate, methyl acrylate, methyl methacrylate, butyl acrylate and butyl methacrylate.
Among them, the fluoropolymer preferably contains units based on a monomer having an alkyl group having a tertiary carbon atom having 3 to 9 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms in a side chain, from the viewpoint of Tg of the fluoropolymer. However, this unit does not contain a fluorine atom and a crosslinkable group.
Examples of the alkyl group having a tertiary carbon atom and having 3 to 9 carbon atoms or the cycloalkyl group having 4 to 10 carbon atoms include a tert-butyl group, a neononyl group, a cyclohexyl group, a cyclohexylmethyl group, a 4-cyclohexylcyclohexyl group, and a 1-decahydronaphthyl group.
Specific examples of the above units include cyclohexyl vinyl ether, t-butyl vinyl ether, vinyl pivalate, vinyl t-butyl benzoate and vinyl neononanoate. The above units may be used in combination of 2 or more.
The content of the unit based on the monomer having no fluorine atom and no crosslinkable group in all the units contained in the fluoropolymer is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, from the viewpoint of Tg of the fluoropolymer and flexibility of the cured film.
The fluorine-containing polymer is more preferably composed of only a unit based on a fluoroolefin, a unit based on a monomer having a crosslinkable group, and a unit based on a monomer containing no fluorine atom and having no crosslinkable group. The content of the fluoroolefin-based unit, the crosslinkable group-containing monomer-based unit, and the fluorine atom-free crosslinkable group-free monomer-based unit in the fluoropolymer are preferably 20 to 70 mol%, 10 to 55 mol%, and 5 to 60 mol%, in this order, based on all units of the fluoropolymer.
The Mn of the fluoropolymer is preferably 3000 to 50000, more preferably 5000 to 30000, from the viewpoint of water resistance and smoothness of the cured film.
When the fluororesin contains a fluorine-containing polymer having hydroxyl groups, the hydroxyl value is preferably 5 to 200mg KOH/g, more preferably 10 to 150mg KOH/g.
When the fluororesin contains a fluorine-containing polymer having a carboxyl group, the acid value is preferably 1 to 150mg KOH/g, more preferably 3 to 100mg KOH/g, and particularly preferably 5 to 50mg KOH/g.
The fluoropolymer may have only either one of the acid value and the hydroxyl value, or both of them. When the fluoropolymer has both an acid value and a hydroxyl value, the total of the acid value and the hydroxyl value is preferably 1 to 80mg KOH/g. When the total of the acid value and the hydroxyl value is within the above range, the Tg of the fluoropolymer can be appropriately adjusted, and the cured film has excellent physical properties.
In one embodiment of the present invention, the fluororesin is a crosslinked product containing a fluoropolymer having a crosslinkable group and a curing agent. The crosslinkable group may, for example, be a hydroxyl group, a carboxyl group, an amino group, an alkoxysilyl group or an epoxy group, and from the viewpoint of water resistance, chemical resistance, impact resistance and the like of the cured film, a hydroxyl group or a carboxyl group is preferred, and a hydroxyl group is more preferred. As the curing agent, known compounds can be used, and examples thereof include isocyanate-based curing agents, amine-based curing agents such as melamine resins, guanamine resins, sulfonamide resins, urea resins and aniline resins, β -hydroxyalkylamide-based curing agents and triglycidyl isocyanurate-based curing agents. The curing agent may be used in combination of 2 or more. The curing agent is preferably an isocyanate curing agent, the glass transition temperature of the curing agent is 30-100 ℃, and the content of isocyanate groups relative to the total mass of the curing agent can be 0.1-30.0 mass%. The content of the curing agent is preferably 1 to 50% by mass, and more preferably 3 to 30% by mass, based on 100% by mass of the fluoropolymer.
The glass transition temperature of the fluorine-containing polymer is preferably 10 ℃ or higher, more preferably 30 to 150 ℃, still more preferably 40 to 120 ℃, and further preferably 50 to 100 ℃.
The melting point of the fluororesin is preferably 300 ℃ or lower, more preferably 200 ℃ or lower, and particularly preferably 180 ℃ or lower. The fluororesin preferably has a glass transition temperature Tg of 30 to 150 ℃, more preferably 40 to 120 ℃, and still more preferably 50 to 100 ℃ from the viewpoint of blocking resistance and smoothness of the cured film.
In the present invention, the fluorine atom content of the fluororesin is 50 mass% or less. In one embodiment of the present invention, the fluorine atom content of the fluororesin is 10 to 50% by mass, preferably 15 to 40% by mass, and more preferably 20 to 30% by mass. When the fluorine atom content of the fluororesin is within this range, the fluororesin has good dispersibility in the non-fluororesin, can be uniformly dispersed in the non-fluororesin after melting, and can protect other components such as a lubricant and a light stabilizer in the film, thereby further extending the weather resistance and chemical resistance and obtaining excellent film performance.
In one embodiment of the present invention, the content of the fluororesin is 0.1 to 20.0% by mass, preferably 0.5 to 15.0% by mass, and more preferably 1 to 10.0% by mass, based on the total mass of the non-fluororesin. When the relative content of the fluororesin is within this range, the fluororesin has good dispersibility in the non-fluororesin, can be uniformly dispersed in the non-fluororesin after melting, does not cause embrittlement of the film, and can protect other components such as a lubricant and a light stabilizer in the film, thereby further improving the weather resistance and chemical resistance and obtaining excellent film performance.
In one embodiment of the present invention, the fluororesin is obtained as a powder by introducing an organic solvent, a fluoroolefin monomer, optionally a crosslinkable group-containing monomer, a fluorine atom-free crosslinkable group-free monomer, and a polymerization initiator into an autoclave, and heating the mixture to perform a polymerization reaction.
In one embodiment of the present invention, a film is produced by melt-kneading a raw material containing the non-fluororesin and the fluororesin, wherein the total mass of the fluororesin and the non-fluororesin may be 50 to 100 mass%, 60 to 99.5 mass%, or 80 to 99 mass%, based on the total mass of the raw material.
< curing agent >
In one embodiment of the present invention, the raw material may contain a curing agent in addition to the fluororesin and the non-fluororesin. However, the curing agent may be added after the fluororesin and the non-fluororesin are kneaded and pulverized, without adding the curing agent at the stage of the raw material. In addition, the fluororesin and the non-fluororesin may not be added with the curing agent if they can be cured by other methods without the curing agent.
As the curing agent, known compounds can be used, and examples thereof include isocyanate-based curing agents, amine-based curing agents such as melamine resins, guanamine resins, sulfonamide resins, urea resins and aniline resins, β -hydroxyalkylamide-based curing agents and triglycidyl isocyanurate-based curing agents. The curing agent may be used in combination of 2 or more. The curing agent is preferably an isocyanate curing agent, the glass transition temperature of the curing agent is 30-100 ℃, and the content of isocyanate groups relative to the total mass of the curing agent can be 0.1-30.0 mass%.
The softening temperature of the curing agent is preferably 10-120 ℃, and more preferably 40-100 ℃. When the softening temperature is 10 ℃ or higher, the raw material can be prevented from solidifying at room temperature and forming a granular lump. When the temperature is 120 ℃ or lower, the curing agent can be homogeneously dispersed in the raw material in the kneading step, and the smoothness of the obtained cured film, the strength of the cured film, and the like can be improved.
The content of the curing agent is preferably 1 to 50% by mass, and more preferably 3 to 30% by mass, based on 100% by mass of the raw material.
< other ingredients >
The raw material may optionally contain other components in addition to the fluororesin, the non-fluororesin and the curing agent. Examples of the other components include plasticizers, lubricants, light stabilizers, pigments, curing catalysts, degassing agents, surface conditioning agents, ultraviolet absorbers, matting agents such as ultrafine synthetic silica, nonionic, cationic or anionic surfactants, leveling agents, fillers, heat stabilizers, tackifiers, dispersants, antistatic agents, rust inhibitors, silane coupling agents, antifouling agents, and low-pollution treatment agents.
The plasticizer is at least 1 selected from aliphatic dibasic acid esters, phthalic acid esters, benzenepolycarboxylic acid esters, benzoic acid esters, polyhydric alcohol esters, chlorinated hydrocarbons, epoxies, citric acid esters, polyesters, and the like. A phthalate plasticizer is preferably used, and phthalate esters, terephthalate esters and the like can be exemplified as the phthalate plasticizer. It is preferable to use a phthalic acid ester, and examples of the phthalic acid ester include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, dioctyl phthalate, and diisononyl phthalate. In one embodiment of the present invention, the content of the plasticizer in the raw material may be 10 to 50 mass%, preferably 12 to 40 mass%, and more preferably 15 to 30 mass%.
The lubricant may be selected from silica, fatty acid amides, oleic acid, polyesters, synthetic esters, carboxylic acids, and the like. Preferably, a silica-based lubricant such as ソルスフェア H31 (commercially available from AGC エスアイテック) is used. In one embodiment of the present invention, the content of the lubricant in the raw material may be 0.1 to 20 mass%, preferably 0.2 to 10 mass%, and more preferably 0.5 to 1 mass%.
As the light stabilizer, ultraviolet absorbers such as benzotriazoles, benzophenones and salicylates, radical scavengers such as hindered amines, for example, CHIMASSORB 944 (a product of Qianye specialty Chemicals Co., Ltd.) can be used. In one embodiment of the present invention, the content of the light stabilizer in the raw material may be 0.1 to 20% by mass, preferably 0.2 to 10% by mass, and more preferably 0.5 to 1% by mass.
As the pigment, at least 1 selected from the group consisting of a bright pigment, an anticorrosive pigment, a coloring pigment and a filling pigment is preferable. Examples of the bright pigment include aluminum powder, nickel powder, stainless steel powder, copper powder, bronze powder, gold powder, silver powder, mica powder, graphite powder, glass flake, and scale-like iron oxide powder. As the rust preventive pigment, preferred are lead-free rust preventive pigments which are small in load on the environment, and examples thereof include zinc cyanamide, zinc oxide, zinc phosphate, calcium magnesium phosphate, zinc molybdate, barium borate, calcium cyanamide zinc, and the like. The coloring pigment is a pigment for coloring the cured film. Examples of the coloring pigment include titanium oxide, carbon black, iron oxide, phthalocyanine blue, phthalocyanine green, quinacridone, isoindolinone, benzimidazolone, and dioxazine. Examples of the filler pigment include talc, barium sulfate, mica, and calcium carbonate. In one embodiment of the present invention, the content of the pigment in the raw material is preferably 20 to 200% by mass, and more preferably 50 to 150% by mass, based on 100% by mass of the fluororesin.
The curing catalyst may be, for example, a tin catalyst such as tin octylate, tributyltin dilaurate or dibutyltin dilaurate. The curing catalyst may be used in combination of 2 or more. The content of the curing catalyst is preferably 0.0001 to 10.0 parts by mass based on 100 parts by mass of the total solid content other than the pigment.
[ method for producing film ]
The method for producing a film of the present invention includes melt-kneading a raw material containing the non-fluororesin and the fluororesin to produce a film.
In one embodiment of the present invention, the raw material contains the non-fluororesin and the fluororesin. In the production of the raw material, the fluororesin, the non-fluororesin, and other components such as a plasticizer, a lubricant, and a light stabilizer as needed are fed into an extruder and melt-kneaded to form a film.
The kneading may be carried out by a common kneading technique, and for example, it may be carried out by a mixer, a kneader, an extruder, and other various known blending devices and mixing devices. In one embodiment of the present invention, the raw material components are melt-kneaded using an inflatable co-extruder equipped with an extruder.
The kneading temperature in the kneading step is preferably higher than or equal to the higher of the glass transition temperature of the fluororesin and the glass transition temperature of the non-fluororesin contained in the raw material. The kneading temperature in the kneading step is preferably not higher than the solidification start temperature of the raw materials. Here, the curing start temperature of the raw material is the lower temperature of the curing start temperature of the fluororesin and the curing start temperature of the non-fluororesin. In addition, when the raw material contains a curing agent, the curing temperature is lower in the mixture of the fluororesin and the curing agent than in the mixture of the non-fluororesin and the curing agent. By setting the kneading temperature to the above-mentioned temperature, the resins can be uniformly mixed with each other, and the raw materials can be prevented from being solidified in the kneading extruder and from hindering the kneading. The kneading temperature may be 100 ℃ or higher, preferably 110 ℃ or higher, from the viewpoint of controlling thickening of the raw materials during melt kneading and uniformly mixing. In addition, from the viewpoint of uniformly mixing the raw materials at the time of melt kneading and preventing the raw materials from solidifying in the kneading extruder and inhibiting kneading, the temperature may be 300 ℃ or lower, and preferably 190 ℃ or lower.
The film-forming method may be a known method, for example, a melt extrusion method, a solution casting method, a calendering method, or the like.
The thickness of the film is 0.03-0.2 mm, preferably 0.05-0.15 mm, and more preferably 0.08-0.12 mm. Too thin gives insufficient strength, and too thick gives inconvenience to the film forming operation and subsequent processing (cutting the film, taking up it in a greenhouse form, spreading it on a greenhouse, etc.).
The membrane of the invention has the following technical effects: the weather resistance is excellent, and the service life is greatly prolonged; excellent chemical resistance, maintaining good chemical resistance even after being subjected to acid rain or pesticide spreading; the film is not easy to adhere to soil, so that the weight of the film is reduced when the film is reused or discarded; the light transmittance is high, and the light-transmitting film is particularly useful for the cultivation and growth of plants; the film is prevented from becoming brittle, elution of other components such as a plasticizer in the film component is avoided, and embrittlement is not easily caused even in long-term use. Therefore, the film of the present invention can be widely used for applications such as mold release films, films for building structures, agricultural films, films for protecting wind turbine blades, decorative films, packaging films, protective films for automotive finishes, films for communication towers, and films for airplanes.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to these examples. Examples 1 to 3, 5 to 6 and 9 to 10 are examples, examples 4, 7 to 8 and 11 are comparative examples, and example 12 is a reference example.
Production example
Production example 1 (production of fluororesin F1)
Xylene (503g), ethanol (142g), CTFE (387g), CHVE (326g), HBVE (84.9g), potassium carbonate (12.3g) and a xylene solution (20mL) containing 50 mass% t-butylperoxypivalate were introduced into the autoclave, and polymerization was carried out at 65 ℃ for 11 hours. Then, the autoclave solution was filtered to obtain a solution containing a fluorine resin F1 composed of a fluorine-containing polymer. The solvent in the resulting solution was removed by vacuum drying at 65 ℃ for 24 hours, and further vacuum dried at 130 ℃ for 20 minutes. The obtained block-shaped fluororesin F1 was pulverized to obtain a powdery fluororesin F1.
The fluororesin F1 was a polymer containing, in order relative to the total units contained in the fluororesin F1, 50 mol% of units based on CTFE, 39 mol% of units based on CHVE, and 11 mol% of units based on HBVE (hydroxyl value: 50mg KOH/g, glass transition temperature Tg: 52 ℃, number average molecular weight Mn: 10000, fluorine atom content: 24 mass%, content ratio of units based on vinyl ether: 50 mol%).
Production example 2 (production of fluororesin F2)
Xylene (56g), ethanol (15.8g), CTFE (63.2g), t-BuVE (3.1g), EVE (4.5g), HBVE (12.1g), PV (41.5g), potassium carbonate (1.1g) and a xylene solution (0.7g) containing tert-butyl peroxypivalate in an amount of 50 mass% were introduced into the autoclave, and polymerization was carried out at 55 ℃ for 20 hours. The temperature was further raised to 65 ℃ and the autoclave was kept for 5 hours, followed by cooling, and the autoclave solution was filtered to obtain a solution containing fluorine resin F2 composed of a fluorine-containing polymer. The solvent in the resulting solution was removed by vacuum drying at 65 ℃ for 24 hours, and further vacuum dried at 130 ℃ for 20 minutes. The obtained block-shaped fluororesin F2 was pulverized to obtain a powdery fluororesin F2.
The fluororesin F2 was a polymer containing, in order relative to the total units contained in the fluororesin F2, 50 mol% of units based on CTFE, 3 mol% of units based on t-BuVE, 10 mol% of units based on HBVE, 6 mol% of units based on EVE, and 31 mol% of units based on PV (hydroxyl value: 51mg KOH/g, glass transition temperature Tg: 52 ℃, number average molecular weight Mn: 12000, fluorine atom content: 24 mass%, content ratio of units based on vinyl ether: 19 mol%).
[ abbreviation in production example ]
CTFE: chlorotrifluoroethylene
CHVE: cyclohexyl vinyl ether
HBVE: 4-hydroxybutyl vinyl ether
t-BuVE: tert-butyl vinyl ether
EVE: ethyl vinyl ether
PV: vinyl pivalate
[ measurement method ]
Hydroxyl value and acid value: JIS K0070-3 (1992)
Glass transition temperature Tg: mid-point glass transition temperature of polymers as determined by Differential Scanning Calorimetry (DSC)
Number average molecular weight Mn: value obtained by measuring polystyrene as a standard substance by gel permeation chromatography
A unit: the unit is a general term for a radical which is directly formed by polymerization of a monomer and is derived from 1 molecule of the monomer and a radical obtained by chemically converting a part of the radical. The polymer was analyzed by Nuclear Magnetic Resonance (NMR) method, and the content (mol%) of each unit with respect to the total units contained in the polymer was determined.
Fluorine atom content: the fluorine atom content is a ratio (% by mass) of a mass of a fluorine atom to a total mass of the fluororesin, and is measured by a Nuclear Magnetic Resonance (NMR) method.
Examples 1 to 11
[ production of film ]
Each of the components described in the column of "film component" shown in table 1 below was melt-kneaded using a pneumatic co-extruder equipped with an extruder to form a film having a thickness of 0.1 mm. The obtained film was cut into a size of 1.0m × 1.0m for chemical resistance evaluation described later. The sheet was also cut into a size of 7cm × 15cm for accelerated aging test described later.
Example 12
A fluorine-containing coating film was formed by applying a fluorine-based coating material having a dry film thickness of 10 μm to a commercially available agricultural polyethylene film, drying and curing the coating film, and evaluated as described later.
The results are shown in Table 1 below.
TABLE 1
[ detailed description of the respective ingredients in Table 1 ]
Non-fluororesin:
polyethylene: HI-ZEX 7200F (available from Priman Polymer Co., Ltd.)
Polyvinyl chloride: NOVATECH LV430 (product of Mitsubishi chemical corporation)
Fluororesin:
f1: fluororesin F1 produced in production example 1
F2: fluororesin F2 produced in production example 2
F3: richflon SRF-750P (trade name of fluoroolefin-vinyl ester fluororesin, Sinorrich Co., Ltd., hydroxyl value: 54mgKOH/g, glass transition temperature Tg: 41 ℃, number average molecular weight Mn: 10000, fluorine atom content: 22%, content ratio of vinyl ether-based unit: 0 mol%)
F4: DS203 (polyvinylidene fluoride, trade name of Toyue corporation, melting Point: 179 ℃, fluorine atom content: 59%, content ratio of vinyl ether-based units: 0 mol%)
Plasticizer: di-n-octyl phthalate
Silica-based lubricant: ソルスフェア H31 (AGC エスアイテック Co., Ltd.)
Light stabilizer: CHIMASSORB 944 (available from Qianye specialty Chemicals Co., Ltd.)
[ evaluation method ]
Chemical resistance
The film was immersed in acidic water for 8 hours, and then covered on a round can filled with hot water at a constant temperature of 60 ℃ and allowed to stand for 50 days, and the change in appearance of the film was visually observed. Evaluation was performed according to the following criteria.
A: no change in appearance of the film
B: the film had a dirty appearance
C: the film had a damaged appearance
Weather resistance: accelerated aging tests were carried out for a test time of 1000 hours using an accelerated aging tester (model: QUV/SE, manufactured by Q-PANNEL LAB PRODUCTS Co., Ltd.). The appearance of the film after the test was visually confirmed and evaluated according to the following criteria.
A: no change in appearance of the film
B: the film had a dirty appearance
C: the film had a damaged appearance
As is clear from the results in table 1, examples 1, 3, 9, and 10, the fluororesin was uniformly diffused in the non-fluororesin after melting, and other components such as the light stabilizer in the film were protected, and the film was excellent in film performance, and extremely excellent in chemical resistance and weather resistance. Example 2 is similar, but since the content of the fluororesin is slightly higher than the total mass of the non-fluororesin, the film becomes somewhat brittle and the chemical resistance is slightly weak. In example 5, when a fluororesin having a slightly smaller content of vinyl ether-based units was used, the lubricant was slightly easily removed and the chemical resistance was slightly poor. In example 6, when a fluororesin containing no vinyl ether-based unit was used, the lubricant was slightly detached and the chemical resistance was slightly poor.
On the other hand, in example 4 as a comparative example, when the content of the fluororesin is too high relative to the total mass of the non-fluororesin, the film becomes brittle and is poor in chemical resistance and weather resistance. In example 7 as a comparative example, when a fluororesin having an excessively high fluorine atom content was used, the dispersibility of the fluororesin was deteriorated, and the chemical resistance and weather resistance were not good. In comparative example 8, since a fluororesin was not used, the film performance was poor, and the chemical resistance and weather resistance were not good. In comparative example 11, when a fluororesin having an excessively high fluorine atom content was used, the plasticizer eluted, the film performance was poor, and the chemical resistance and weather resistance were not good. In example 12 as a reference example, a laminate of a fluororesin coating film and a non-fluororesin coating film was formed by applying a fluorine-based coating material to a commercially available agricultural polyethylene film, and as a result, the interface between the fluororesin coating film and the non-fluororesin coating film began to deteriorate, and peeling of the coating film occurred.
Possibility of industrial utilization
The film of the invention has excellent weather resistance and greatly prolonged service life; excellent chemical resistance, maintaining good chemical resistance even after being subjected to acid rain or pesticide spreading; the film is not easy to adhere to soil, so that the weight of the film is reduced when the film is reused or discarded; the light transmittance is high, and the light-transmitting film is particularly useful for the cultivation and growth of plants; the film is prevented from becoming brittle, elution of other components such as a plasticizer in the film component is avoided, and embrittlement is not easily caused even in long-term use. Therefore, the film of the present invention can be widely used for applications such as mold release films, films for building structures, agricultural films, films for protecting wind turbine blades, decorative films, packaging films, protective films for automotive finishes, films for communication towers, and films for airplanes.
Claims (10)
1. A film which is a film comprising a non-fluororesin and a fluororesin,
the content of the fluororesin is 0.1-20.0% by mass relative to the total mass of the non-fluororesin,
the fluorine atom content of the fluororesin is 50 mass% or less.
2. The film of claim 1, wherein the non-fluororesin is selected from at least one of polyethylene, polyvinyl chloride, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polyvinyl alcohol, polystyrene, polyurethane, polyester, polycarbonate, (meth) acrylic resin, vinyl chloride resin, vinyl ester resin.
3. The membrane of claim 1, wherein the fluororesin comprises a fluoropolymer comprising fluoroolefin-based units, the fluoroolefin being selected from the group consisting of CF2＝CF2、CF2＝CFCl、CF2＝CHF、CH2＝CF2、CF2＝CFCF3、CF2＝CHCF3、CF3CH＝CHF、CF3CF＝CH2At least one of (1).
4. The membrane of claim 1, wherein the fluororesin comprises a fluoropolymer comprising units based on a fluoroolefin selected from the group consisting of CF and units based on a non-fluorinated monomer2＝CF2、CF2＝CFCl、CF2＝CHF、CH2＝CF2、CF2＝CFCF3、CF2＝CHCF3、CF3CH＝CHF、CF3CF＝CH2At least one of (1).
5. The film according to claim 4, wherein the unit based on the non-fluorine monomer contained in the fluororesin contains a unit based on a monomer having a crosslinkable group selected from at least one of a carboxylic acid polymerizable with vinyl alcohol or a fluoroolefin, and a vinyl ether, a vinyl ester, an allyl ether, an allyl ester, an acrylic ester, and a methacrylic ester having a crosslinkable group.
6. The film of claim 5, wherein the monomer having a crosslinkable group is selected from CH2＝CHCOOH、CH(CH3)＝CHCOOH、CH2＝C(CH3)COOH、
CH2＝CH(CH2)n2COOH、CH2＝CHO-CH2-Ring C6H10-CH2OH、CH2＝CHCH2O-CH2-Ring C6H10-CH2OH、CH2＝CHOCH2CH2OH、CH2＝CHCH2OCH2CH2OH、CH2＝CHOCH2CH2CH2CH2OH、CH2＝CHCH2OCH2CH2CH2CH2OH、CH2＝CHCOOCH2CH2OH、CH2＝C(CH3)COOCH2CH2At least one of OH, wherein n2 represents an integer of 1 to 10.
7. The film of claim 3 or 4, wherein the fluoropolymer has a glass transition temperature of greater than 10 ℃.
8. The film according to any one of claims 1 to 6, which is obtained by melt-kneading raw materials comprising the non-fluororesin and the fluororesin.
9. A method for producing a film according to any one of claims 1 to 8, comprising melt-kneading a raw material containing the non-fluororesin and the fluororesin to produce a film,
the content of the fluororesin is 0.1-20.0% by mass relative to the total mass of the non-fluororesin,
the fluorine atom content of the fluororesin is 50 mass% or less.
10. Use of the film according to any one of claims 1 to 8 as a mold release film, a film for building structures, an agricultural film, a film for protecting wind-power-generating blades, a decorative film, a packaging film, a protective film for automobile finish, a film for communication towers, or a film for aircraft.
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| PCT/JP2021/028517 WO2022030417A1 (en) | 2020-08-03 | 2021-07-30 | Film, method for producing film and use of film |
| CN202180061212.9A CN116249725A (en) | 2020-08-03 | 2021-07-30 | Film, method for producing film, and use of film |
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| TW302384B (en) * | 1992-12-02 | 1997-04-11 | Hoechst Ag | |
| ES2438533T3 (en) * | 2004-06-25 | 2014-01-17 | Daikin Industries, Ltd. | Composition of resin and molded thereof |
| JP5930971B2 (en) * | 2010-12-01 | 2016-06-08 | 日産化学工業株式会社 | Surface modified extrusion film |
| KR102372956B1 (en) * | 2013-12-17 | 2022-03-10 | 에이지씨 가부시키가이샤 | Negative photosensitive resin composition, resin cured film, partition wall, and optical element |
| CN104031199A (en) * | 2014-05-22 | 2014-09-10 | 巨化集团技术中心 | Method of preparing fluororesin for electrostatic spraying by dispersion polymerization and coating application of resin |
| WO2016006252A1 (en) * | 2014-07-10 | 2016-01-14 | 東レ・ダウコーニング株式会社 | Delamination control agent, silicone delamination agent composition containing same, delamination sheet, and laminate body |
| JP6617704B2 (en) * | 2014-07-18 | 2019-12-11 | Ａｇｃ株式会社 | Protein adhesion inhibitor |
| CN108026345A (en) * | 2015-09-11 | 2018-05-11 | 三菱化学株式会社 | Poly (vinyl chloride) resin composition and formed body |
| WO2019044019A1 (en) * | 2017-08-31 | 2019-03-07 | ハリマ化成株式会社 | Multilayer film and two-liquid curable coating agent |
| TWI702254B (en) * | 2017-09-11 | 2020-08-21 | 南亞塑膠工業股份有限公司 | Method for manufacturing cross-linked and weather-resistant polyolefin sheet for solar cell backplane |
| EP3730295B1 (en) * | 2017-12-20 | 2024-11-06 | Agc Inc. | Decorative film and manufacturing method for three-dimensional molding with decorative film |
| JP2019214719A (en) * | 2018-06-12 | 2019-12-19 | Ａｇｃ株式会社 | Powdered paint and method for manufacturing powdered paint |
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