WO2016121260A1 - Agent d'alkylation acide, procédé de production de produit alkylé par un acide, composition de résine et film de polyester - Google Patents

Agent d'alkylation acide, procédé de production de produit alkylé par un acide, composition de résine et film de polyester Download PDF

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WO2016121260A1
WO2016121260A1 PCT/JP2015/085284 JP2015085284W WO2016121260A1 WO 2016121260 A1 WO2016121260 A1 WO 2016121260A1 JP 2015085284 W JP2015085284 W JP 2015085284W WO 2016121260 A1 WO2016121260 A1 WO 2016121260A1
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group
acid
general formula
compound
alkylating agent
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PCT/JP2015/085284
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Japanese (ja)
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上平　茂生
福田　誠
倫弘 小川
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富士フイルム株式会社
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Publication of WO2016121260A1 publication Critical patent/WO2016121260A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/14—Preparation of ethers by exchange of organic parts on the ether-oxygen for other organic parts, e.g. by trans-etherification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/04—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers
    • C07C257/08—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines without replacement of the other oxygen atom of the carboxyl group, e.g. imino-ethers having carbon atoms of imino-carboxyl groups bound to carbon atoms of six-membered aromatic rings

Definitions

  • the present invention relates to an acid alkylating agent, a method for producing an acid alkylated product, a resin composition, and a polyester film.
  • Polymers are widely used in various fields, both indoors and outdoors. For example, when the polymer is heated to a high temperature during molding or used in a product that is exclusively installed outdoors, the polymer may be exposed to a severe environment of high temperature or high humidity for a long period of time.
  • a trace amount of acid may be present in the polymer.
  • deterioration of the polymer may be promoted when the polymer is exposed to high-temperature or high-humidity environmental conditions as described above. Specifically, it may cause thermal degradation of the polymer at the time of molding, and even after molding, depending on the usage environment, it may be deteriorated by promoting hydrolysis of the polymer by being exposed to a humid heat environment for a long time. .
  • the presence of a small amount of acid similarly causes deterioration of the polymer regardless of whether the acid itself is bonded to the polymer chain or the acid is mixed.
  • a polymer film typified by a polyester film such as polyethylene terephthalate has been used for a backsheet disposed for protecting the back surface of a solar cell.
  • polyester is known to have poor hydrolysis resistance and easily become brittle because a carboxylic acid group present at the end of a polymer chain promotes hydrolysis.
  • a method of sealing the carboxylic acid group remaining at the polymer chain end of the polyester is known.
  • carbodiimide compounds and cyclic imino ether compounds are known.
  • a polyester film containing an oxazoline compound and an oxazine compound which are carbodiimide compounds or cyclic imino ether compounds is disclosed (for example, see JP 2010-031174 A).
  • a carbodiimide compound or a cyclic imino ether compound is reacted with a carboxylic acid group present at the polyester terminal to improve the dimensional stability and hydrolysis resistance of the polyester.
  • the carbodiimide compound has a problem that free isocyanate is volatilized as an irritating gas after reacting with a carboxylic acid group.
  • Cyclic imino ether compounds are known to self-polymerize. When the cyclic imino ether compound is examined, the self-polymerized cyclic imino ether compound is likely to exist as a gel component in the resin, and the gel component increases the viscosity of the resin. The presence of the gel component causes gel defects when the film is formed, and is a factor that impairs the surface state of the formed film (hereinafter also simply referred to as “planar shape”). .
  • the gel-like irregularity refers to a convex abnormal portion that is visually recognized as a bright spot on a smooth and uniform film surface, and has a major axis when observed from a direction perpendicular to the film surface. In many cases, it is about several tens of ⁇ m to several mm.
  • One embodiment of the present invention provides an acid alkylating agent and a method for producing an acid alkylated product that suppress generation of an irritating gas and suppress generation of a gel component (eg, a gel component in a resin). This is the issue.
  • Another object of one embodiment of the present invention is to provide a resin composition in which deterioration due to acidic groups and increase in viscosity are suppressed.
  • An acid alkylating agent represented by the following general formula (1), which acid-alkylates a compound having at least one acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • R 2 represents an alkyl group, an aryl group, or an alkoxy group
  • R 3 is represented by an alkyl group represented by the following general formula (2) or the following general formula (3).
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
  • R 2 , R 3 , R 11 , R 12 , and R 13 may be bonded to each other to form a ring.
  • R 31 , R 32 , and R 33 each independently represent a hydrogen atom or a substituent, and R 31 , R 32 , and R 33 are connected to each other to form a ring. Also good.
  • R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, the plurality of R 41 may be the same or different.
  • "*" in General formula (2) and General formula (3) represents the coupling
  • An acid alkylating agent represented by the following general formula (6) which acid-alkylates a compound having at least one acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • R ⁇ 11> , R ⁇ 12 > and R ⁇ 13 > represent a hydrogen atom, an alkyl group, or an aryl group each independently.
  • R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, the plurality of R 41 may be the same or different.
  • p represents an integer of 2 to 4.
  • L 1 represents a p-valent group in which the bond terminal to the carbon atom of the N ⁇ C—O moiety is an alkylene moiety, an arylene moiety, or an alkyleneoxy moiety.
  • An acid alkylating agent represented by the following general formula (7) which acid-alkylates a compound having at least one acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • R 2 represents an alkyl group, an aryl group, or an alkoxy group
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, an alkyl group, or an aryl group
  • p represents an integer of 2 to 4
  • L 2 represents a p-valent group in which the bond terminal to the nitrogen atom of the N ⁇ CO site is an arylene site or a cycloalkylene site.
  • R 2 represents an alkyl group, an aryl group, or an alkoxy group.
  • R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, the plurality of R 41 may be the same or different.
  • p represents an integer of 2 to 4
  • L 3 represents a p-valent group in which the bond terminal to the oxygen atom of the N ⁇ CO site is an alkylene site.
  • a resin composition comprising.
  • an acid alkylating agent and a method for producing an acid alkylated product that suppress generation of an irritating gas and suppress generation of a gel component for example, a gel component in a resin.
  • a gel component for example, a gel component in a resin.
  • the resin composition in which deterioration derived from an acidic group and a viscosity rise were suppressed is provided.
  • a polyester film having a small number of granular materials and an excellent surface shape.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the acid alkylating agent of the present disclosure is represented by the following general formula (1) and has a compound having at least one acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group (hereinafter simply referred to as “acidic” It is also referred to as a “compound having a group”).
  • Polymers may be exposed, for example, during molding or use, under severe environmental conditions of high temperature or high humidity, sometimes for extended periods of time. Such a situation tends to cause deterioration of the polymer.
  • an acidic group is present in the polymer, deterioration of the polymer may be promoted due to the acidic group.
  • polyester often contains a carboxylic acid group, and embrittlement associated with hydrolysis may be promoted due to the carboxylic acid group.
  • a carbodiimide compound or a cyclic iminoether compound as described in JP 2010-031174 A has been conventionally used to seal a terminal carboxylic acid group.
  • the carbodiimide compound described in Japanese Patent Application Laid-Open No. 2010-031174 generates an irritating gas along with the sealing of the carboxylic acid group
  • the cyclic imino ether compound described in Japanese Patent Application Laid-Open No. 2010-031174 is an
  • the viscosity of the polymer is increased due to self-polymerization and the film surface state is liable to be deteriorated.
  • the deterioration of the polymer is not limited to the case where the acidic group is bonded to the polymer chain, but may be caused by mixing the acid component into the polymer for various reasons in the raw material, the production process and the like.
  • the N ⁇ C—O linking site does not form a ring structure like an oxazoline ring in the structure, and N ⁇ C—
  • an imino ether compound having a chain structure having an alkoxy moiety in which alkyl is bonded to an oxygen atom at the O moiety is effective in preventing deterioration of the polymer without self-polymerization.
  • Alkylation of a compound having an acidic group with an imino ether compound having a structural portion of “N ⁇ C-alkoxy” is a reaction that prevents deterioration of the compound while maintaining the working environment and resin performance, and is a conventional sealing method. It is considered that the action is not observed in the reaction.
  • an acid alkylating agent represented by the general formula (1) which is an imino ether compound the acidic group is alkylated and sealed, and the volatilization of irritating gas and It becomes difficult to generate the gel component, and the deterioration of the compound having an acidic group can be suppressed.
  • embrittlement and thickening of a resin having an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group can be effectively suppressed.
  • a film excellent in the film surface can be obtained with few granular materials present on the film surface.
  • Acid alkylation refers to a reaction in which a hydrogen atom of an acidic group in a compound having an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group is substituted with an alkyl group. It is called an alkylating agent. Specifically, for example, as shown in the following reaction scheme, an alkylation reaction proceeds between a structural portion of “N ⁇ C-alkoxy” and a terminal sulfonic acid group (SO 3 H), and an acid alkylated product is converted into an acid alkylated product. Generate.
  • the acid alkylating agent (imino ether compound) represented by the general formula (1) reacts with the sulfonic acid group to be an amide compound and is contained in the resin composition.
  • the acid alkylating agent of the present disclosure which is an imino ether compound is represented by the following general formula (1).
  • R 2 is an alkyl group (including an optionally substituted cycloalkyl group) which may have a substituent, an aryl group which may have a substituent, or a substituent.
  • R 3 represents an alkyl group represented by the following general formula (2) or an aryl group represented by the following general formula (3)
  • R 11 , R 12 And R 13 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • R 2 , R 3 , R 11 , R 12 , and R 13 may be bonded to each other to form a ring.
  • R 31 , R 32 , and R 33 each independently represent a hydrogen atom or a substituent, and R 31 , R 32 , and R 33 are connected to each other to form a ring. Also good.
  • R 41 represents a substituent, and n represents an integer of 0 to 5. When n represents an integer of 2 or more and a plurality of R 41 are present, the plurality of R 41 may be the same or different.
  • "*" in General formula (2) and General formula (3) represents the coupling
  • the alkyl group represented by R 2 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.
  • the alkyl group represented by R 2 may be linear or branched. Further, the alkyl group represented by R 2 may be a cycloalkyl group. Examples of the alkyl group represented by R 2 include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, iso-butyl group, and n-pentyl.
  • the alkyl group represented by R 2 is more preferably a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an iso-butyl group, or a cyclohexyl group.
  • the alkyl group represented by R 2 may further have a substituent.
  • the number of carbon atoms in the alkyl group represented by R 2, indicate the number of carbon that does not contain a substituent group.
  • substituent for the alkyl group examples include an aryl group, an alkoxy group, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group.
  • the aryl group represented by R 2 is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.
  • Examples of the aryl group represented by R 2 include a phenyl group and a naphthyl group, and among them, a phenyl group is preferable.
  • the aryl group represented by R 2 may further have a substituent.
  • the number of carbon atoms of the aryl group represented by R 2 indicate the number of carbon that does not contain a substituent group.
  • the substituent of the aryl group is not particularly limited as long as the reaction between the imino ether group and the acidic group can proceed.
  • the alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amide group, hydroxyl group, ester Examples include groups, ether groups, aldehyde groups and the like.
  • the alkoxy group represented by R 2 is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 6 carbon atoms. Is particularly preferred.
  • the alkoxy group represented by R 2 may be linear, branched or cyclic. Examples of the alkoxy group represented by R 2 include a group in which —O— is linked to the terminal of the alkyl group represented by R 2 , and the alkoxy group may further have a substituent.
  • the number of carbon atoms of the alkoxy group represented by R 2 indicate the number of carbon that does not contain a substituent group.
  • the substituent of the alkoxy group is not particularly limited as long as the reaction between the imino ether group and the acidic group can proceed.
  • the alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amide group, hydroxyl group, ester Examples include groups, ether groups, aldehyde groups and the like.
  • R 3 represents an alkyl group represented by the general formula (2) or an aryl group represented by the general formula (3).
  • the alkyl group represented by the general formula (2) may be linear or branched.
  • R 31 , R 32 , or R 33 an aryl group, an alkoxy group, a halogen atom, a nitro, as in the substituent of the alkyl group represented by R 2 Groups, amide groups, hydroxyl groups, ester groups, ether groups, aldehyde groups and the like.
  • R 31 , R 32 , and R 33 may all be hydrogen atoms, all may be the same substituent, or may be different from each other.
  • the alkyl group represented by the general formula (2) includes a cycloalkyl group.
  • the alkyl group represented by the general formula (2) is a cycloalkyl group
  • examples of the cycloalkyl group include a cyclohexyl group.
  • examples of the substituent represented by R 41 include an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, and an aldehyde group. Is done.
  • the alkyl group which is a substituent represented by R 41 is synonymous with the alkyl group represented by R 2 , and the preferred embodiment is also the same.
  • n represents an integer of 0 to 5, and when n is 2 or more, a plurality of R 41 may be the same or different. n is more preferably from 0 to 3, more preferably from 0 to 2, from the viewpoint of availability of raw materials.
  • R 3 is preferably an aryl group represented by the general formula (3) and n is 0, that is, a phenyl group.
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent.
  • Alkyl and aryl group has the same meaning as the alkyl group and aryl group represented by R 2, preferred embodiments are also the same.
  • R 11 , R 12 and R 13 may be bonded to each other to form a ring.
  • R 2 , R 3 , R 11 , R 12 and R 13 in the general formula (1) may be bonded to each other to form a ring, but may not be bonded to each other to form a ring. preferable.
  • R 3 is an aryl group represented by the general formula (3)
  • the benzene ring and the ring containing any one of R 11 to R 13 may form a condensed ring.
  • R 3 is an aryl group represented by the general formula (3)
  • R 41 and at least one of R 11 to R 13 may not combine to form a ring.
  • R 3 is an alkyl group represented by the general formula (2)
  • at least one of R 11 to R 13 and at least one of R 31 to R 33 are not bonded to each other to form a ring Is preferred.
  • General formula (1) may include a repeating unit.
  • a hydrogen atom is removed from at least two selected from R 2 , R 3 , and R 11 to R 13 to form a repeating unit by forming two bonds.
  • This repeating unit preferably contains an imino ether (N ⁇ C—O) structure.
  • an imino ether compound represented by the general formula (4) having a benzene skeleton at R 3 in the general formula (1) is preferable. Having a benzene skeleton at the position of R 3 in the general formula (1) is advantageous in that gelation is further suppressed.
  • R 41 and n are respectively synonymous with R 41 and n in the general formula (3), preferable embodiments thereof are also the same.
  • n represents 0 and a phenyl group is bonded to the nitrogen atom of the N ⁇ CO site.
  • the imino ether compound represented by the general formula (5) having a benzene skeleton in R 2 of the general formula (4) is more preferable. Having a benzene skeleton at the R 2 position in the general formula (4) is advantageous in terms of the stability of the compound.
  • R 41 and n are respectively synonymous with R 41 and n in the general formula (3), preferable embodiments thereof are also the same.
  • n represents 0 and a phenyl group is bonded to the nitrogen atom of the N ⁇ CO site.
  • R 21 in the general formula (5) represents a substituent.
  • an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group examples include aldehyde groups.
  • the alkyl group which is a substituent represented by R 21 has the same meaning as the alkyl group represented by R 2 in the general formula (1), and the preferred embodiment is also the same.
  • m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R 21 may be the same or different. From the viewpoint of raw material availability, m is more preferably 0 to 3, and still more preferably 0 to 2.
  • n 0, a phenyl group is bonded to the nitrogen atom of the N ⁇ C—O site, and m represents 0, and the phenyl group is attached to the carbon atom of the N ⁇ C—O site. Is preferable.
  • the acid alkylating agent of the present disclosure is more preferably an imino ether compound having a multimeric structure among the imino ether compounds represented by the general formula (1) in terms of reaction efficiency of acid alkylation.
  • the acid alkylating agent of the present disclosure is preferably an acid alkylating agent which is an imino ether compound multimer represented by any one of the following general formulas (6) to (8).
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent.
  • R 41 represents a substituent
  • n represents an integer of 0 to 5. If R 41 there are a plurality, the plurality of R 41 may be the same or different.
  • p represents an integer of 2 to 4.
  • L 1 may have an alkylene moiety which may have a substituent, a cycloalkylene moiety which may have a substituent, or a substituent at the bond terminal with the carbon atom of the N ⁇ C—O moiety.
  • a p-valent group which is an arylene moiety or an alkyleneoxy moiety which may have a substituent is represented.
  • R 11 in the general formula (6), R 12, and R 13, R 11 in the general formula (1), R 12, and R 13 and have the same meanings, preferable embodiments thereof are also the same.
  • R 41 and n in the general formula (6) is respectively the same meanings as R 41 and n in the general formula (3), and preferred ranges are also the same.
  • L 1 in the general formula (6) includes an alkylene moiety that may have a substituent (including a cycloalkylene moiety that may have a substituent) at the bond terminal to the carbon atom of the N ⁇ C—O moiety. ), An arylene moiety which may have a substituent, or a p-valent group which is an alkyleneoxy moiety which may have a substituent. That is, the p-valent group has the above-described alkylene moiety (including cycloalkylene moiety), arylene moiety, or alkyleneoxy moiety at the bond terminal to the carbon atom of the N ⁇ C—O moiety.
  • p represents an integer of 2 to 4 and is preferably 2 or 3.
  • specific examples of the divalent group include an alkylene group having 1 to 12 carbon atoms (which may have a substituent) which may have a substituent.
  • Preferred cycloalkylene group an arylene group having 6 to 24 carbon atoms which may have a substituent, and an alkyleneoxy group having 1 to 12 carbon atoms which may have a substituent.
  • examples include a group having three bonds after removing one hydrogen atom.
  • L 1 has an alkylene moiety (including a cycloalkylene moiety), an arylene moiety, or an alkyleneoxy moiety at the bond terminal to the carbon atom of the N ⁇ C—O moiety as described above, and has a partial structure of — At least one linking group selected from the group consisting of SO 2 —, —CO—, an alkylene moiety, an alkenylene moiety, an alkynylene moiety, a phenylene moiety, a biphenylene moiety, a naphthylene moiety, —O—, —S—, and —SO—. Group which has.
  • alkylene moiety, alkenylene moiety, alkynylene moiety, phenylene moiety, biphenylene moiety, and naphthylene moiety as the partial structure may be unsubstituted or may have a substituent.
  • L 1 include, for example, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted ethylene, substituted or unsubstituted n-butylene, substituted or unsubstituted Cyclohexylene, substituted or unsubstituted —C 6 H 10 —C 6 H 10 —, substituted or unsubstituted —C 6 H 10 —CH 2 —C 6 H 10 —, substituted or unsubstituted —C 6 H 4 —C (CH 3 ) 2 —C 6 H 4 —, substituted or unsubstituted —C 6 H 4 —CH 2 —C 6 H 4 —, substituted or unsubstituted —C 6 H 4 —C (O) — C 6 H 4 —, substituted or unsubstituted —C 6 H
  • P in the general formula (6) is preferably an integer of 2 to 4.
  • p is in the range of 2 to 4, a compound having two or more N ⁇ C—O moieties (iminoether moieties) in one molecule can be obtained.
  • a compound having two or more N ⁇ C—O moieties in one molecule has a low imino ether value (total molecular weight / number of functional groups of imino ether), and acid alkylation of an acidic group of a compound having an acidic group with an imino ether compound It is suitable for allowing the reaction to proceed efficiently.
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom or an alkyl group that may have a substituent, and n is 0.
  • a phenyl group is bonded to the nitrogen atom of the N ⁇ C—O site, p is 2 or 3, and L 1 is substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted
  • a compound representing —C 6 H 4 —NHC (O) —C 6 H 4 — is preferred.
  • R 2 represents an alkyl group that may have a substituent (including a cycloalkyl group that may have a substituent), an aryl group that may have a substituent, or a substituent.
  • R 11 , R 12 , and R 13 may each independently have a hydrogen atom, an alkyl group that may have a substituent, or a substituent.
  • p represents an integer of 2 to 4
  • L 2 may have an arylene moiety that may have a substituent, or a substituent at the bond terminal to the nitrogen atom of the N ⁇ C—O moiety. It represents a p-valent group that is a cycloalkylene moiety.
  • L 2 in the general formula (7) represents an arylene moiety having 6 to 48 carbon atoms which may have a substituent, or a cycloalkylene moiety having 3 to 6 carbon atoms which may have a substituent.
  • This represents a p-valent group at the terminal of the CO bond with the nitrogen atom.
  • L 2 is preferably a p-valent group whose bond terminal to the nitrogen atom is an arylene moiety that may have a substituent.
  • p represents an integer of 2 to 4, and is preferably 2 or 3 from the viewpoint of excellent acid alkylation reaction of an acidic group in a compound having an acidic group by an acid alkylating agent.
  • L 2 has an arylene moiety or a cycloalkylene moiety at the bond terminal with the nitrogen atom of the N ⁇ C—O moiety as described above, and has a partial structure of —SO 2 —, —CO—, an alkylene moiety, And a group having at least one linking group selected from the group consisting of an alkenylene moiety, an alkynylene moiety, a phenylene moiety, a biphenylene moiety, a naphthylene moiety, —O—, —S—, and —SO—.
  • alkylene moiety, alkenylene moiety, alkynylene moiety, phenylene moiety, biphenylene moiety, and naphthylene moiety as the partial structure may be unsubstituted or may have a substituent.
  • Preferred examples of L 2 include substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted cyclohexylene, substituted or unsubstituted —C 6 H 10 —C 6.
  • R 2 represents an aryl group which may have a substituent
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom.
  • R 11 , R 12 , and R 13 are each independently a hydrogen atom.
  • p represents 2 or 3
  • L 2 has an arylene moiety at the bond terminal with the nitrogen atom of the N ⁇ CO moiety, and as a partial structure
  • R 11 , R 12 , and R 13 each independently represents a hydrogen atom or an alkyl group that may have a substituent
  • p represents 2 or 3
  • L 2 represents -C 6 H 4 substituted or unsubstituted O-C 6 H 4 -C ( CH 3) 2 -C 6 H 4 -O-C 6 H 4 -, substituted or unsubstituted -C 6 H 4 -NHC (O) -C 6 H 4 -, or
  • a compound representing a substituted or unsubstituted —C 6 H 4 —O— (C 6 H 4 ) 2 —O—C 6 H 4 —, and particularly preferably R 2 may have a substituent.
  • R 11 , R 12 , and R 13 each independently represents a hydrogen atom or an alkyl group which may have a substituent, p represents 2, and L 2 represents a substituted or unsubstituted group -C 6 H 4 —O—C 6 H 4 —C (CH 3 ) 2 —C 6 H 4 —O—C 6 H 4 —.
  • R 2 represents an alkyl group that may have a substituent (including a cycloalkyl group that may have a substituent), an aryl group that may have a substituent, or a substituent.
  • An alkoxy group which may have a group is represented.
  • R 41 represents a substituent, and when R 41 there are a plurality, the plurality of R 41 may be the same or different.
  • n represents an integer of 0 to 5.
  • p represents an integer of 2 to 4.
  • L 3 represents a p-valent group in which the bond terminal to the oxygen atom of the N ⁇ C—O moiety is an alkylene moiety. However, in the alkylene portion of L 3 , a part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • R 2 in the general formula (8) has the same meaning as R 2 in the general formula (1), a preferable embodiment thereof is also the same.
  • R 41 and n in the general formula (8) is respectively the same meanings as R 41 and n in the general formula (3), preferable embodiments thereof are also the same.
  • L 3 in the general formula (8) represents a p-valent group in which the bond terminal with the oxygen atom of the N ⁇ CO site is an alkylene site. That is, the p-valent group has an alkylene moiety at the terminal of the bond with the oxygen atom of the N ⁇ C—O moiety.
  • the alkylene moiety of L 3 may be a substituted alkylene moiety in which some or all of the hydrogen atoms are substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • p represents an integer of 2 to 4, and is preferably 2 or 3 from the viewpoint of excellent acid alkylation reaction of an acidic group-containing compound with an imino ether compound.
  • L 3 include an alkylene group.
  • L 3 has an alkylene moiety at the bond terminal with the oxygen atom of the N ⁇ C—O moiety as described above, and has a partial structure of —SO 2 —, —CO—, an alkylene group, an alkenylene group, an alkynylene.
  • a group having at least one linking group selected from the group consisting of a group, a phenylene group, a biphenylene group, a naphthylene group, —O—, —S—, and —SO—.
  • alkylene moiety, alkenylene moiety, alkynylene moiety, phenylene moiety, biphenylene moiety, and naphthylene moiety as the partial structure may be unsubstituted or may have a substituent.
  • Preferable L 3 is substituted or unsubstituted ethylene, substituted or unsubstituted n-butylene, substituted or unsubstituted —CH 2 —C (CH 3 ) 2 —CH 2 —, substituted or unsubstituted —CH 2 —C 6 H 4 —CH 2 —, substituted or unsubstituted —C 2 H 4 —CO—C 6 H 4 —COO—C 2 H 4 — and the like can be mentioned.
  • the imino ether compound that is an acid alkylating agent of the present disclosure is used in the form of a multimer as represented by the above general formulas (6) to (8) from the viewpoint of efficiently performing acid sealing by an acid alkylation reaction. It is preferable.
  • the nitrogen atom is small in that there is little concern about the change in liquid properties when polymerized, for example, the increase in viscosity when a resin composition is prepared.
  • An imino ether compound represented by the general formula (6) or (7) that is linked by (N) or a carbon atom (O) to form a multimer is preferable.
  • the molecular weight per iminoether (N ⁇ C—O) structure of the acid alkylating agent (iminoether compound) represented by the general formula (1) is preferably in the range of 1000 or less, more preferably in the range of 750 or less. The range of 500 or less is more preferable.
  • the lower limit of the molecular weight per iminoether structure is preferably 200. When the molecular weight per imino ether structure is within the above range, acid alkylation (acid sealing) of an acidic group can be effectively performed even with a small addition amount.
  • the molecular weight per imino ether structure represents a molecular weight obtained by dividing the molecular weight of a compound by the number of imino ether (N ⁇ C—O) structures in the compound.
  • the acid alkylating agent (imino ether compound) represented by the general formula (1) is reacted with a compound (for example, a resin) having an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, thereby forming an acidic group.
  • a compound for example, a resin
  • the reaction temperature is preferably selected based on the melting point (Tm) of the compound having an acidic group.
  • the reaction temperature can be, for example, in the range of (Tm + 5) ° C. to (Tm + 100) ° C., and is preferably in the range of (Tm + 10) ° C. to (Tm + 80) ° C.
  • reaction temperature is (Tm + 5) ° C. or higher, the acid alkylation reaction proceeds well and gelation is effectively suppressed. Further, when the reaction temperature is (Tm + 100) ° C. or lower, the thermal decomposition of the compound having an acidic group is suppressed, and the hydrolysis resistance is excellent.
  • an amide compound is converted to imidoyl chloride and reacted with an alkoxide, and a method of reacting an aniline compound and an orthoester compound. It has been known.
  • a synthesis method any method may be used, but a method of reacting an aniline compound and an ortho ester compound is preferable.
  • An imino ether compound synthesized by a method of reacting an aniline compound and an ortho ester compound is preferable in that the hydrolysis resistance of the compound having a color and an acidic group is further improved.
  • the reason why the hydrolysis resistance of the compound having a color and an acidic group is further improved is that the aniline compound and the ortho ester compound are reacted.
  • the method of reacting an aniline compound and an ortho ester compound is preferable also from the point which can synthesize
  • aniline when preparing a resin composition containing an acid alkylating agent represented by the general formula (1) and a resin having an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, aniline is used.
  • the resin composition to which an imino ether compound synthesized by a method of reacting a compound and an ortho ester compound is added has excellent hydrolysis resistance and color, and can be applied to various applications.
  • it is suitably used for a solar cell backsheet.
  • a back sheet for a solar cell is produced using a resin composition with little coloring, the power generation efficiency of the solar cell can be improved without reducing the reflectance of sunlight.
  • the ortho ester compound used for the synthesis of the imino ether compound which is an acid alkylating agent represented by the general formula (1) is preferably a compound represented by the following general formula (9).
  • R 4 represents an alkyl group that may have a substituent (including a cycloalkyl group that may have a substituent), an aryl group that may have a substituent, or a substituent.
  • R 4 represents an alkoxy group which may have a group
  • R 51 , R 52 and R 53 each independently have a hydrogen atom, an alkyl group which may have a substituent, or a substituent.
  • Orthoester compounds include trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, tribenzyl orthoacetate, trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, tribenzyl orthoformate, orthopropion Trimethyl acid, triethyl orthopropionate, tripropyl orthopropionate, tributyl orthopropionate, tribenzyl orthopropionate, trimethyl orthobenzoate, triethyl orthobenzoate, tripropyl orthobenzoate, tributyl orthobenzoate, tribenzyl orthobenzoate, etc. Is mentioned.
  • the ortho ester compound a commercially available product may be used, or it may be synthesized and used as desired.
  • the ortho ester compound can be synthesized by a method in which a nitrile compound such as hydrogen cyanide, acetonitrile, propionitrile, n-butyronitrile, or benzonitrile is imidate and reacted with alcohol, or a method in which trichlorobenzene and alkoxide are reacted. .
  • the method for producing an acid alkylated product of the present disclosure includes the above-described acid alkylating agent of the present disclosure and a compound having at least one acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group (an acidic group).
  • Compound) and an acid alkylated product by reacting the compound with the compound in the temperature range of 100 ° C to 350 ° C. Since acid alkylation of acidic groups is performed using the acid alkylating agent of the present disclosure, generation of irritating odor accompanying acid alkylation, and thickening or gelation when acid alkylated products are generated can be suppressed. .
  • acid alkylation (acid capping) of an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group includes a sulfonic acid group, a phosphoric acid group, and a phenolic group. It is carried out by mixing and reacting a compound having at least one acidic group selected from a hydroxyl group (for example, a resin) and an acid alkylating agent represented by the general formula (1) in a molten state.
  • the reaction temperature during the reaction is in the temperature range of 100 ° C to 350 ° C.
  • the acid alkylation reaction of the acidic group-containing compound with the acidic group iminoether compound proceeds efficiently. That is, when the reaction temperature is 100 ° C. or higher, the acid alkylation reaction proceeds more favorably and does not accompany gelation. A film is obtained.
  • the reaction temperature is 350 ° C. or lower, thermal decomposition of the compound having an acidic group is suppressed, and the hydrolysis resistance is excellent.
  • the reaction temperature of 350 ° C. or lower is particularly effective when the compound having an acidic group is a resin.
  • the reaction temperature at the time of reaction is, for example, the following temperature range: It can be.
  • the reaction temperature is preferably 265 ° C to 350 ° C, more preferably 270 ° C to 340 ° C.
  • the reaction temperature is preferably 230 ° C. to 325 ° C., more preferably 235 ° C. to 305 ° C.
  • polyethylene-2,6-naphthalate it is preferably 270 ° C. to 350 ° C., more preferably 275 ° C. to 345 ° C.
  • the reaction time is preferably 1 minute to 60 minutes, more preferably 1 minute to 30 minutes, and further preferably 1 minute to 15 minutes.
  • the imino ether compound and the compound having an acidic group are reacted in a temperature range of 100 ° C. to 350 ° C.
  • the imino ether group and An acid alkylated product is produced by reacting with an acidic group and alkylating the acidic group.
  • the imino ether compound that is an acid alkylating agent reacts with an acidic group to become an amide compound.
  • the reaction rate between the acid alkylating agent represented by the general formula (1) and the compound having an acidic group can be in the range of 0.1% to 99%, and 1% to 90% is more Preferably, 2% to 80% is more preferable.
  • the reaction rate is within the above range, the hydrolysis resistance of the compound having an acidic group (particularly a resin) can be further improved.
  • a resin is used as the compound having an acidic group, in the resin composition containing the acid alkylating agent represented by the general formula (1) and the resin, the generated amide compound bleeds out from the resin composition. The phenomenon is suppressed, and the generation of granular materials on the film surface when the film is formed using the resin composition is suppressed, and as a result, the film has an excellent film surface shape.
  • a compound having a specific acidic group is acid alkylated using an acid alkylating agent represented by the general formula (1).
  • An imino ether compound having a ring structure such as oxazoline or the like that is, having no chain structure containing an N ⁇ C—O moiety and having a chain-like “N ⁇ C-alkoxy” moiety is obtained by an acid alkylation reaction. Since the nucleophilicity of the group amide is not high, it is considered that self-condensation does not occur. Since self-condensation does not occur, the phenomenon of iminoether compound gelation can be suppressed.
  • the resin composition of the present disclosure contains the acid alkylating agent of the present disclosure described above and a resin having at least one acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and is necessary. Depending on the case, other components may be contained.
  • the details of the acid alkylating agent of the present disclosure are as described above, and the same applies to preferred embodiments.
  • the content of the acid alkylating agent in the resin composition is preferably 0.05% by mass to 10% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total solid content of the resin composition. 0.1 mass% to 5 mass% is more preferable, and 0.4 mass% to 3 mass% is particularly preferable.
  • the content of the acid alkylating agent is 0.05% by mass or more, the acid alkylating reaction of the acidic group proceeds well.
  • the content of the acid alkylating agent is 10% by mass or less, it is advantageous in that the resin performance is not changed.
  • the resin composition of the present disclosure may contain a compound capable of acid alkylation other than the acid alkylating agent of the present disclosure depending on the purpose and the case.
  • the acid alkylating agent of the present disclosure may be used in combination with a carbodiimide compound, a ketene imine compound, an epoxy compound, an oxazoline compound, and the like.
  • content of the acid alkylating agent of this indication with respect to the total mass of organic compounds other than resin contained in a resin composition is 70 mass% or more. Is preferable, 80 mass% or more is more preferable, and 90 mass% or more is still more preferable.
  • the resin is not particularly limited as long as the resin has an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group.
  • a resin having at least one acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group includes a sulfonic acid group, a phosphoric acid group, a chain structure in a molecule (so-called polymer chain),
  • a resin having an acidic group selected from a phenolic hydroxyl group, a compound having an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group as a polymerization catalyst or additive in the resin Includes a resin having an acidic group.
  • the resins in the present disclosure include polyesters, polyolefins, polyamides, polyurethanes, (meth) acrylic resins, fluororesins, mixed resins thereof, and the like.
  • polyesters and mixed resins of polyesters and other resins are used. is there.
  • a mixed resin obtained by blending a small amount of other types of resin such as polyimide with polyester may be used.
  • Polyester is used for, for example, a solar cell backsheet, and a resin used for the solar cell backsheet is required to have excellent wet heat resistance (particularly hydrolysis resistance) over a long period of time.
  • polyesters may have sulfonic acid groups, phosphoric acid groups, and phenolic hydroxyl groups due to contamination from raw materials used, polymerization catalysts, and the like.
  • acid alkylating agent of the present disclosure By acid alkylating these acidic groups using the acid alkylating agent of the present disclosure, a polyester having a high wet heat resistance (i.e., hydrolysis resistance) is obtained.
  • the resin composition of the present disclosure is obtained by mixing the acid alkylating agent of the present disclosure and a resin having an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group in a molten state.
  • the resin composition is preferably a resin composition in which an acidic group is acid-alkylated (acid-sealed) by a reaction in between.
  • a saturated polyester is preferable.
  • Saturated polyester provides a polyester film having superior mechanical strength compared to unsaturated polyester.
  • the polyester has an ester (—COO—) bond or an oxycarbonyl (—OCO—) bond in one molecular chain, and may be either a homopolymer or a copolymer.
  • a linear saturated polyester synthesized from a group dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof is preferred. Linear saturated polyesters are described in JP2009-155479A, JP2010-235824A, and the like.
  • linear saturated polyesters examples include polyethylene terephthalate (PET), polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate, and the like.
  • PET polyethylene terephthalate
  • Polyethylene terephthalate is preferable in terms of the balance between physical properties and cost.
  • polyester you may use crystalline polyester which can form anisotropy at the time of melt film forming.
  • the molecular weight of the polyester is preferably 5,000 to 100,000, more preferably 8,000 to 80,000 in terms of weight average molecular weight (Mw), from the viewpoint of heat resistance and viscosity, and 12,000. More preferably, it is ⁇ 60,000.
  • the weight average molecular weight of the polyester is a value measured as a converted value of polymethyl methacrylate (PMMA) using gel permeation chromatography (GPC).
  • the calibration curves are "F-40", “F-20”, “F-4”, “F-1”, “A-5000”, “A-2500”, “A-1000”, and "n-" Propylbenzene ”was prepared from 8 samples.
  • the measurement conditions are as follows.
  • Polyester which is a preferable resin can be synthesized by a known polycondensation method, ring-opening polymerization method, or the like, and may be either a transesterification reaction or a reaction by direct polymerization.
  • the polyester is a polymer obtained by a condensation reaction mainly comprising an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, an aromatic dibasic acid or an ester thereof is formed It can synthesize
  • the component derived from the carboxylic acid of the polyester is a component derived from an aromatic dibasic acid or an ester-forming derivative thereof.
  • the carboxylic acid value or intrinsic viscosity of polyester can be controlled by selecting the raw material or reaction conditions.
  • a polymerization catalyst for the reaction, a compound selected from an aluminum compound, an antimony compound, a germanium compound, and a titanium compound is preferable from the viewpoint of keeping the carboxylic acid group in a small range of a predetermined amount or less, and particularly a titanium compound. Is preferred.
  • titanium compound When a titanium compound is used, an embodiment in which the titanium compound is added as a polymerization catalyst in the range of 1 ppm to 30 ppm for polymerization is preferred, and an embodiment in which the titanium compound is added as a polymerization catalyst in the range of 3 ppm to 15 ppm for polymerization is more preferred.
  • the amount of the titanium compound used is within the above range, the carboxylic acid group of the polyester is small, and the hydrolysis resistance can be kept low.
  • Polyesters using titanium compounds are synthesized in Japanese Patent Publication No. 8-301198, Japanese Patent No. 2543624, Japanese Patent No. 3335683, Japanese Patent No. 3717380, Japanese Patent No. 397756, Japanese Patent No. 396226, Patent Japanese Patent No.
  • the polyester is preferably solid-phase polymerized after polymerization.
  • the solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, and after slowly flowing for a predetermined time while heating, and then sent out), or a batch method (a resin is put into a container, A method of heating for a predetermined time) may be used.
  • the solid phase polymerization temperature is preferably 170 ° C to 240 ° C, more preferably 180 ° C to 230 ° C.
  • the solid phase polymerization time is preferably 5 to 100 hours, more preferably 10 to 75 hours.
  • the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
  • Japanese Patent No. 2621563 Japanese Patent No.
  • Japanese Patent No. 3136774 Japanese Patent No. 3603585, Japanese Patent No. 3616522, Japanese Patent No. 3617340, Japanese Patent No. 3680523, Japanese Patent No. 3680523 are disclosed.
  • the methods described in Japanese Patent No. 3717392 and Japanese Patent No. 4167159 can be applied.
  • the content ratio of the acid alkylating agent to the resin having an acidic group in the resin composition is preferably 0.05% by mass to 5% by mass, 0.1% More preferred is 4% by weight to 4% by weight, still more preferred is 0.1% by weight to 2% by weight, and particularly preferred is 0.4% by weight to 2% by weight.
  • the content ratio of the acid alkylating agent is 0.05% by mass or more, the acid alkylating agent is not decreased too much, so that the hydrolysis resistance of the resin composition and the film thereof is improved.
  • the content ratio of the acid alkylating agent is 5% by mass or less, the amount of the acid alkylating agent does not increase so much that the gelation of the resin composition is suppressed and the film thickness uniformity in the case of forming a film is improved. be able to. Moreover, the hydrolysis resistance of a resin composition and its film can be effectively improved because the content rate of an acid alkylating agent shall be in the said range.
  • the resin composition of the present disclosure includes a compatibilizer, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, as long as the effects of the present disclosure are not impaired.
  • Various additives such as a conductive agent, an ultraviolet absorber, a flame retardant, a flame retardant aid, a pigment, and a dye can be contained.
  • the polyester film of the present disclosure is a polyester film formed using the resin composition of the present disclosure described above. Since the polyester film of the present disclosure is molded using the resin composition of the present disclosure, the polyester film has a planar shape with less generation of particulates due to gelation of the resin composition.
  • the thickness of the polyester film varies depending on the application, but when used as a member for a solar cell backsheet, it is preferably 25 ⁇ m to 300 ⁇ m, more preferably 120 ⁇ m to 300 ⁇ m. When the thickness of the polyester film is 25 ⁇ m or more, sufficient mechanical strength is obtained, and when it is 300 ⁇ m or less, there is a cost advantage.
  • the polyester film is preferably stretched, more preferably biaxially stretched, more preferably planar biaxially stretched as compared to stretch of tubular or the like, and biaxially stretched sequentially. It is particularly preferable.
  • the biaxially stretched polyester film is stretched in the longitudinal direction (MD: Machine Direction) (hereinafter also referred to as “longitudinal stretching” or “MD stretching”) and in the width direction (TD: Transverse Direction) (hereinafter referred to as “Transverse Direction”). It is also referred to as “lateral stretching” or “TD stretching”.
  • MD Machine Direction
  • TD Transverse Direction
  • TD stretching Transverse Direction
  • the longitudinal stretching and the lateral stretching may each be performed once or may be performed a plurality of times. Moreover, you may extend
  • the MD orientation degree and the TD orientation degree of the polyester film are each preferably 0.14 or more, more preferably 0.155 or more, and particularly preferably 0.16 or more.
  • the MD orientation degree and the TD orientation degree were measured using an Abbe refractometer, a monochromatic light sodium D-line as a light source, methylene iodide as a mounting solution, and an x of the biaxially oriented film in an atmosphere at 25 ° C. , Y, z direction refractive index is measured, MD orientation degree can be calculated from ⁇ n (xz), and TD orientation degree can be calculated from ⁇ n (yz).
  • the terminal carboxyl group content in the polyester film is preferably 25 eq / ton (equivalent / ton; the same shall apply hereinafter) or less with respect to the polyester, and 20 eq / ton or less. More preferably, it is more preferably 16 eq / ton or less, and particularly preferably 15 eq / ton or less.
  • the polyester film preferably has a carboxylic acid value of 200 eq / ton or less, more preferably 100 eq / ton or less, and more preferably 50 eq / ton or less after storage treatment at 120 ° C. and a relative humidity of 100% for 105 hours. More preferably.
  • the carboxylic acid value in the polyester can be adjusted by polymerization catalyst species, polymerization time, and film forming conditions (film forming temperature and time).
  • the carboxylic acid value is H.264. A. Pohl, Anal. Chem. 26 (1954) 2145, and can be measured by a titration method.
  • the carboxylic acid value (eq / ton) is determined appropriately by dissolving polyester in benzyl alcohol at 205 ° C., adding phenol red indicator, and titrating with sodium hydroxide in water / methanol / benzyl alcohol. Is calculated from
  • the terminal hydroxyl group content in the polyester film is preferably 120 eq / ton or less, more preferably 90 eq / ton or less, based on the polyester.
  • the lower limit of the hydroxyl group content is preferably 20 eq / ton or more from the viewpoint of adhesion to the adjacent layer.
  • the hydroxyl group content in the polyester can be adjusted by the polymerization catalyst species, the polymerization time, and the film forming conditions (film forming temperature and time).
  • the terminal hydroxyl group content in the polyester is a value measured by proton nuclear magnetic resonance ( 1 H-Nuclear Magnetic Resonance, 1 H-NMR) using a deuterated hexafluoroisopropanol solvent.
  • the intrinsic viscosity (IV) of the polyester film is preferably 0.55 dl / g to 0.94 dl / g, more preferably 0.60 dl / g to 0.84 dl / g, and 0.70 dl / g to 0.84 dl / g. Is more preferable.
  • the intrinsic viscosity of the polyester film is 0.55 dl / g or more, the film-forming property is improved and the film thickness is excellent.
  • the intrinsic viscosity (IV) of the mixed polyester obtained by mixing two or more kinds of polyesters is: It is preferable to satisfy the above range.
  • Intrinsic viscosity is calculated
  • ⁇ sp / C [ ⁇ ] + K [ ⁇ ] 2 ⁇ C
  • ⁇ sp represents (solution viscosity / solvent viscosity) -1.
  • C represents the mass of the polyester dissolved per 100 ml of the solvent (in this measurement, 1 g / 100 ml), and K represents the Huggins constant (0.343).
  • the solution viscosity and the solvent viscosity are values measured using an Ostwald viscometer. ]
  • a resin composition for forming a polyester film specifically, polyester, imino ether compound, etc. are charged into an extruder and melt-kneaded, and the extruded melt (melt) is passed through a gear pump and a filter. Extrude to a cooling roll in a film form through a die. The extruded melt is brought into close contact with the cooling roll using an electrostatic application method. An unstretched film can be formed by cooling and solidifying the melt adhered to the cooling roll. The surface temperature of the cooling roll can be 10 ° C. to 40 ° C.
  • the film formed in the film forming step can be subjected to a stretching treatment in the next stretching step to obtain a stretched film.
  • the film cooled and solidified by the cooling roll is preferably stretched in one direction or two directions as desired and stretched in two directions.
  • stretching to 2 directions each extending
  • the stretching treatment is preferably performed in the range of the glass transition temperature [Tg [° C.]] to (Tg + 60) ° C. of the film, more preferably in the range of (Tg + 3) ° C. to (Tg + 40) ° C., More preferably, it is carried out in the range of (Tg + 5) ° C. or higher and (Tg + 30) ° C. or lower.
  • the stretching ratio in at least one direction is preferably 280% to 500%, more preferably 300% to 480%, and further preferably 320% to 460%.
  • stretching in two directions biaxial stretching
  • stretching unevenly you may enlarge any draw ratio of the longitudinal direction (MD) or the width direction (TD) of a film.
  • a draw ratio is calculated
  • equation. Stretch ratio (%) 100 ⁇ (length after stretching) / (length before stretching)
  • the film is stretched once or twice at Tg ° C. or more (Tg + 60) ° C. so that the total draw ratio becomes 3 to 6 times, and then the width direction ( TD) may be stretched at Tg ° C. or more and (Tg + 60) ° C. or less so that the draw ratio is 3 to 5 times.
  • biaxial stretching two or more pairs of nip rolls with increased downstream rotational speed (peripheral speed) are used to stretch in the longitudinal direction (MD) (longitudinal stretching) and then to both ends in the width direction of the film stretched in MD. Is held by a chuck and stretched (laterally stretched) in a direction perpendicular to MD.
  • the film in the stretching step, can be heat-treated before or after the stretching process (preferably after the stretching process).
  • the film By subjecting the film to heat treatment, crystallites can be generated, and the mechanical properties and durability of the film can be improved.
  • the film may be heat-treated at about 180 ° C. to 210 ° C. (preferably 185 ° C. to 220 ° C.) for 1 second to 60 seconds (preferably 2 seconds to 30 seconds).
  • a thermal relaxation treatment can be performed after the heat treatment.
  • the thermal relaxation treatment is a treatment for shrinking the film by applying heat to the film for stress relaxation.
  • the thermal relaxation treatment is preferably performed in both the MD and TD directions of the film.
  • the various conditions in the thermal relaxation treatment are preferably treatment at a temperature lower than the heat treatment temperature, for example, 130 ° C. to 220 ° C. is preferable.
  • the thermal shrinkage of the film at 150 ° C. is preferably 1% to 12% for MD and TD, more preferably 1% to 10%.
  • the heat shrinkage rate at 150 ° C. can be obtained as follows by cutting out a sample having a length direction of 350 mm and a width direction of 50 mm as the measurement direction.
  • a film for example, a polyester film
  • the polyester film of the present disclosure can be suitably used as a protective sheet for a solar cell module (so-called solar cell backsheet), and can also be used for other applications.
  • at least one functional group selected from a carboxyl group (COOH), a hydroxyl group (OH), a sulfonic acid group (SO 3 H), an amino group (NH 2 ), and a salt thereof is provided.
  • a layer including the coating layer may be provided and used as a laminated film.
  • the laminated film may be, for example, a laminated film in which a coating layer such as an easy adhesion layer is provided on the polyester film of the present disclosure.
  • the polyester film and laminated film of the present disclosure are used for various applications.
  • a solar cell backsheet (a back surface protection sheet of a solar cell module) is preferably exemplified. Since the polyester film of the present disclosure is excellent in film surface shape and has good adhesion and moisture and heat resistance, when used in a solar cell backsheet, the power generation efficiency of the solar cell module over a long period of time. Can be held.
  • the solar cell backsheet can be formed, for example, by providing a desired functional layer on the polyester film of the present disclosure.
  • the functional layer includes a reflective layer (colored layer) that reflects the light that has reached the backsheet out of the sunlight incident on the solar cell module and returns it to the solar cell, and an overcoat that contributes to adhesion to the sealing material Examples include a layer, a back surface layer for protecting the back surface, and a back surface protective layer.
  • a functional layer it is preferable to form an easily bonding layer previously on a polyester film, and to provide a functional layer through an easily bonding layer.
  • the solar cell backsheet is preferably provided with a reflective layer that reflects light on the side of the polyester film that contacts the sealing material that seals the solar cells.
  • a reflective layer on the side of the polyester film that contacts the sealing material that seals the solar cells, the light that has passed through the solar cells and reached the back sheet out of the sunlight incident on the solar cell module It can return to a photovoltaic cell and can improve power generation efficiency.
  • the reflective layer preferably contains a binder and a colorant (preferably a white pigment).
  • Preferred examples of the white pigment include titanium oxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin and talc.
  • the thickness of the reflective layer is preferably 3 ⁇ m to 10 ⁇ m, more preferably 4 ⁇ m to 8 ⁇ m. When the thickness of the reflective layer is within the above range, both necessary reflectance and adhesiveness can be achieved.
  • the reflective layer can be formed using a known coating method such as a roll coat method, a bar coater method, a slide die method, or a gravure coater method.
  • the solar cell backsheet may have an overcoat layer on the reflective layer.
  • the overcoat layer preferably contains a binder.
  • the thickness of the overcoat layer is preferably 0.1 ⁇ m to 1.0 ⁇ m, more preferably 0.2 to 0.8 ⁇ m. When the thickness of the overcoat layer is within the above range, strong adhesiveness with the sealing material for sealing the solar battery cell can be obtained.
  • the overcoat layer can be formed using a known coating method such as a roll coat method, a bar coater method, a slide die method, or a gravure coater method.
  • the solar cell backsheet has the back surface layer which protects a polyester film on the opposite side to the side which contact
  • the back surface layer preferably contains a binder, and as an example of the binder, a silicone-based composite polymer is preferable in terms of durability and adhesion to a polyester film.
  • a silicone-based composite polymer is a polymer that includes a — (Si (R 1 ) (R 2 ) —O) n — moiety and a polymer structure moiety that is copolymerized with this moiety in the molecule.
  • the back surface layer may contain an ultraviolet absorber, a white pigment, or the like, if necessary.
  • the thickness of the back layer is preferably 3 ⁇ m to 12 ⁇ m, more preferably 4 ⁇ m to 8 ⁇ m. If the thickness of the back layer is within the above range, both durability and adhesiveness can be achieved.
  • the back layer can be formed using a known coating method such as a roll coat method, a bar coater method, a slide die method, or a gravure coater method.
  • the back sheet for solar cells may further have a back surface protective layer on the back surface layer.
  • the back surface protective layer preferably contains a binder.
  • the binder is preferably a fluoropolymer from the viewpoint of durability.
  • the fluorine-based polymer is a polymer having a structural unit derived from a fluorine-containing monomer in the main chain or side chain.
  • the fluorine-based polymer may have a structural unit derived from a fluorine-containing monomer in either the main chain or the side chain, but is preferably in the main chain from the viewpoint of durability.
  • the back surface layer may contain a slip agent, colloidal silica, or the like, if necessary.
  • the thickness of the back surface protective layer is preferably 0.5 ⁇ m to 6 ⁇ m, more preferably 1 ⁇ m to 5 ⁇ m. When the thickness of the back surface protective layer is within the above range, the durability is excellent.
  • the back surface protective layer can be formed using a known coating method such as a roll coating method, a bar coater method, a slide die method, or a gravure coater method.
  • a solar cell module can be produced using the polyester film of the present disclosure or the solar cell backsheet described above.
  • the solar cell module includes a solar cell (solar cell element) that converts light energy of sunlight into electric energy, a transparent substrate on which sunlight is incident, and the polyester film of the present disclosure described above (back for solar cell). Sheet). Between the substrate and the polyester film, the solar battery cells can be sealed with a resin such as an ethylene-vinyl acetate copolymer (so-called sealing material).
  • the members other than the solar battery module, the solar battery cell, and the back sheet are described in detail in, for example, “Photovoltaic power generation system constituent materials” (supervised by Eiichi Sugimoto, Industrial Research Co., Ltd., issued in 2008). .
  • the substrate having transparency may be appropriately selected from base materials that transmit light, as long as the substrate has light transmittance through which sunlight can pass. From the viewpoint of power generation efficiency, as the substrate having transparency, a substrate having higher light transmittance is preferable, and as such a substrate, a glass substrate, a substrate of a transparent resin such as an acrylic resin, or the like can be suitably used. .
  • Solar cells include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and group III-V or II such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, etc.
  • group III-V or II such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, etc.
  • group III-V or II such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, etc.
  • group III-V or II such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, etc.
  • Various known solar cell elements such as -VI group compound semiconductor systems can be
  • a suspension obtained by mixing 32 g (0.1 mol) of the compound (1-1), 400 ml of thionyl chloride and 0.3 ml of N, N-dimethylformamide was stirred for 11 hours while heating under reflux to obtain a reaction solution.
  • 0.3 ml of N, N-dimethylformamide was added and further stirred for 4 hours to completely dissolve the solid content in the reaction solution.
  • Thionyl chloride in the reaction solution in which the solid content was completely dissolved was distilled off, and 300 ml of hexane was added to precipitate a solid. The precipitated solid was collected by filtration to obtain 35 g (quant.) Of compound (1-2).
  • a suspension obtained by mixing 32 g (0.1 mol) of the compound (22-1) and 150 ml of thionyl chloride was stirred for 6 hours under heating to reflux to obtain a reaction solution. After confirming that the solid content in the obtained reaction solution was completely dissolved, the mixture was further stirred for 2 hours. Thionyl chloride was distilled off from the reaction solution after stirring, and 300 ml of hexane was added to precipitate a solid. The precipitated solid was collected by filtration to obtain 35 g (quant.) Of compound (22-2).
  • Paratoluenesulfonic acid monohydrate was added to 50 ml of a toluene solution of 23.6 g (105.6 mmol) of triethyl orthobenzoate and 16.2 g (44 mmol) of 4,4 ′-[(4,4′-biphenylylene) bisoxy] bisaniline.
  • a catalyst amount was added, and the mixture was stirred for 5 hours under reflux with heating to obtain a reaction solution.
  • the methanol refluxed at a reaction system temperature of 100 ° C. or lower was removed with a Dean-Stark apparatus.
  • Example 1 Preparation of saturated polyester resin> -Process (A)- 4.7 tons of high-purity terephthalic acid and 1.8 tons of ethylene glycol were mixed for 90 minutes to form a slurry, which was continuously supplied to the first esterification reactor at a flow rate of 3800 kg / h.
  • an ethylene glycol solution of a citric acid chelate titanium complex (“VERTEC AC-420” manufactured by Johnson Matthey) in which citric acid is coordinated to titanium (Ti) metal is continuously supplied to the first esterification reaction tank.
  • the reaction was carried out with an average residence time of about 4.4 hours while stirring at an internal temperature of 250 ° C. to obtain an oligomer.
  • the citric acid chelate titanium complex was continuously added so that the amount of Ti added was 9 ppm in terms of element.
  • the oligomer obtained had a carboxylic acid value of 500 eq / ton.
  • the obtained oligomer was transferred to the second esterification reaction tank and reacted under the conditions of a reaction tank temperature of 250 ° C. and an average residence time of 1.2 hours to obtain an oligomer having a carboxylic acid value of 180 eq / ton. .
  • the inside of the second esterification reaction tank is divided into three zones, the first zone to the third zone.
  • the ethylene glycol solution of magnesium acetate is added in terms of element (magnesium (Mg)).
  • Mg magnesium
  • an ethylene glycol solution of trimethyl phosphate was continuously supplied so that the addition amount of phosphorus (P) was 65 ppm in terms of element.
  • the ethylene glycol solution of trimethyl phosphate was prepared by adding a 25 ° C. trimethyl phosphate solution to a 25 ° C. ethylene glycol solution and stirring at 25 ° C. for 2 hours (phosphorus compound content in the solution: 3 .8% by mass). As described above, an esterification reaction product was obtained.
  • the esterification reaction product obtained in the step (A) is continuously supplied to the first polycondensation reaction tank, and the reaction temperature is 270 ° C. and the reaction tank pressure is 20 torr (2.67 ⁇ 10 ⁇ 3 MPa). While the esterification reaction product was stirred under the conditions, polycondensation (transesterification reaction) was performed under the condition of an average residence time of about 1.8 hours.
  • the obtained reaction product was transferred from the first polycondensation reaction tank to the second double condensation reaction tank. Thereafter, in the second double condensation reaction tank, the reaction product was stirred under the conditions of a reaction tank temperature of 276 ° C. and a reaction tank pressure of 5 torr (6.67 ⁇ 10 ⁇ 4 MPa), and a residence time of about 1.2 hours. (Transesterification reaction).
  • the reaction product obtained by the transesterification reaction was transferred from the second double condensation reaction tank to the third triple condensation reaction tank.
  • the reaction was carried out under the conditions of a residence time of 1.5 hours while stirring under conditions of a reaction tank temperature of 276 ° C. and a reaction tank pressure of 1.5 torr (2.0 ⁇ 10 ⁇ 4 MPa).
  • Transesterification reaction was performed to obtain polyethylene terephthalate (PET) as a reaction product.
  • PET had a carboxylic acid value (Acid Value, AV) of 22 eq / ton and an IV (intrinsic viscosity) of 0.65 dl / g.
  • AV is calculated from an appropriate amount obtained by dissolving polyester in benzyl alcohol at 205 ° C., adding a phenol red indicator, and titrating with a water / methanol / benzyl alcohol solution of sodium hydroxide.
  • IV is obtained from the following equation from the solution viscosity obtained by measuring a solution of polyester in orthochlorophenol at 25 ° C.
  • ⁇ sp / C [ ⁇ ] + K [ ⁇ ] 2 ⁇ C
  • ⁇ sp represents (solution viscosity / solvent viscosity) -1.
  • C represents the mass of the polyester dissolved per 100 ml of the solvent (in this measurement, 1 g / 100 ml)
  • K represents the Huggins constant (0.343)
  • the solution viscosity and the solvent viscosity are measured using an Ostwald viscometer. It is a value measured using.
  • polyester film Preparation of polyester film> -Extrusion molding-
  • the PET obtained above was introduced into the hopper of a twin-screw kneading extruder in which a screw having a diameter of 50 mm in the cylinder was placed in the main feeder, and the iminoether compound synthesized above (represented by the general formula (1)).
  • 10 parts of the exemplified compound (122)) of the acid alkylating agent and 0.1 part of paratoluenesulfonic acid (a-1) are charged in a sub-feeder and melt kneaded at 280 ° C. for 1 minute to obtain a resin composition
  • the product was extruded to obtain a resin composition.
  • the content ratio of Exemplified Compound (1) to PET was 0.05 (5% by mass).
  • the extruded melt (melt) After passing the extruded melt (melt) through a gear pump and a filter (pore size 20 ⁇ m), it is extruded from a die to a cooling roll at 20 ° C., and solidified by adhering to the cooling roll using an electrostatic application method. A characteristic film was obtained.
  • Example 1 a polyester film was prepared and evaluated in the same manner as in Example 1 except that the acid alkylating agent, the addition amount of the acid alkylating agent, and the organic acid were changed as shown in Table 1 below. went.
  • Example 1 a polyester film was prepared and evaluated in the same manner as in Example 1 except that the acid alkylating agent, the addition amount of the acid alkylating agent, and the organic acid were changed as shown in Table 1 below. went.
  • a polyester film was prepared in the same manner as in Example 1 except that the acid alkylating agent and the organic acid were not added in Example 1, and used as a reference film.
  • the present disclosure includes a compound having an acidic group selected from a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group, and is suitable for a field where excellent durability performance is required.
  • it is suitably used as an acid sealant for a resin film (eg, polyester film) used for a solar cell backsheet, which requires hydrolysis resistance over a long period of time.

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Abstract

L'invention concerne : un agent d'alkylation acide représenté par la formule générale (1), par lequel un composé ayant au moins un groupe acide sélectionné parmi un groupe acide sulfonique, un groupe acide phosphorique et un groupe hydroxyle phénolique est alkylé par un acide; un procédé de production d'un produit alkylé par un acide; une composition de résine; et un film de polyester. Dans la formule, R2 représente un groupe alkyle, un groupe aryle ou un groupe alcoxy; R3 représente une fraction représentée par la formule générale (2) ou la formule générale (3); chacun de R11 à R13 représente un atome d'hydrogène, un groupe alkyle ou un groupe aryle; R2, R3, R11, R12 et R13 peuvent se combiner ensemble pour former un cycle; chacun de R31 à R33 représente un atome d'hydrogène ou un substituant; R31 à R33 peuvent se combiner ensemble pour former un cycle; R41 représente un substituant; n représente un nombre entier de 0 à 5; et * représente la position de liaison avec un atome d'azote dans la formule générale (1).
PCT/JP2015/085284 2015-01-27 2015-12-16 Agent d'alkylation acide, procédé de production de produit alkylé par un acide, composition de résine et film de polyester WO2016121260A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637583A (en) * 1968-10-23 1972-01-25 Mobay Chemical Corp Polyesterurethanes stabilized with iminocarbonates
JPH06220005A (ja) * 1992-07-30 1994-08-09 Sandoz Ag 新規なイミノエーテル
WO2015087834A1 (fr) * 2013-12-09 2015-06-18 富士フイルム株式会社 Composé imino éther, composition de résine de polyester, procédé de production d'ester d'acide carboxylique, film de polyester, feuille de support pour modules de cellules solaires, et module de cellules solaires
WO2015182546A1 (fr) * 2014-05-30 2015-12-03 富士フイルム株式会社 Composition de résine de polyester, pastille maître, film de polyester, feuille arrière pour module photovoltaïque et module photovoltaïque
WO2015194661A1 (fr) * 2014-06-20 2015-12-23 富士フイルム株式会社 Composition de résine, film de polyester et article moulé

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637583A (en) * 1968-10-23 1972-01-25 Mobay Chemical Corp Polyesterurethanes stabilized with iminocarbonates
JPH06220005A (ja) * 1992-07-30 1994-08-09 Sandoz Ag 新規なイミノエーテル
WO2015087834A1 (fr) * 2013-12-09 2015-06-18 富士フイルム株式会社 Composé imino éther, composition de résine de polyester, procédé de production d'ester d'acide carboxylique, film de polyester, feuille de support pour modules de cellules solaires, et module de cellules solaires
WO2015182546A1 (fr) * 2014-05-30 2015-12-03 富士フイルム株式会社 Composition de résine de polyester, pastille maître, film de polyester, feuille arrière pour module photovoltaïque et module photovoltaïque
WO2015194661A1 (fr) * 2014-06-20 2015-12-23 富士フイルム株式会社 Composition de résine, film de polyester et article moulé

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