WO2018003432A1 - Resin composition, coating liquid, release film-equipped mold, and method for producing same - Google Patents

Resin composition, coating liquid, release film-equipped mold, and method for producing same Download PDF

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Publication number
WO2018003432A1
WO2018003432A1 PCT/JP2017/021023 JP2017021023W WO2018003432A1 WO 2018003432 A1 WO2018003432 A1 WO 2018003432A1 JP 2017021023 W JP2017021023 W JP 2017021023W WO 2018003432 A1 WO2018003432 A1 WO 2018003432A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
group
unit
resin composition
compound
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Application number
PCT/JP2017/021023
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French (fr)
Japanese (ja)
Inventor
正樹 小尾
太平 谷口
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to CN201780039821.8A priority Critical patent/CN109415550A/en
Priority to KR1020187031063A priority patent/KR20190022459A/en
Priority to JP2018524996A priority patent/JPWO2018003432A1/en
Publication of WO2018003432A1 publication Critical patent/WO2018003432A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/58—Applying the releasing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • 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
    • C08K5/04—Oxygen-containing compounds
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08L101/04—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/04—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing halogen atoms

Definitions

  • the present invention relates to a resin composition, a coating liquid, a mold with a release film, and a manufacturing method thereof.
  • mold release agents with excellent mold release properties (for example, Patent Document 1).
  • a mold release agent is formed on the surface of a mold for molding a resin, rubber, metal or the like, for example. Thereby, the mold release property of the molded product from a metal mold
  • An object of the present invention is to provide a resin composition and a coating liquid that can form a film having excellent releasability and excellent durability, and a release film having a releasable film that has excellent releasability and excellent durability
  • An object of the present invention is to provide an attached die and a manufacturing method thereof.
  • the present invention provides a resin composition, a coating liquid, a mold with a release film, and a method for producing the same, having the following configurations [1] to [15].
  • a resin composition comprising a copolymer (A1) having the following unit (u1), the following unit (u2) and the following unit (u3), and the following compound (B).
  • Unit (u1) A unit derived from a monomer having an organic group having one or more fluorine atoms (but not having a block isocyanate group and an active hydrogen atom-containing functional group).
  • Unit (u2) A unit derived from a monomer having a block isocyanate group (but not having an active hydrogen atom-containing functional group).
  • Unit (u3) A unit derived from a monomer having an active hydrogen atom-containing functional group (but not having a block isocyanate group).
  • the unit (u1) is 5 to 40 mol%
  • the unit (u2) is 30 to 48 mol%
  • a copolymer (A2) having the following unit (u1) and the following unit (u2) and not having the following unit (u3), the unit (u1) and the unit (u3) A resin composition comprising a copolymer (A3) having no unit (u2) and the following compound (B).
  • Unit (u1) A unit derived from a monomer having an organic group having one or more fluorine atoms (but not having a block isocyanate group and an active hydrogen atom-containing functional group).
  • Unit (u3) A unit derived from a monomer having an active hydrogen atom-containing functional group (but not having a block isocyanate group).
  • Compound (B) having at least two functional groups selected from the group consisting of a hydroxyl group, an amino group and a carboxy group, the boiling point of which is not less than the block dissociation temperature of the block isocyanate group in the copolymer (A2); A compound that is 400 ° C. or lower.
  • the unit (u1) is 5 to 40 mol% and the unit (u2) is 60 to 95 mol% with respect to all the units in the copolymer (A2).
  • a copolymer comprising The copolymer (A3) contains 5-40 mol% of units (u1) and 60-95 mol% of units (u3) with respect to all units in the copolymer (A3). United, [5] The resin composition. [7] The copolymer (A2) has a mass average molecular weight of 5,000 to 200,000, and the copolymer (A3) has a mass average molecular weight of 5,000 to 200,000. [5] Or the resin composition of [6]. [8] The content of the compound (B) is 20 to 60 parts by mass with respect to 100 parts by mass in total of the copolymer (A2) and the copolymer (A3). 7].
  • a coating solution comprising the resin composition of any one of [1] to [11] and a solvent.
  • a mold with a release film comprising a release film formed from the resin composition of any one of [1] to [10] on the surface of the mold.
  • the mold with a release film of the present invention is provided with a release film that is excellent in releasability and excellent in durability. According to the method for manufacturing a mold with a release film of the present invention, it is possible to manufacture a mold with a release film having a release film that is excellent in mold release properties and excellent in durability.
  • the “unit” in the polymer means a portion derived from the monomer formed by polymerization of the monomer.
  • the unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
  • the “(meth) acryloyloxy group” is a general term for an acryloyloxy group and a methacryloyloxy group.
  • “(Meth) acrylate” is a general term for acrylate and methacrylate.
  • Release film refers to a film having a film surface that is formed on a substrate or the like that is superior in release properties compared to a portion where the film is not formed, specifically, the peel strength of a substance attached to the film surface is It means a film that is smaller than the part where no film is formed.
  • the resin composition of the present invention is a composition containing a copolymer (A1) and a compound (B) described later (hereinafter also referred to as “resin composition (1)”), or a copolymer (A2). And a copolymer (A3) and a compound (B) (hereinafter also referred to as “resin composition (2)”).
  • resin composition (1) a copolymer containing a copolymer (A1) and a compound (B) described later
  • A2 a copolymer (A2)
  • A3 and a compound (B) hereinafter also referred to as “resin composition (2)
  • the resin composition may further contain other components as necessary.
  • the weight average molecular weight (Mw) of each of the copolymer (A1), the copolymer (A2), and the copolymer (A3) is preferably 5,000 to 200,000, particularly preferably 10,000 to 150,000. . If the Mw of the copolymer (A1), the copolymer (A2), and the copolymer (A3) is equal to or greater than the lower limit of the above range, the durability of the release agent film is more excellent, and is not greater than the upper limit of the above range. If so, the solubility in a solvent is more excellent.
  • the mass average molecular weight (Mw) is a value in terms of polymethyl metallate measured by gel permeation chromatography (GPC).
  • Each unit contained in the copolymer (A1), the copolymer (A2), and the copolymer (A3) is as follows.
  • the unit (u1) has an organic group having one or more fluorine atoms (however, it does not have a block isocyanate group and an active hydrogen atom-containing functional group) and is a monomer (hereinafter referred to as “monomer (m1)”). It is a unit derived from.
  • the copolymers (A1) to (A3) have the unit (u1), the film formed from the resin composition is excellent in releasability.
  • a polyfluoroalkyl group or a group having an etheric oxygen atom between carbon atoms of the polyfluoroalkyl group is preferable from the viewpoint of more excellent releasability, and a perfluoroalkyl group, Or the group which has an etheric oxygen atom between the carbon atoms of a perfluoroalkyl group is especially preferable.
  • the number of carbon atoms of the polyfluoroalkyl group and the group having an etheric oxygen atom between the carbon atoms of the polyfluoroalkyl group is preferably 4 or more from the viewpoint of releasability. 6 or less is preferable from the viewpoint of little influence on the environment.
  • the carbon number is more preferably 4 to 6, and particularly preferably 6.
  • the number of etheric oxygen atoms is preferably 1 to 3, particularly preferably 1 to 2.
  • the polyfluoroalkyl group may be linear or branched, and is preferably linear. That is, examples of the organic group having one or more fluorine atoms include 1 to 3 carbon atoms between carbon atoms of a linear perfluoroalkyl group having 4 to 6 carbon atoms or a linear perfluoroalkyl group having 4 to 6 carbon atoms.
  • a group having an etheric oxygen atom is preferred, and a straight-chain perfluoroalkyl group having 6 carbon atoms or a group having 1 to 2 etheric oxygen atoms between carbon atoms of a straight-chain perfluoroalkyl group having 6 carbon atoms. Particularly preferred.
  • the monomer (m1) preferably has a structure in which a group having a polymerizable double bond and an organic group having one or more fluorine atoms are bonded directly or via a linking group.
  • the number of polymerizable double bonds and one or more organic groups having one or more fluorine atoms bonded directly or via a linking group is preferably one.
  • Examples of the group having a polymerizable double bond include a vinyl group, an allyl group, a (meth) acryloyloxy group, an ⁇ -halogenoacryloyloxy group, and the like. Of these, a (meth) acryloyloxy group is preferable from the viewpoint of easily controlling the molecular weight of the copolymer.
  • Examples of the linking group include a divalent hydrocarbon group.
  • Examples of the divalent hydrocarbon group include an alkylene group and an arylene group.
  • an alkylene group is preferable from the viewpoint of durability, and an alkylene group having 1 to 6 carbon atoms is particularly preferable.
  • the alkylene group may be linear or branched and is preferably linear.
  • R 11 is a hydrogen atom, a methyl group or a halogen atom (fluorine atom, chlorine atom, etc.)
  • R 12 is an alkylene group
  • R f is a C 4-6 perfluoroalkyl group or carbon number A group having an etheric oxygen atom between carbon atoms of 4 to 6 perfluoroalkyl groups.
  • R 11 is preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
  • R 12 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably —CH 2 — or —C 2 H 4 —.
  • R f includes — (CF 2 ) 3 CF 3 , — (CF 2 ) 4 CF 3 , — (CF 2 ) 5 CF 3 , —CF (CF 3 ) OCF 2 CF 2 CF 3 , —CF 2 OCF 2 CF 2 OCF 3 , —CF 2 OCF 2 CF 2 OCF 3 , —CF 2 OCF 2 CF 2 OCF 2 CF 3 , and —CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3 are preferable.
  • Examples of the monomer represented by CH 2 ⁇ C (R 11 ) C (O) O—R 12 —R f include the following compounds. CH 2 ⁇ C (CH 3 ) C (O) O—C 2 H 4 — (CF 2 ) 3 CF 3 , CH 2 ⁇ C (CH 3 ) C (O) O—C 2 H 4 — (CF 2 ) 4 CF 3 , CH 2 ⁇ C (CH 3 ) C (O) O—C 2 H 4 — (CF 2 ) 5 CF 3 , CH 2 ⁇ C (CH 3 ) C (O) O—CH 2 —CF (CF 3 ) OCF 2 CF 2 CF 3 , CH 2 ⁇ C (CH 3 ) C (O) O—CH 2 —CF 2 OCF 2 CF 2 OCF 3 , CH 2 ⁇ C (CH 3 ) C (O) O—CH 2 —CF 2 OCF 2 CF 2 OCF 3 , CH 2 ⁇ C (CH 3 ) C (O) O—CH
  • a monomer (m1) may be used individually by 1 type, and may use 2 or more types together.
  • the unit (u2) is a unit derived from a monomer having a block isocyanate group (but not having an active hydrogen atom-containing functional group) (hereinafter also referred to as “monomer (m2)”).
  • the blocked isocyanate group is a group obtained by blocking an isocyanate group with a blocking agent.
  • the blocking agent that blocks the isocyanate group include oximes and pyrazoles.
  • the monomer (m2) preferably has a structure in which a group having a polymerizable double bond and a block isocyanate group are bonded directly or via a linking group.
  • the number of polymerizable double bonds and block isocyanate groups bonded directly or via a linking group is preferably one each.
  • Examples of the group having a polymerizable double bond and the linking group include the same groups as the group having a polymerizable double bond and the linking group in the monomer (m1), and preferred embodiments are also the same.
  • the monomer (m2) is preferably a monomer represented by CH 2 ⁇ C (R 13 ) C (O) O—R 14 —NHC (O) R 15 from the viewpoint of easy crosslinking reaction.
  • R 13 is a hydrogen atom, a methyl group or a halogen atom (fluorine atom, chlorine atom, etc.)
  • R 14 is an alkylene group
  • R 15 is a monovalent organic group.
  • —NHC (O) R 15 corresponds to a blocked isocyanate group.
  • R 13 is preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.
  • R 14 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably —CH 2 — or —C 2 H 4 —.
  • R 15 is preferably a group represented by the following formula (5a), a group represented by the following formula (5b), or a group represented by the following formula (5c).
  • R 51 , R 52 , R 53 and R 54 are each independently an alkyl group having 1 to 4 carbon atoms.
  • a monomer (m2) may be used individually by 1 type, and may use 2 or more types together.
  • the unit (u3) is a unit derived from a monomer having an active hydrogen atom-containing functional group (but not having a block isocyanate group) (hereinafter also referred to as “monomer (m3)”).
  • a hydroxyl group (OH) or an amino group (NH 2 ) is preferable, and a hydroxyl group is particularly preferable.
  • the monomer (m3) preferably has a structure in which a group having a polymerizable double bond and an active hydrogen atom-containing functional group are bonded directly or via a linking group.
  • Examples of the group having a polymerizable double bond and the linking group include the same groups as the group having a polymerizable double bond and the linking group in the monomer (m1), and preferred embodiments are also the same.
  • R 16 is a hydrogen atom, a methyl group or a halogen atom (fluorine atom, chlorine atom, etc.), R 17 is an alkylene group.
  • R 16 is preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.
  • R 17 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably —CH 2 — or —C 2 H 4 —.
  • a monomer (m3) may be used individually by 1 type, and may use 2 or more types together.
  • Copolymer (A1), copolymer (A2) and copolymer (A3) are units (u1), units (u2) and units other than unit (u3) (hereinafter referred to as “other units”, respectively). May be included).
  • the other unit is a unit derived from a monomer other than the monomer (m1), the monomer (m2) and the monomer (m3) (hereinafter also referred to as “monomer (m4)”). is there.
  • the monomer (m4) include alkyl (meth) acrylate, alkyl vinyl ether, vinyl chloride and the like.
  • a monomer (m4) may be used individually by 1 type, and may use 2 or more types together.
  • the copolymer (A1) has a unit (u1), a unit (u2), and a unit (u3).
  • the copolymer (A1) may further have other units as necessary.
  • the proportion of the unit (u1) is preferably from 5 to 40 mol%, particularly preferably from 10 to 30 mol%, based on the total units of the copolymer (A1). If the ratio of the unit (u1) is not less than the lower limit of the above range, the mold release property of the formed film is more excellent. When the ratio of the unit (u1) is not more than the upper limit of the above range, the durability of the formed film is more excellent.
  • the ratio of the unit (u2) is preferably 30 to 48 mol%, particularly preferably 35 to 45 mol%, based on all units of the copolymer (A1).
  • the ratio of the unit (u2) is not less than the lower limit of the above range, the durability of the formed film is more excellent. If the ratio of the unit (u2) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
  • the proportion of the unit (u3) is preferably 30 to 48 mol%, particularly preferably 35 to 45 mol%, based on all units of the copolymer (A1).
  • the ratio of the unit (u3) is not less than the lower limit of the above range, the durability of the formed film is more excellent.
  • the ratio of the unit (u3) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
  • the unit (u1) in all the units of the copolymer (A1), the unit (u1) is 5 to 40 mol%, the unit (u2) is 30 to 48 mol%, and the unit (u3) is 30%.
  • the molar ratio of unit (u2) to unit (u3) (unit (u2) / unit (u3)) is preferably 30/70 to 70/30, and preferably 40/60 to 60/40. Particularly preferred.
  • unit (u2) / unit (u3) is within the above range, it is possible to achieve both better release properties and better durability.
  • the block dissociation temperature of the block isocyanate group in the copolymer (A1) is substantially equal to the block dissociation temperature of the block isocyanate group in the monomer (m2). Therefore, the block dissociation temperature of the block isocyanate group in the copolymer (A1) can be adjusted by selecting the block isocyanate group in the monomer (m2). The same applies to the copolymer (A2) described later.
  • the block dissociation temperature in the monomer or copolymer is not limited to one point but varies, in the present invention, the block dissociation temperature in the copolymer (A1) and the copolymer (A2) is 30 minutes of heating.
  • the temperature at which 50% of the block isocyanate groups are deblocked is defined as the “block dissociation temperature” of the copolymer.
  • the block dissociation temperature of the block isocyanate group in the copolymer (A1) and the copolymer (A2) is represented by T D (° C.).
  • a copolymer (A2) is a copolymer which has a unit (u1) and a unit (u2), and does not have a unit (u3).
  • the copolymer (A2) may further have other units as necessary.
  • the ratio of the unit (u1) is preferably from 5 to 40 mol%, particularly preferably from 5 to 30 mol%, based on the total units of the copolymer (A2). If the ratio of the unit (u1) is not less than the lower limit of the above range, the mold release property of the formed film is more excellent. When the ratio of the unit (u1) is not more than the upper limit of the above range, the durability of the formed film is more excellent.
  • the proportion of the unit (u2) is preferably 60 to 95 mol%, particularly preferably 70 to 95 mol%, based on all units of the copolymer (A2).
  • the ratio of the unit (u2) is not less than the lower limit of the above range, the durability of the formed film is more excellent. If the ratio of the unit (u2) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
  • the copolymer (A2) is preferably one containing 5 to 40 mol% of the unit (u1) and 60 to 95 mol% of the unit (u2) in all the units of the copolymer (A2). Particularly preferred are those containing 5 to 30 mol% of units (u1) and 70 to 95 mol% of units (u2).
  • the copolymer (A3) has a unit (u1) and a unit (u3), and does not have a unit (u2). Since both the copolymer (A2) and the copolymer (A3) have the unit (u1), the miscibility is good.
  • the unit (u1) in the copolymer (A2) and the unit (u1) in the copolymer (A3) may be the same or different.
  • the copolymer (A3) may further have other units as necessary.
  • the proportion of the unit (u1) is preferably from 5 to 40 mol%, particularly preferably from 10 to 40 mol%, based on the total units of the copolymer (A3). If the ratio of the unit (u1) is not less than the lower limit of the above range, the mold release property of the formed film is more excellent. When the ratio of the unit (u1) is not more than the upper limit of the above range, the durability of the formed film is more excellent.
  • the proportion of the unit (u3) is preferably 60 to 95 mol%, particularly preferably 60 to 90 mol%, based on all units of the copolymer (A3).
  • the ratio of the unit (u3) is not less than the lower limit of the above range, the durability of the formed film is more excellent.
  • the ratio of the unit (u3) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
  • the copolymer (A3) preferably contains 5 to 40 mol% of the unit (u1) and 60 to 95 mol% of the unit (u3) in all the units of the copolymer (A3). Particularly preferred are those containing 10 to 40 mol% of the unit (u1) and 60 to 90 mol% of the unit (u3).
  • the compound (B) is a compound having at least one functional group selected from the group consisting of a hydroxyl group, an amino group and a carboxy group (hereinafter also referred to as “functional group (I)”).
  • the number of functional groups (I) possessed by the compound (B) is preferably 2 to 10, more preferably 2 to 8, and particularly preferably 2 or 3. If the number of functional groups (I) is within the above range, the releasability of the formed film is more excellent.
  • the functional group (I) is preferably a hydroxyl group or an amino group, particularly preferably a hydroxyl group.
  • the boiling point of the compound (B) is T D to 400 ° C. If the boiling point of a compound (B) is in the said range, the mold release property of the film
  • the lower limit of the boiling point of the compound (B) is preferably T D + 10 ° C., particularly preferably T D + 30 ° C.
  • the upper limit of the boiling point of the compound (B) is preferably 300 ° C, particularly preferably 250 ° C.
  • the compound (B) may be an aromatic compound having an aromatic ring or a non-aromatic compound having no aromatic ring.
  • the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.
  • the non-aromatic compound may be a linear or branched aliphatic compound or an alicyclic compound having an alicyclic group. It is preferable that a compound (B) does not have a fluorine atom.
  • the compound (B) include the following compounds.
  • Aromatic compounds such as phloroglucinol, hydroquinone, resorcinol, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,4-phenylenediamine,
  • Non-aromatic compounds such as trimethylolpropane, ethylene glycol, and propylene glycol.
  • the compound (B) preferably has an aromatic ring in terms of more excellent releasability.
  • Compound (B) includes phloroglucinol, hydroquinone, resorcinol, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,4-phenylenediamine and the like, and two or more bonded to the aromatic ring
  • a compound having the functional group (I) is particularly preferred.
  • a compound (B) may be used individually by 1 type, and may use 2 or more types together.
  • Examples of other components include a surfactant, an adhesion improver with a base material (such as a mold), a urethanization catalyst (such as a tin catalyst), and a block dissociation catalyst for a block isocyanate group.
  • a surfactant such as a surfactant
  • an adhesion improver with a base material such as a mold
  • a urethanization catalyst such as a tin catalyst
  • a block dissociation catalyst for a block isocyanate group such as a block isocyanate group.
  • the copolymer (A2) or the copolymer (A3) in the case of the resin composition (2), the copolymer (A1) may be included as another component. Yes, but not necessarily.
  • the resin composition in this invention says what does not contain a solvent.
  • the total content of the union (A3) and the compound (B) is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and particularly preferably 20 to 100% by mass with respect to the total mass of the resin composition. preferable. If this total content is equal to or greater than the lower limit of the above range, the formed film is more releasable and more durable.
  • the content of the compound (B) is 100 parts by mass of the copolymer (A1) in the case of the resin composition (1), and the copolymer (2) in the case of the resin composition (2).
  • the amount is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, and particularly preferably 20 to 60 parts by weight with respect to 100 parts by weight of the total of A2) and the copolymer (A3). If content of a compound (B) is more than the lower limit of the said range, the effect by a compound (B) will fully be exhibited, and the mold release property of the film
  • the resin composition (1) does not contain other components other than the copolymer (A1) and the compound (B).
  • the resin composition (2) preferably contains no other components than the copolymers (A2) to (A3) and the compound (B).
  • the content of each of the copolymer (A2) and the copolymer (A3) in the resin composition (2) is the molar ratio of the unit (u2) to the unit (u3) (unit (u2) / unit (u3)). ) Is preferably 30/70 to 70/30, more preferably 40/60 to 60/40. When the unit (u2) / unit (u3) is within the above range, it is possible to achieve both better release properties and better durability.
  • the ratio of the unit (u1) is preferably 5 to 40 mol%, particularly preferably 10 to 30 mol%. If the ratio of the unit (u1) is not less than the lower limit of the above range, the mold release property of the formed film is more excellent. When the ratio of the unit (u1) is not more than the upper limit of the above range, the durability of the formed film is more excellent.
  • the proportion of the unit (u2) is preferably 30 to 48 mol%, particularly preferably 35 to 45 mol%.
  • the ratio of the unit (u2) is not less than the lower limit of the above range, the durability of the formed film is more excellent. If the ratio of the unit (u2) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
  • the proportion of the unit (u3) is preferably 30 to 48 mol%, particularly preferably 35 to 45 mol%.
  • the ratio of the unit (u3) is not less than the lower limit of the above range, the durability of the formed film is more excellent.
  • the ratio of the unit (u3) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
  • the resin composition since it contains the copolymer (A1), the copolymer (A2) and the copolymer (A3), and the compound (B), it has excellent releasability and durability.
  • a cured film (same as the release film in the present invention) can be formed.
  • the copolymer (A1), or the copolymer (A2) and the copolymer (A3) all the units (u1) to (u3) are present in the resin composition.
  • the organic group having one or more fluorine atoms in the unit (u1) lowers the surface energy of the cured film formed from the resin composition and contributes to the improvement of the release property.
  • the presence of the unit (u2) and the unit (u3) contributes to improvement in durability of the cured film formed from the resin composition.
  • the uncured film made of the resin composition is heated to a temperature at which the block isocyanate group in the unit (u2) is deblocked to become an isocyanate group (ie, T D ) or higher, the resulting isocyanate group and unit ( The active hydrogen atom-containing functional group in u3) reacts to form a crosslinked structure.
  • the deblocked isocyanate group also reacts with the functional group of the compound (B) to form a crosslinked structure.
  • a resin composition contains a compound (B), compared with the case where a compound (B) is not included, mold release property is excellent. This is because the functional group (I) of the compound (B) has a high polarity, so the affinity between the compound (B) and the organic group in the unit (u1) is low, and an uncured film is formed on the mold surface. When formed, the organic group tends to be unevenly distributed on the free surface side surface of the film by the compound (B) present in the uncured film, and then the uncured film is cured in that state, whereby the cured film This is thought to be because the organic group tends to be unevenly distributed on the surface of the free surface.
  • the above-mentioned effect by the compound (B) is sufficiently exhibited when all the units (u1) to (u3) are present in the resin composition.
  • the unit (u2) is not present in the resin composition, there is a possibility that the effect of improving the releasability is not observed.
  • the coating liquid of the present invention (hereinafter also referred to as “the present coating liquid”) is a liquid composition containing the resin composition and a solvent.
  • solvent examples include a fluorine-containing solvent and a hydrocarbon solvent.
  • a solvent may be used individually by 1 type and may use 2 or more types together.
  • the boiling point of these solvents is preferably less than the boiling point of the compound (B) so that the compound (B) is not removed during the solvent removal.
  • the boiling point is preferably 20 ° C. or more lower than the boiling point of the compound (B).
  • the lower limit of the boiling point is preferably 80 ° C., particularly preferably 100 ° C., from the viewpoint of excellent surface flatness after coating.
  • the upper limit of the boiling point of the solvent is preferably 300 ° C. from the viewpoint of easy removal by heating.
  • the boiling point may be a temperature above T D.
  • T D temperature above state continues for a long time and the cross-linking reaction in the presence of a solvent after the isocyanate group generation advances, than it is difficult to produce a good film flatness, the drying temperature (solvent heating It is preferable to quickly shift from the temperature for removal to the curing temperature.
  • the boiling point of the solvent composed of the compound having no active hydrogen atom-containing functional group is preferably T D + 50 ° C. or less, and more preferably T D + 30 ° C. or less.
  • boiling point of the solvent composed of the active hydrogen atom-containing compound is preferably sufficiently lower than T D. Its boiling point is preferably T D ⁇ 30 ° C. or lower, and more preferably T D ⁇ 50 ° C. or lower.
  • fluorine-containing solvent examples include the following compounds. Asahiclin (trademark) manufactured by Asahi Glass Co., Ltd., 1H-tridecafluorohexane (AC2000, boiling point: 71 ° C.); 1,1,1,2,2,3,3,4,4,5,5,6 6-tridecafluorooctane (AC6000, boiling point: 115 ° C.); 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (AE3000, boiling point: 56 ° C.); dichloro And pentafluoropropane (AK-225, boiling point: 54 ° C.).
  • Asahiclin trademark manufactured by Asahi Glass Co., Ltd.
  • 1H-tridecafluorohexane AC2000, boiling point: 71 ° C.
  • 1,1,1,2,2,3,3,4,4,5,5,6 6-tridecafluorooctane AC6000, boiling point: 115 ° C.
  • Cytop (trademark) CT-solv 100E (Asahi Glass Co., Ltd., boiling point: 98 ° C.); 1-methoxynonafluorobutane (manufactured by 3M Japan, Novec (trademark) 7100, boiling point: 61 ° C.); 1-ethoxynona Fluorobutane (manufactured by 3M Japan, Novec TM 7200, boiling point: 76 ° C.); 1,1,1,2,3,3-hexafluoro-4- (1,1,2,3,3,3- Hexafluoropropoxy) pentane (manufactured by 3M Japan, Novec (trademark) 7600, boiling point: 131 ° C); 2H, 3H-perfluoropentane (manufactured by Mitsui DuPont Fluorochemicals, Vertrel (trademark) XF, boiling point: 55 ° C); 3,3,4,4,5,5,6,6,7,7,8,8,8,
  • hydrocarbon solvent examples include the following compounds. Ketones such as cyclopentanone, cyclohexanone, methyl amyl ketone, 2-butanone; ethyl lactate, methyl benzoate, ethyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene Esters such as glycol monoethyl ether acetate; ethers such as tetrahydrofuran, dioxane, dimethoxyethane, diethoxyethane, anisole, diglyme, triglyme, carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-propanol, 2-butano Le
  • the ratio of the resin composition is preferably 0.1 to 30% by mass, particularly preferably 1 to 30% by mass, based on the total mass of the present coating liquid.
  • the ratio of the solvent is preferably from 70 to 99.9% by mass, particularly preferably from 70 to 99% by mass, based on the total mass of the present coating liquid.
  • the present coating liquid contains the resin composition, a film having excellent releasability and excellent durability can be formed.
  • the mold with a release film of the present invention includes a release film formed from the resin composition on the surface of the mold.
  • the material of the mold is typically a metal, and examples thereof include iron, nickel, aluminum, stainless steel, nickel alloy, and duralumin.
  • the thickness of the release film is not particularly limited, but is preferably 0.05 to 5 ⁇ m, particularly preferably 0.1 to 2 ⁇ m.
  • the mold with a release film can be produced by, for example, the following method for producing a mold with a release film.
  • a method of forming a release film by heating to obtain a mold with a release film is preferred.
  • the heating temperature is preferably the boiling point of the solvent + 10 ° C. or more (however, less than the boiling point of the compound (B)) and T D + 30 ° C. or more, the boiling point of the solvent + 20 ° C. or more (however, less than the boiling point of the compound (B)) and T D + 50 ° C. or more is more preferable.
  • the upper limit of the heating temperature is preferably 300 ° C.
  • this coating solution is applied and heated at a temperature equal to or higher than the above heating temperature, the solvent is removed to form a film made of the resin composition, and an isocyanate group is generated from the block isocyanate group in the unit (u2).
  • the isocyanate group reacts with the active hydrogen atom-containing functional group in the unit (u3) or compound (B) to form a crosslinked structure. Thereby, the release film which consists of hardened
  • the applied main coating liquid may be dried (removed from the solvent) at a temperature of less than 150 ° C. to form a dry film made of the resin composition.
  • the coating method of this coating liquid is not particularly limited, and a known wet coating method such as spraying, dipping, brush coating, spin coating or the like can be used.
  • the heating temperature for forming the release film is preferably 150 ° C. or higher.
  • the heating temperature is preferably 400 ° C. or lower.
  • the heating temperature is the mold surface temperature.
  • the heating time can be, for example, 5 to 60 minutes.
  • the mold with a release film can be used for manufacturing molded articles of various molding materials.
  • the molding material that is molded by the mold with a release film to form a molded product is not particularly limited, and may be various known molding materials such as metal, resin, and rubber.
  • the processing method using the mold according to the present invention is preferably press processing or injection molding.
  • the processing pressure is preferably 1 to 50 MPa. If it is 1 MPa or more, it will be excellent in workability, and if it is 50 MPa or less, it will be excellent in the durability of a metal mold
  • the processing temperature is preferably 150 to 250 ° C.
  • the processing object is not particularly limited, but resin materials such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, polycarbonate, polyamide, polyester, phenol resin, acrylic resin, epoxy resin, ABS resin, natural rubber, styrene butadiene rubber, Examples include rubber materials such as isoprene rubber, butadiene rubber, acrylonitrile butadiene rubber, urethane rubber, acrylic rubber, silicone rubber, and fluorine rubber, and metals such as iron, nickel, aluminum, titanium, stainless steel, nickel alloy, and duralumin.
  • resin materials such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, polycarbonate, polyamide, polyester, phenol resin, acrylic resin, epoxy resin, ABS resin, natural rubber, styrene butadiene rubber, Examples include rubber materials such as isoprene rubber, butadiene rubber, acrylonitrile butadiene
  • the release film is excellent in releasability. Moreover, it is excellent in durability and is less likely to be scraped or peeled off due to friction or the like. Therefore, by using the mold with a release film, the molded product can be easily released. In addition, with mold release agents used in conventional molds, when the molding is repeated, the release film tends to be scraped or peeled off due to contact with the molding material, etc., and it is necessary to re-form the release film frequently. was there. In the mold with a release film, since the durability of the release film is excellent, the frequency of re-forming the release film can be reduced as compared with the related art.
  • the release property and durability of a release film are excellent, it can suppress that a release film transfers to the surface of a molded article.
  • This transition can be measured by the contact angle of water on the surface of the resulting molded product. For example, if the contact angle of water on the surface of the metal (molded product) after processing is larger than the contact angle of water on the surface of the metal before processing, the release film is transferred.
  • examples 1 to 21 are examples, and examples 15 to 21 are comparative examples.
  • the measurement method used in each example is shown below.
  • composition ratio of copolymer The above-mentioned NMR measurement was performed and calculated from the integration ratio of 3.6 ppm, 3.8 ppm, and 4.3 ppm.
  • C6FMA CH 2 ⁇ C (CH 3 ) COO—C 2 H 4 —C 6 F 13
  • C6FMA was produced by the method described in Example 1 of JP-A No. 2004-359616).
  • Monomer (m1-1) CH 2 ⁇ C (CH 3 ) COO—CH 2 —CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3 (Monomer (m1-1) is Production Example 1 described below. Manufactured by.) MOI-BM:.
  • a compound represented by the following formula (i) (2-methacrylate (O-[1'-methyl propylidene amino] carboxyamino) ethyl .T D is 0.99 ° C. trade name "Karenz MOI-BM” (Made by Showa Denko).
  • HEMA 2-hydroxyethyl methacrylate (manufactured by Junsei Co., Ltd.).
  • MEK 2-butanone (manufactured by Kanto Chemical Co., Inc.).
  • Compound (B-1) Phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 220 ° C., molecular weight 126).
  • Compound (B-2) Hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 287 ° C., molecular weight 110).
  • Compound (B-3) Resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 277 ° C., molecular weight 110).
  • Compound (B-4) 2,7-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 375 ° C., molecular weight 160).
  • Compound (B-5) 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 375 ° C., molecular weight 160).
  • Compound (B-6) 1,4-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 267 ° C., molecular weight 108).
  • Compound (B-7) Trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 160 ° C., molecular weight 134).
  • Compound (B-8) Ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 197 ° C., molecular weight 62).
  • Compound (X-1) Isopropanol (manufactured by Kanto Chemical Co., Inc., boiling point 83 ° C., molecular weight 74).
  • Example 1 1.0 g of the copolymer (A1-1), 0.3 g of phloroglucinol, and 4.0 g of cyclohexanone as a solvent were placed in a glass vial (20 mL) and sufficiently stirred to obtain a homogeneous solution. The obtained solution was filtered through a PTFE filter having a nominal pore size of 0.20 ⁇ m to prepare a coating solution.
  • Example 2 1.0 g of copolymer (A1-1), 0.5 g of phloroglucinol, and 4.0 g of cyclohexanone as a solvent were placed in a glass vial (20 mL) and stirred well to obtain a homogeneous solution. The obtained solution was filtered through a PTFE filter having a nominal pore size of 0.20 ⁇ m to prepare a coating solution.
  • Examples 3 to 12, 15 to 21 A coating solution was prepared in the same manner as in Example 1 except that the copolymers and compounds shown in Tables 2 to 4 were used.
  • Example 13 0.5 g of copolymer (A2-1), 0.5 g of copolymer (A3-1), 0.3 g of phloroglucinol, and 4.0 g of cyclohexanone as a solvent were placed in a glass vial (20 mL). The solution was sufficiently stirred to obtain a uniform solution. The obtained solution was filtered through a PTFE filter having a nominal pore size of 0.20 ⁇ m to prepare a coating solution.
  • Example 14 A coating solution was prepared in the same manner as in Example 13 except that the compounds shown in Table 3 were used.
  • the release films formed from the coating liquids of Examples 1 to 14 had a low peel strength of the adhesive tape and excellent mold release properties. Further, the film hardness was F or more, and the durability was excellent.
  • the release film formed from the coating solution of Example 16 using the above compound had high peel strength and was inferior in release properties.
  • the release films formed from the coating liquids of Examples 17 to 20 containing no unit (u2) had low film hardness and poor durability.
  • the resin composition and coating liquid of the present invention are useful for producing, for example, a mold with a release film, an article with an antifouling coat, an article with a liquid repellent coat, and the like.
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2016-126690 filed on June 27, 2016 are incorporated herein as the disclosure of the specification of the present invention. It is.

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Abstract

Provided are the following: a resin composition and coating liquid which can form a film having excellent mold release properties and excellent durability; a release film-equipped mold which is provided with a release film having excellent mold release properties and excellent durability; and a method for producing same. This resin composition contains a copolymer (A1), which has units derived from a monomer having an organic group having 1 or more fluorine atoms (however, the monomer does not have a blocked isocyanate group or an active hydrogen atom-containing functional group), units derived from a monomer having a blocked isocyanate group (however, the monomer does not have an active hydrogen atom-containing functional group) and units derived from a monomer having an active hydrogen atom-containing functional group (however, the monomer does not have a blocked isocyanate group), and a compound (B) which has 2 or more of at least 1 type of functional group selected from the group consisting of hydroxyl groups, amino groups and carboxyl groups and which has a boiling point that is not lower than the block dissociation temperature of blocked isocyanate groups in the copolymer (A1) and not higher than 400ºC.

Description

樹脂組成物、コーティング液、離型膜付き金型およびその製造方法RESIN COMPOSITION, COATING LIQUID, RELEASE MEMBRANE MOLD, AND METHOD FOR PRODUCING THE SAME
　本発明は、樹脂組成物、コーティング液、離型膜付き金型およびその製造方法に関する。 The present invention relates to a resin composition, a coating liquid, a mold with a release film, and a manufacturing method thereof.
　従来から、離型性に優れる離型剤として、含フッ素化合物が用いられてきた（例えば特許文献１）。かかる離型剤は、例えば、樹脂、ゴム、金属等を成形する金型の表面に成膜される。これにより金型からの成形品の離型性が向上する。 Conventionally, fluorine-containing compounds have been used as mold release agents with excellent mold release properties (for example, Patent Document 1). Such a mold release agent is formed on the surface of a mold for molding a resin, rubber, metal or the like, for example. Thereby, the mold release property of the molded product from a metal mold | die improves.
特開２０１０－１８０３８号公報JP 2010-18038 A
　しかし、特許文献１に記載の離型剤の膜（以下、「離型膜」とも記す。）の耐久性は充分ではなく、成形品の成形を繰り返すうちに、流動する樹脂やゴムによって離型膜が削られたり、離型膜が成形品に移行したりして、離型膜が損なわれる問題がある。
　本発明の目的は、離型性に優れ、かつ耐久性に優れた膜を形成できる樹脂組成物およびコーティング液、ならびに離型性に優れ、かつ耐久性に優れた離型膜を備える離型膜付き金型およびその製造方法を提供することにある。 However, the durability of the release agent film described in Patent Document 1 (hereinafter also referred to as “release film”) is not sufficient, and the mold is released by a resin or rubber that flows while the molded product is repeatedly molded. There is a problem that the release film is damaged because the film is scraped or the release film is transferred to a molded product.
An object of the present invention is to provide a resin composition and a coating liquid that can form a film having excellent releasability and excellent durability, and a release film having a releasable film that has excellent releasability and excellent durability An object of the present invention is to provide an attached die and a manufacturing method thereof.
　本発明は、以下の［１］～［１５］の構成を有する、樹脂組成物、コーティング液、離型膜付き金型およびその製造方法を提供する。
　［１］下記単位（ｕ１）と下記単位（ｕ２）と下記単位（ｕ３）とを有する共重合体（Ａ１）と、下記化合物（Ｂ）とを含むことを特徴とする樹脂組成物。
　単位（ｕ１）：フッ素原子を１つ以上有する有機基を有する（ただしブロックイソシアナート基および活性水素原子含有官能基を有しない。）単量体に由来する単位。
　単位（ｕ２）：ブロックイソシアナート基を有する（ただし活性水素原子含有官能基を有しない。）単量体に由来する単位。
　単位（ｕ３）：活性水素原子含有官能基を有する（ただしブロックイソシアナート基を有しない。）単量体に由来する単位。
　化合物（Ｂ）：水酸基、アミノ基およびカルボキシ基からなる群から選ばれる少なくとも１種の官能基を２以上有し、その沸点が共重合体（Ａ１）におけるブロックイソシアナート基のブロック解離温度以上かつ４００℃以下である、化合物。
　［２］前記共重合体（Ａ１）が、共重合体（Ａ１）中の全単位に対して、単位（ｕ１）を５～４０モル％、単位（ｕ２）を３０～４８モル％および単位（ｕ３）を３０～４８モル％の割合で含む共重合体である、［１］の樹脂組成物。
　［３］前記共重合体（Ａ１）の質量平均分子量が５，０００～２００，０００である、［１］または［２］の樹脂組成物。
　［４］前記化合物（Ｂ）の含有量が、前記共重合体（Ａ１）の１００質量部に対して２０～６０質量部である、［１］～［３］のいずれかの樹脂組成物。 The present invention provides a resin composition, a coating liquid, a mold with a release film, and a method for producing the same, having the following configurations [1] to [15].
[1] A resin composition comprising a copolymer (A1) having the following unit (u1), the following unit (u2) and the following unit (u3), and the following compound (B).
Unit (u1): A unit derived from a monomer having an organic group having one or more fluorine atoms (but not having a block isocyanate group and an active hydrogen atom-containing functional group).
Unit (u2): A unit derived from a monomer having a block isocyanate group (but not having an active hydrogen atom-containing functional group).
Unit (u3): A unit derived from a monomer having an active hydrogen atom-containing functional group (but not having a block isocyanate group).
Compound (B): having at least two functional groups selected from the group consisting of a hydroxyl group, an amino group and a carboxy group, the boiling point of which is not less than the block dissociation temperature of the block isocyanate group in the copolymer (A1); A compound that is 400 ° C. or lower.
[2] In the copolymer (A1), the unit (u1) is 5 to 40 mol%, the unit (u2) is 30 to 48 mol% and the unit (u1) with respect to all units in the copolymer (A1). The resin composition according to [1], which is a copolymer containing u3) in a proportion of 30 to 48 mol%.
[3] The resin composition according to [1] or [2], wherein the copolymer (A1) has a mass average molecular weight of 5,000 to 200,000.
[4] The resin composition according to any one of [1] to [3], wherein the content of the compound (B) is 20 to 60 parts by mass with respect to 100 parts by mass of the copolymer (A1).
　［５］下記単位（ｕ１）と下記単位（ｕ２）とを有し、下記単位（ｕ３）を有しない共重合体（Ａ２）と、前記単位（ｕ１）と前記単位（ｕ３）とを有し、前記単位（ｕ２）を有しない共重合体（Ａ３）と、下記化合物（Ｂ）とを含むことを特徴とする樹脂組成物。
　単位（ｕ１）：フッ素原子を１つ以上有する有機基を有する（ただしブロックイソシアナート基および活性水素原子含有官能基を有しない。）単量体に由来する単位。
　単位（ｕ２）：ブロックイソシアナート基を有する（ただし活性水素原子含有官能基を有しない。）単量体に由来する単位。
　単位（ｕ３）：活性水素原子含有官能基を有する（ただしブロックイソシアナート基を有しない。）単量体に由来する単位。
　化合物（Ｂ）：水酸基、アミノ基およびカルボキシ基からなる群から選ばれる少なくとも１種の官能基を２以上有し、その沸点が共重合体（Ａ２）におけるブロックイソシアナート基のブロック解離温度以上かつ４００℃以下である、化合物。
　［６］前記共重合体（Ａ２）が、共重合体（Ａ２）中の全単位に対して、単位（ｕ１）を５～４０モル％および単位（ｕ２）を６０～９５モル％の割合で含む共重合体であり、
　前記共重合体（Ａ３）が、共重合体（Ａ３）中の全単位に対して、単位（ｕ１）を５～４０モル％および単位（ｕ３）を６０～９５モル％の割合で含む共重合体である、
［５］の樹脂組成物。
　［７］前記共重合体（Ａ２）の質量平均分子量が５，０００～２００，０００であり、前記共重合体（Ａ３）の質量平均分子量が５，０００～２００，０００である、［５］または［６］の樹脂組成物。
　［８］前記化合物（Ｂ）の含有量が、前記共重合体（Ａ２）と前記共重合体（Ａ３）との合計１００質量部に対して２０～６０質量部である、［５］～［７］のいずれかの樹脂組成物。 [5] A copolymer (A2) having the following unit (u1) and the following unit (u2) and not having the following unit (u3), the unit (u1) and the unit (u3) A resin composition comprising a copolymer (A3) having no unit (u2) and the following compound (B).
Unit (u1): A unit derived from a monomer having an organic group having one or more fluorine atoms (but not having a block isocyanate group and an active hydrogen atom-containing functional group).
Unit (u2): A unit derived from a monomer having a block isocyanate group (but not having an active hydrogen atom-containing functional group).
Unit (u3): A unit derived from a monomer having an active hydrogen atom-containing functional group (but not having a block isocyanate group).
Compound (B): having at least two functional groups selected from the group consisting of a hydroxyl group, an amino group and a carboxy group, the boiling point of which is not less than the block dissociation temperature of the block isocyanate group in the copolymer (A2); A compound that is 400 ° C. or lower.
[6] In the copolymer (A2), the unit (u1) is 5 to 40 mol% and the unit (u2) is 60 to 95 mol% with respect to all the units in the copolymer (A2). A copolymer comprising
The copolymer (A3) contains 5-40 mol% of units (u1) and 60-95 mol% of units (u3) with respect to all units in the copolymer (A3). United,
[5] The resin composition.
[7] The copolymer (A2) has a mass average molecular weight of 5,000 to 200,000, and the copolymer (A3) has a mass average molecular weight of 5,000 to 200,000. [5] Or the resin composition of [6].
[8] The content of the compound (B) is 20 to 60 parts by mass with respect to 100 parts by mass in total of the copolymer (A2) and the copolymer (A3). 7].
　［９］前記単位（ｕ１）が、フッ素原子を１つ以上有する有機基として、炭素数４～６の直鎖のペルフルオロアルキル基、または炭素数４～６の直鎖のペルフルオロアルキル基の炭素原子間に１～３個のエーテル性酸素原子を有する基を有する、［１］～［８］のいずれかの樹脂組成物。
　［１０］前記共重合体におけるブロックイソシアナート基のブロック解離温度が１２０～２００℃である、［１］～［９］のいずれかの樹脂組成物。
　［１１］前記化合物（Ｂ）が芳香環を有する、［１］～［１０］のいずれかの樹脂組成物。 [9] The carbon atom of the linear perfluoroalkyl group having 4 to 6 carbon atoms or the linear perfluoroalkyl group having 4 to 6 carbon atoms as the organic group in which the unit (u1) has one or more fluorine atoms The resin composition according to any one of [1] to [8], which has a group having 1 to 3 etheric oxygen atoms in between.
[10] The resin composition according to any one of [1] to [9], wherein the block dissociation temperature of the block isocyanate group in the copolymer is 120 to 200 ° C.
[11] The resin composition according to any one of [1] to [10], wherein the compound (B) has an aromatic ring.
　［１２］前記［１］～［１１］のいずれかの樹脂組成物と、溶剤とを含むことを特徴とするコーティング液。
　［１３］前記溶剤の含有割合が、コーティング液の総質量に対して、７０～９９．９質量％である、［１２］のコーティング液。
　［１４］金型の表面に、［１］～［１０］のいずれかの樹脂組成物から形成された離型膜を備えることを特徴とする離型膜付き金型。
　［１５］金型の表面に、［１２］のコーティング液を塗布し、ブロックイソシアナート基のブロック解離温度以上の温度で加熱して離型膜を形成し、離型膜付き金型を得ることを特徴とする離型膜付き金型の製造方法。 [12] A coating solution comprising the resin composition of any one of [1] to [11] and a solvent.
[13] The coating liquid according to [12], wherein the content ratio of the solvent is 70 to 99.9% by mass with respect to the total mass of the coating liquid.
[14] A mold with a release film, comprising a release film formed from the resin composition of any one of [1] to [10] on the surface of the mold.
[15] Applying the coating liquid of [12] to the surface of the mold and heating at a temperature equal to or higher than the block dissociation temperature of the block isocyanate group to form a release film, thereby obtaining a mold with a release film The manufacturing method of the metal mold | die with a release film characterized by these.
　本発明の樹脂組成物およびコーティング液によれば、離型性に優れ、かつ耐久性に優れた膜を形成できる。
　本発明の離型膜付き金型は、離型性に優れ、かつ耐久性に優れた離型膜を備える。
　本発明の離型膜付き金型の製造方法によれば、離型性に優れ、かつ耐久性に優れた離型膜を備える離型膜付き金型を製造できる。 According to the resin composition and the coating liquid of the present invention, a film having excellent releasability and excellent durability can be formed.
The mold with a release film of the present invention is provided with a release film that is excellent in releasability and excellent in durability.
According to the method for manufacturing a mold with a release film of the present invention, it is possible to manufacture a mold with a release film having a release film that is excellent in mold release properties and excellent in durability.
　本明細書における下記の用語の意味は以下の通りである。
　重合体における「単位」とは、単量体が重合することによって形成された該単量体に由来する部分を意味する。単位は、重合反応によって直接形成された単位であってもよく、重合体を処理することによって該単位の一部が別の構造に変換された単位であってもよい。
　「（メタ）アクリロイルオキシ基」とは、アクリロイルオキシ基およびメタクリロイルオキシ基の総称である。
　「（メタ）アクリレート」とは、アクリレートおよびメタクリレートの総称である。
　「離型膜」とは、基材等に形成された膜表面が該膜の形成されていない部分に比べ離型性に優れる膜、具体的には膜表面に付着した物質の剥離強度が該膜の形成されていない部分に比べて小さい膜を意味する。 The meanings of the following terms in this specification are as follows.
The “unit” in the polymer means a portion derived from the monomer formed by polymerization of the monomer. The unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treating the polymer.
The “(meth) acryloyloxy group” is a general term for an acryloyloxy group and a methacryloyloxy group.
“(Meth) acrylate” is a general term for acrylate and methacrylate.
“Release film” refers to a film having a film surface that is formed on a substrate or the like that is superior in release properties compared to a portion where the film is not formed, specifically, the peel strength of a substance attached to the film surface is It means a film that is smaller than the part where no film is formed.
〔樹脂組成物〕
　本発明の樹脂組成物は、後述の共重合体（Ａ１）と化合物（Ｂ）とを含む組成物（以下、「樹脂組成物（１）」とも記す。）、または、共重合体（Ａ２）と共重合体（Ａ３）と化合物（Ｂ）とを含む組成物（以下、「樹脂組成物（２）」とも記す。）である。なお、単に「樹脂組成物」という場合、樹脂組成物（１）および樹脂組成物（２）の両方を意味する。
　樹脂組成物は、必要に応じて、他の成分をさらに含んでもよい。 (Resin composition)
The resin composition of the present invention is a composition containing a copolymer (A1) and a compound (B) described later (hereinafter also referred to as “resin composition (1)”), or a copolymer (A2). And a copolymer (A3) and a compound (B) (hereinafter also referred to as “resin composition (2)”). In addition, when only calling it a "resin composition", both the resin composition (1) and the resin composition (2) are meant.
The resin composition may further contain other components as necessary.
　共重合体（Ａ１）、共重合体（Ａ２）、共重合体（Ａ３）の質量平均分子量（Ｍｗ）はそれぞれ、５，０００～２００，０００が好ましく、１０，０００～１５０，０００が特に好ましい。共重合体（Ａ１）、共重合体（Ａ２）、共重合体（Ａ３）のＭｗが前記範囲の下限値以上であれば離型剤の膜の耐久性がより優れ、前記範囲の上限値以下であれば溶剤への溶解性がより優れる。
　質量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）で測定されるポリメチルメタリレート換算の値である。 The weight average molecular weight (Mw) of each of the copolymer (A1), the copolymer (A2), and the copolymer (A3) is preferably 5,000 to 200,000, particularly preferably 10,000 to 150,000. . If the Mw of the copolymer (A1), the copolymer (A2), and the copolymer (A3) is equal to or greater than the lower limit of the above range, the durability of the release agent film is more excellent, and is not greater than the upper limit of the above range. If so, the solubility in a solvent is more excellent.
The mass average molecular weight (Mw) is a value in terms of polymethyl metallate measured by gel permeation chromatography (GPC).
　共重合体（Ａ１）、共重合体（Ａ２）、共重合体（Ａ３）中に含まれる各単位は以下の通りである。
（単位（ｕ１））
　単位（ｕ１）は、フッ素原子を１つ以上有する有機基を有する（ただしブロックイソシアナート基および活性水素原子含有官能基を有しない。）単量体（以下、「単量体（ｍ１）」とも記す。）に由来する単位である。
　共重合体（Ａ１）～（Ａ３）が単位（ｕ１）を有することによって、樹脂組成物から形成される膜が、離型性に優れる。 Each unit contained in the copolymer (A1), the copolymer (A2), and the copolymer (A3) is as follows.
(Unit (u1))
The unit (u1) has an organic group having one or more fluorine atoms (however, it does not have a block isocyanate group and an active hydrogen atom-containing functional group) and is a monomer (hereinafter referred to as “monomer (m1)”). It is a unit derived from.
When the copolymers (A1) to (A3) have the unit (u1), the film formed from the resin composition is excellent in releasability.
　フッ素原子を１つ以上有する有機基としては、離型性がより優れる点から、ポリフルオロアルキル基、またはポリフルオロアルキル基の炭素原子間にエーテル性酸素原子を有する基が好ましく、ペルフルオロアルキル基、またはペルフルオロアルキル基の炭素原子間にエーテル性酸素原子を有する基が特に好ましい。
　ポリフルオロアルキル基およびポリフルオロアルキル基の炭素原子間にエーテル性酸素原子を有する基の炭素数は、離型性の点からは、４以上が好ましい。環境に対する影響が少ない点からは、６以下が好ましい。よって前記炭素数は、４～６がより好ましく、６が特に好ましい。エーテル性酸素原子の数は１～３が好ましく、１～２が特に好ましい。
　ポリフルオロアルキル基は、直鎖でも分岐鎖でもよく、直鎖が好ましい。
　すなわち、フッ素原子を１つ以上有する有機基としては、炭素数４～６の直鎖のペルフルオロアルキル基、または炭素数４～６の直鎖のペルフルオロアルキル基の炭素原子間に１～３個のエーテル性酸素原子を有する基が好ましく、炭素数６の直鎖のペルフルオロアルキル基、または炭素数６の直鎖のペルフルオロアルキル基の炭素原子間に１～２個のエーテル性酸素原子を有する基が特に好ましい。 As the organic group having one or more fluorine atoms, a polyfluoroalkyl group or a group having an etheric oxygen atom between carbon atoms of the polyfluoroalkyl group is preferable from the viewpoint of more excellent releasability, and a perfluoroalkyl group, Or the group which has an etheric oxygen atom between the carbon atoms of a perfluoroalkyl group is especially preferable.
The number of carbon atoms of the polyfluoroalkyl group and the group having an etheric oxygen atom between the carbon atoms of the polyfluoroalkyl group is preferably 4 or more from the viewpoint of releasability. 6 or less is preferable from the viewpoint of little influence on the environment. Therefore, the carbon number is more preferably 4 to 6, and particularly preferably 6. The number of etheric oxygen atoms is preferably 1 to 3, particularly preferably 1 to 2.
The polyfluoroalkyl group may be linear or branched, and is preferably linear.
That is, examples of the organic group having one or more fluorine atoms include 1 to 3 carbon atoms between carbon atoms of a linear perfluoroalkyl group having 4 to 6 carbon atoms or a linear perfluoroalkyl group having 4 to 6 carbon atoms. A group having an etheric oxygen atom is preferred, and a straight-chain perfluoroalkyl group having 6 carbon atoms or a group having 1 to 2 etheric oxygen atoms between carbon atoms of a straight-chain perfluoroalkyl group having 6 carbon atoms. Particularly preferred.
　単量体（ｍ１）は、重合性二重結合を有する基とフッ素原子を１つ以上有する有機基とが直接または連結基を介して結合した構造であることが好ましい。
　直接または連結基を介して結合する重合性二重結合およびフッ素原子を１つ以上有する有機基の数はそれぞれ１つであることが好ましい。 The monomer (m1) preferably has a structure in which a group having a polymerizable double bond and an organic group having one or more fluorine atoms are bonded directly or via a linking group.
The number of polymerizable double bonds and one or more organic groups having one or more fluorine atoms bonded directly or via a linking group is preferably one.
　重合性二重結合を有する基としては、例えばビニル基、アリル基、（メタ）アクリロイルオキシ基、α－ハロゲノアクリロイルオキシ基等が挙げられる。これらのうち、共重合体の分子量を制御しやすい点から、（メタ）アクリロイルオキシ基が好ましい。 Examples of the group having a polymerizable double bond include a vinyl group, an allyl group, a (meth) acryloyloxy group, an α-halogenoacryloyloxy group, and the like. Of these, a (meth) acryloyloxy group is preferable from the viewpoint of easily controlling the molecular weight of the copolymer.
　連結基としては、例えば２価の炭化水素基が挙げられる。２価の炭化水素基としては、例えばアルキレン基、アリーレン基等が挙げられる。該連結基としては、耐久性の観点から、アルキレン基が好ましく、炭素数１～６のアルキレン基が特に好ましい。アルキレン基は、直鎖でも分岐鎖でもよく、直鎖が好ましい。 Examples of the linking group include a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group and an arylene group. As the linking group, an alkylene group is preferable from the viewpoint of durability, and an alkylene group having 1 to 6 carbon atoms is particularly preferable. The alkylene group may be linear or branched and is preferably linear.
　単量体（ｍ１）としては、形成される膜の離型性がより優れ、環境に対する影響が少なく、入手容易な点から、ＣＨ２＝Ｃ（Ｒ１１）Ｃ（Ｏ）Ｏ－Ｒ１２－Ｒｆで表される単量体が好ましい。ただし、Ｒ１１は、水素原子、メチル基またはハロゲン原子（フッ素原子、塩素原子等）であり、Ｒ１２は、アルキレン基であり、Ｒｆは、炭素数４～６のペルフルオロアルキル基または炭素数４～６のペルフルオロアルキル基の炭素原子間にエーテル性酸素原子を有する基である。 As the monomer (m1), CH 2 ═C (R 11 ) C (O) O—R 12 — is more easily obtained because it has better mold releasability, less influence on the environment, and is easily available. A monomer represented by R f is preferred. However, R 11 is a hydrogen atom, a methyl group or a halogen atom (fluorine atom, chlorine atom, etc.), R 12 is an alkylene group, R f is a C 4-6 perfluoroalkyl group or carbon number A group having an etheric oxygen atom between carbon atoms of 4 to 6 perfluoroalkyl groups.
　Ｒ１１としては、水素原子またはメチル基が好ましく、メチル基が特に好ましい。
　Ｒ１２としては、炭素数１～６のアルキレン基が好ましく、－ＣＨ２－、－Ｃ２Ｈ４－が特に好ましい。
　Ｒｆとしては、－（ＣＦ２）３ＣＦ３、－（ＣＦ２）４ＣＦ３、－（ＣＦ２）５ＣＦ３、－ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３、－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３、－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３が好ましい。 R 11 is preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
R 12 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably —CH 2 — or —C 2 H 4 —.
R f includes — (CF 2 ) 3 CF 3 , — (CF 2 ) 4 CF 3 , — (CF 2 ) 5 CF 3 , —CF (CF 3 ) OCF 2 CF 2 CF 3 , —CF 2 OCF 2 CF 2 OCF 3 , —CF 2 OCF 2 CF 2 OCF 2 CF 3 , and —CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3 are preferable.
　ＣＨ２＝Ｃ（Ｒ１１）Ｃ（Ｏ）Ｏ－Ｒ１２－Ｒｆで表される単量体としては、下記の化合物が挙げられる。
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３、
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３、
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
　ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
　ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
　ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
　ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＣＦ３、
　ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
　ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ３、
　ＣＨ２＝ＣＨＣ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３、
　ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）３ＣＦ３、
　ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）４ＣＦ３、
　ＣＨ２＝Ｃ（Ｃｌ）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３等。 Examples of the monomer represented by CH 2 ═C (R 11 ) C (O) O—R 12 —R f include the following compounds.
CH 2 ═C (CH 3 ) C (O) O—C 2 H 4 — (CF 2 ) 3 CF 3 ,
CH 2 ═C (CH 3 ) C (O) O—C 2 H 4 — (CF 2 ) 4 CF 3 ,
CH 2 ═C (CH 3 ) C (O) O—C 2 H 4 — (CF 2 ) 5 CF 3 ,
CH 2 ═C (CH 3 ) C (O) O—CH 2 —CF (CF 3 ) OCF 2 CF 2 CF 3 ,
CH 2 ═C (CH 3 ) C (O) O—CH 2 —CF 2 OCF 2 CF 2 OCF 3 ,
CH 2 ═C (CH 3 ) C (O) O—CH 2 —CF 2 OCF 2 CF 2 OCF 2 CF 3 ,
CH 2 ═C (CH 3 ) C (O) O—CH 2 —CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3 ,
CH 2 = CHC (O) O—C 2 H 4 — (CF 2 ) 3 CF 3 ,
CH 2 = CHC (O) O—C 2 H 4 — (CF 2 ) 4 CF 3 ,
CH 2 = CHC (O) O—C 2 H 4 — (CF 2 ) 5 CF 3 ,
CH 2 ═CHC (O) O—CH 2 —CF (CF 3 ) OCF 2 CF 2 CF 3 ,
CH 2 ═CHC (O) O—CH 2 —CF 2 OCF 2 CF 2 OCF 3 ,
CH 2 ═CHC (O) O—CH 2 —CF 2 OCF 2 CF 2 OCF 2 CF 3 ,
CH 2 ═CHC (O) O—CH 2 —CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3 ,
CH 2 ═C (Cl) C (O) O—C 2 H 4 — (CF 2 ) 3 CF 3 ,
CH 2 ═C (Cl) C (O) O—C 2 H 4 — (CF 2 ) 4 CF 3 ,
CH 2 ═C (Cl) C (O) O—C 2 H 4 — (CF 2 ) 5 CF 3 etc.
　単量体（ｍ１）としては、下記の化合物が特に好ましい。
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－Ｃ２Ｈ４－（ＣＦ２）５ＣＦ３、
　ＣＨ２＝Ｃ（ＣＨ３）Ｃ（Ｏ）Ｏ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３。
　単量体（ｍ１）は、１種を単独で用いてもよく、２種以上を併用してもよい。 As the monomer (m1), the following compounds are particularly preferable.
CH 2 ═C (CH 3 ) C (O) O—C 2 H 4 — (CF 2 ) 5 CF 3 ,
CH 2 = C (CH 3) C (O) O-CH 2 -CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3.
A monomer (m1) may be used individually by 1 type, and may use 2 or more types together.
（単位（ｕ２））
　単位（ｕ２）は、ブロックイソシアナート基を有する（ただし活性水素原子含有官能基を有しない。）単量体（以下、「単量体（ｍ２）」とも記す。）に由来する単位である。 (Unit (u2))
The unit (u2) is a unit derived from a monomer having a block isocyanate group (but not having an active hydrogen atom-containing functional group) (hereinafter also referred to as “monomer (m2)”).
　ブロックイソシアナート基は、イソシアナート基をブロック剤でブロックした基である。イソシアナート基をブロックするブロック剤としては、例えばオキシム類、ピラゾール類等が挙げられる。 The blocked isocyanate group is a group obtained by blocking an isocyanate group with a blocking agent. Examples of the blocking agent that blocks the isocyanate group include oximes and pyrazoles.
　単量体（ｍ２）は、重合性二重結合を有する基とブロックイソシアナート基とが直接または連結基を介して結合した構造であることが好ましい。
　直接または連結基を介して結合する重合性二重結合およびブロックイソシアナート基の数はそれぞれ１つであることが好ましい。
　重合性二重結合を有する基および連結基としてはそれぞれ、単量体（ｍ１）における重合性二重結合を有する基および連結基と同じ基が挙げられ、好ましい態様も同様である。 The monomer (m2) preferably has a structure in which a group having a polymerizable double bond and a block isocyanate group are bonded directly or via a linking group.
The number of polymerizable double bonds and block isocyanate groups bonded directly or via a linking group is preferably one each.
Examples of the group having a polymerizable double bond and the linking group include the same groups as the group having a polymerizable double bond and the linking group in the monomer (m1), and preferred embodiments are also the same.
　単量体（ｍ２）としては、架橋反応の容易性の点から、ＣＨ２＝Ｃ（Ｒ１３）Ｃ（Ｏ）Ｏ－Ｒ１４－ＮＨＣ（Ｏ）Ｒ１５で表される単量体が好ましい。ただし、Ｒ１３は、水素原子、メチル基またはハロゲン原子（フッ素原子、塩素原子等）であり、Ｒ１４は、アルキレン基であり、Ｒ１５は、１価の有機基である。
　－ＮＨＣ（Ｏ）Ｒ１５がブロックイソシアナート基に相当する。 The monomer (m2) is preferably a monomer represented by CH 2 ═C (R 13 ) C (O) O—R 14 —NHC (O) R 15 from the viewpoint of easy crosslinking reaction. . However, R 13 is a hydrogen atom, a methyl group or a halogen atom (fluorine atom, chlorine atom, etc.), R 14 is an alkylene group, R 15 is a monovalent organic group.
—NHC (O) R 15 corresponds to a blocked isocyanate group.
　Ｒ１３としては、水素原子またはメチル基が好ましく、メチル基が特に好ましい。
　Ｒ１４としては、炭素数１～６のアルキレン基が好ましく、－ＣＨ２－、－Ｃ２Ｈ４－が特に好ましい。
　Ｒ１５としては、下記式（５ａ）で表される基、下記式（５ｂ）で表される基、または下記式（５ｃ）で表される基が好ましい。ただしＲ５１、Ｒ５２、Ｒ５３およびＲ５４はそれぞれ独立に炭素数１～４のアルキル基である。
　単量体（ｍ２）は、１種を単独で用いてもよく、２種以上を併用してもよい。 R 13 is preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.
R 14 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably —CH 2 — or —C 2 H 4 —.
R 15 is preferably a group represented by the following formula (5a), a group represented by the following formula (5b), or a group represented by the following formula (5c). However, R 51 , R 52 , R 53 and R 54 are each independently an alkyl group having 1 to 4 carbon atoms.
A monomer (m2) may be used individually by 1 type, and may use 2 or more types together.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
（単位（ｕ３））
　単位（ｕ３）は、活性水素原子含有官能基を有する（ただしブロックイソシアナート基を有しない。）単量体（以下、「単量体（ｍ３）」とも記す。）に由来する単位である。 (Unit (u3))
The unit (u3) is a unit derived from a monomer having an active hydrogen atom-containing functional group (but not having a block isocyanate group) (hereinafter also referred to as “monomer (m3)”).
　活性水素原子含有官能基としては、水酸基（ＯＨ）またはアミノ基（ＮＨ２）が好ましく、水酸基が特に好ましい。 As the active hydrogen atom-containing functional group, a hydroxyl group (OH) or an amino group (NH 2 ) is preferable, and a hydroxyl group is particularly preferable.
　単量体（ｍ３）は、重合性二重結合を有する基と活性水素原子含有官能基とが直接または連結基を介して結合した構造であることが好ましい。
　重合性二重結合を有する基および連結基としてはそれぞれ、単量体（ｍ１）における重合性二重結合を有する基および連結基と同じ基が挙げられ、好ましい態様も同様である。 The monomer (m3) preferably has a structure in which a group having a polymerizable double bond and an active hydrogen atom-containing functional group are bonded directly or via a linking group.
Examples of the group having a polymerizable double bond and the linking group include the same groups as the group having a polymerizable double bond and the linking group in the monomer (m1), and preferred embodiments are also the same.
　単量体（ｍ３）としては、架橋反応の容易性の点から、ＣＨ２＝Ｃ（Ｒ１６）Ｃ（Ｏ）Ｏ－Ｒ１７－ＯＨで表される単量体が好ましい。ただし、Ｒ１６は、水素原子、メチル基またはハロゲン原子（フッ素原子、塩素原子等）であり、Ｒ１７は、アルキレン基である。 As the monomer (m3), a monomer represented by CH 2 ═C (R 16 ) C (O) O—R 17 —OH is preferable from the viewpoint of easy crosslinking reaction. However, R 16 is a hydrogen atom, a methyl group or a halogen atom (fluorine atom, chlorine atom, etc.), R 17 is an alkylene group.
　Ｒ１６としては、水素原子またはメチル基が好ましく、メチル基が特に好ましい。
　Ｒ１７としては、炭素数１～６のアルキレン基が好ましく、－ＣＨ２－、－Ｃ２Ｈ４－が特に好ましい。
　単量体（ｍ３）は、１種を単独で用いてもよく、２種以上を併用してもよい。 R 16 is preferably a hydrogen atom or a methyl group, particularly preferably a methyl group.
R 17 is preferably an alkylene group having 1 to 6 carbon atoms, particularly preferably —CH 2 — or —C 2 H 4 —.
A monomer (m3) may be used individually by 1 type, and may use 2 or more types together.
（他の単位）
　共重合体（Ａ１）、共重合体（Ａ２）および共重合体（Ａ３）は、それぞれ、単位（ｕ１）、単位（ｕ２）および単位（ｕ３）以外の単位（以下、「他の単位」と記す。）を有していてもよい。
　他の単位は、単量体（ｍ１）、単量体（ｍ２）および単量体（ｍ３）以外の単量体（以下、「単量体（ｍ４）」とも記す。）に由来する単位である。
　単量体（ｍ４）としては、例えば、アルキル（メタ）アクリレート、アルキルビニルエーテル、塩化ビニル等が挙げられる。
　単量体（ｍ４）は、１種を単独で用いてもよく、２種以上を併用してもよい。 (Other units)
Copolymer (A1), copolymer (A2) and copolymer (A3) are units (u1), units (u2) and units other than unit (u3) (hereinafter referred to as “other units”, respectively). May be included).
The other unit is a unit derived from a monomer other than the monomer (m1), the monomer (m2) and the monomer (m3) (hereinafter also referred to as “monomer (m4)”). is there.
Examples of the monomer (m4) include alkyl (meth) acrylate, alkyl vinyl ether, vinyl chloride and the like.
A monomer (m4) may be used individually by 1 type, and may use 2 or more types together.
（共重合体（Ａ１））
　共重合体（Ａ１）は、単位（ｕ１）と単位（ｕ２）と単位（ｕ３）とを有する。
　共重合体（Ａ１）は、必要に応じて、他の単位をさらに有していてもよい。 (Copolymer (A1))
The copolymer (A1) has a unit (u1), a unit (u2), and a unit (u3).
The copolymer (A1) may further have other units as necessary.
　共重合体（Ａ１）において、単位（ｕ１）の割合は、共重合体（Ａ１）の全単位中、５～４０モル％が好ましく、１０～３０モル％が特に好ましい。単位（ｕ１）の割合が前記範囲の下限値以上であれば、形成される膜の離型性がより優れる。単位（ｕ１）の割合が前記範囲の上限値以下であれば、形成される膜の耐久性がより優れる。 In the copolymer (A1), the proportion of the unit (u1) is preferably from 5 to 40 mol%, particularly preferably from 10 to 30 mol%, based on the total units of the copolymer (A1). If the ratio of the unit (u1) is not less than the lower limit of the above range, the mold release property of the formed film is more excellent. When the ratio of the unit (u1) is not more than the upper limit of the above range, the durability of the formed film is more excellent.
　単位（ｕ２）の割合は、共重合体（Ａ１）の全単位中、３０～４８モル％が好ましく、３５～４５モル％が特に好ましい。単位（ｕ２）の割合が前記範囲の下限値以上であれば、形成される膜の耐久性がより優れる。単位（ｕ２）の割合が前記範囲の上限値以下であれば、形成される膜の離型性がより優れる。 The ratio of the unit (u2) is preferably 30 to 48 mol%, particularly preferably 35 to 45 mol%, based on all units of the copolymer (A1). When the ratio of the unit (u2) is not less than the lower limit of the above range, the durability of the formed film is more excellent. If the ratio of the unit (u2) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
　単位（ｕ３）の割合は、共重合体（Ａ１）の全単位中、３０～４８モル％が好ましく、３５～４５モル％が特に好ましい。単位（ｕ３）の割合が前記範囲の下限値以上であれば、形成される膜の耐久性がより優れる。単位（ｕ３）の割合が前記範囲の上限値以下であれば、形成される膜の離型性がより優れる。 The proportion of the unit (u3) is preferably 30 to 48 mol%, particularly preferably 35 to 45 mol%, based on all units of the copolymer (A1). When the ratio of the unit (u3) is not less than the lower limit of the above range, the durability of the formed film is more excellent. When the ratio of the unit (u3) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
　したがって、共重合体（Ａ１）としては、共重合体（Ａ１）の全単位中、単位（ｕ１）を５～４０モル％、単位（ｕ２）を３０～４８モル％、単位（ｕ３）を３０～４８モル％の割合で含むものが好ましく、単位（ｕ１）を１０～３０モル％、単位（ｕ２）を３５～４５モル％、単位（ｕ３）を３５～４５モル％の割合で含むものが特に好ましい。 Therefore, as the copolymer (A1), in all the units of the copolymer (A1), the unit (u1) is 5 to 40 mol%, the unit (u2) is 30 to 48 mol%, and the unit (u3) is 30%. Those containing at a rate of ˜48 mol%, preferably containing units (u1) at 10-30 mol%, units (u2) at 35-45 mol%, and units (u3) at a rate of 35-45 mol%. Particularly preferred.
　単位（ｕ２）と単位（ｕ３）とのモル比（単位（ｕ２）／単位（ｕ３））は、３０／７０～７０／３０であることが好ましく、４０／６０～６０／４０であることが特に好ましい。単位（ｕ２）／単位（ｕ３）が前記範囲内であれば、より優れた離型性とより優れた耐久性とを両立できる。 The molar ratio of unit (u2) to unit (u3) (unit (u2) / unit (u3)) is preferably 30/70 to 70/30, and preferably 40/60 to 60/40. Particularly preferred. When the unit (u2) / unit (u3) is within the above range, it is possible to achieve both better release properties and better durability.
　共重合体（Ａ１）におけるブロックイソシアナート基のブロック解離温度は、単量体（ｍ２）におけるブロックイソシアナート基のブロック解離温度とほぼ等しい。したがって、単量体（ｍ２）におけるブロックイソシアナート基の選択により、共重合体（Ａ１）におけるブロックイソシアナート基のブロック解離温度を調整できる。後述する共重合体（Ａ２）においても同様である。
　なお、単量体や共重合体におけるブロック解離温度は１点ではなく幅があることより、本発明では共重合体（Ａ１）および共重合体（Ａ２）におけるブロック解離温度は、３０分間の加熱でブロックイソシアナート基の５０％が脱ブロックする温度を共重合体の「ブロック解離温度」とする。
　以下、共重合体（Ａ１）および共重合体（Ａ２）におけるブロックイソシアナート基のブロック解離温度をＴＤ（℃）で表す。 The block dissociation temperature of the block isocyanate group in the copolymer (A1) is substantially equal to the block dissociation temperature of the block isocyanate group in the monomer (m2). Therefore, the block dissociation temperature of the block isocyanate group in the copolymer (A1) can be adjusted by selecting the block isocyanate group in the monomer (m2). The same applies to the copolymer (A2) described later.
In addition, since the block dissociation temperature in the monomer or copolymer is not limited to one point but varies, in the present invention, the block dissociation temperature in the copolymer (A1) and the copolymer (A2) is 30 minutes of heating. The temperature at which 50% of the block isocyanate groups are deblocked is defined as the “block dissociation temperature” of the copolymer.
Hereinafter, the block dissociation temperature of the block isocyanate group in the copolymer (A1) and the copolymer (A2) is represented by T D (° C.).
（共重合体（Ａ２））
　共重合体（Ａ２）は、単位（ｕ１）と単位（ｕ２）とを有し、単位（ｕ３）を有しない共重合体である。
　共重合体（Ａ２）は、必要に応じて、他の単位をさらに有していてもよい。 (Copolymer (A2))
A copolymer (A2) is a copolymer which has a unit (u1) and a unit (u2), and does not have a unit (u3).
The copolymer (A2) may further have other units as necessary.
　共重合体（Ａ２）において、単位（ｕ１）の割合は、共重合体（Ａ２）の全単位中、５～４０モル％が好ましく、５～３０モル％が特に好ましい。単位（ｕ１）の割合が前記範囲の下限値以上であれば、形成される膜の離型性がより優れる。単位（ｕ１）の割合が前記範囲の上限値以下であれば、形成される膜の耐久性がより優れる。 In the copolymer (A2), the ratio of the unit (u1) is preferably from 5 to 40 mol%, particularly preferably from 5 to 30 mol%, based on the total units of the copolymer (A2). If the ratio of the unit (u1) is not less than the lower limit of the above range, the mold release property of the formed film is more excellent. When the ratio of the unit (u1) is not more than the upper limit of the above range, the durability of the formed film is more excellent.
　単位（ｕ２）の割合は、共重合体（Ａ２）の全単位中、６０～９５モル％が好ましく、７０～９５モル％が特に好ましい。単位（ｕ２）の割合が前記範囲の下限値以上であれば、形成される膜の耐久性がより優れる。単位（ｕ２）の割合が前記範囲の上限値以下であれば、形成される膜の離型性がより優れる。 The proportion of the unit (u2) is preferably 60 to 95 mol%, particularly preferably 70 to 95 mol%, based on all units of the copolymer (A2). When the ratio of the unit (u2) is not less than the lower limit of the above range, the durability of the formed film is more excellent. If the ratio of the unit (u2) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
　したがって、共重合体（Ａ２）としては、共重合体（Ａ２）の全単位中、単位（ｕ１）を５～４０モル％、単位（ｕ２）を６０～９５モル％の割合で含むものが好ましく、単位（ｕ１）を５～３０モル％、単位（ｕ２）を７０～９５モル％の割合で含むものが特に好ましい。 Accordingly, the copolymer (A2) is preferably one containing 5 to 40 mol% of the unit (u1) and 60 to 95 mol% of the unit (u2) in all the units of the copolymer (A2). Particularly preferred are those containing 5 to 30 mol% of units (u1) and 70 to 95 mol% of units (u2).
（共重合体（Ａ３））
　共重合体（Ａ３）は、単位（ｕ１）と単位（ｕ３）とを有し、単位（ｕ２）を有しない共重合体である。
　共重合体（Ａ２）および共重合体（Ａ３）は共に単位（ｕ１）を有することから、混和性が良好である。共重合体（Ａ２）中の単位（ｕ１）と共重合体（Ａ３）中の単位（ｕ１）とは同じでも異なっていてもよい。
　共重合体（Ａ３）は、必要に応じて、他の単位をさらに有していてもよい。 (Copolymer (A3))
The copolymer (A3) has a unit (u1) and a unit (u3), and does not have a unit (u2).
Since both the copolymer (A2) and the copolymer (A3) have the unit (u1), the miscibility is good. The unit (u1) in the copolymer (A2) and the unit (u1) in the copolymer (A3) may be the same or different.
The copolymer (A3) may further have other units as necessary.
　共重合体（Ａ３）において、単位（ｕ１）の割合は、共重合体（Ａ３）の全単位中、５～４０モル％が好ましく、１０～４０モル％が特に好ましい。単位（ｕ１）の割合が前記範囲の下限値以上であれば、形成される膜の離型性がより優れる。単位（ｕ１）の割合が前記範囲の上限値以下であれば、形成される膜の耐久性がより優れる。 In the copolymer (A3), the proportion of the unit (u1) is preferably from 5 to 40 mol%, particularly preferably from 10 to 40 mol%, based on the total units of the copolymer (A3). If the ratio of the unit (u1) is not less than the lower limit of the above range, the mold release property of the formed film is more excellent. When the ratio of the unit (u1) is not more than the upper limit of the above range, the durability of the formed film is more excellent.
　単位（ｕ３）の割合は、共重合体（Ａ３）の全単位中、６０～９５モル％が好ましく、６０～９０モル％が特に好ましい。単位（ｕ３）の割合が前記範囲の下限値以上であれば、形成される膜の耐久性がより優れる。単位（ｕ３）の割合が前記範囲の上限値以下であれば、形成される膜の離型性がより優れる。 The proportion of the unit (u3) is preferably 60 to 95 mol%, particularly preferably 60 to 90 mol%, based on all units of the copolymer (A3). When the ratio of the unit (u3) is not less than the lower limit of the above range, the durability of the formed film is more excellent. When the ratio of the unit (u3) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
　したがって、共重合体（Ａ３）としては、共重合体（Ａ３）の全単位中、単位（ｕ１）を５～４０モル％、単位（ｕ３）を６０～９５モル％の割合で含むものが好ましく、単位（ｕ１）を１０～４０モル％、単位（ｕ３）を６０～９０モル％の割合で含むものが特に好ましい。 Therefore, the copolymer (A3) preferably contains 5 to 40 mol% of the unit (u1) and 60 to 95 mol% of the unit (u3) in all the units of the copolymer (A3). Particularly preferred are those containing 10 to 40 mol% of the unit (u1) and 60 to 90 mol% of the unit (u3).
（化合物（Ｂ））
　化合物（Ｂ）は、水酸基、アミノ基およびカルボキシ基からなる群から選ばれる少なくとも１種の官能基（以下、「官能基（Ｉ）」とも記す。）を２以上有する化合物である。
　化合物（Ｂ）が有する官能基（Ｉ）の数は、２～１０が好ましく、２～８がより好ましく、２または３が特に好ましい。官能基（Ｉ）の数が前記範囲内であれば、形成される膜の離型性がより優れる。
　官能基（Ｉ）としては、水酸基またはアミノ基が好ましく、水酸基が特に好ましい。 (Compound (B))
The compound (B) is a compound having at least one functional group selected from the group consisting of a hydroxyl group, an amino group and a carboxy group (hereinafter also referred to as “functional group (I)”).
The number of functional groups (I) possessed by the compound (B) is preferably 2 to 10, more preferably 2 to 8, and particularly preferably 2 or 3. If the number of functional groups (I) is within the above range, the releasability of the formed film is more excellent.
The functional group (I) is preferably a hydroxyl group or an amino group, particularly preferably a hydroxyl group.
　化合物（Ｂ）の沸点はＴＤ～４００℃である。化合物（Ｂ）の沸点が前記範囲内であれば、形成される膜の離型性がより優れる。化合物（Ｂ）の沸点がＴＤ未満であると、樹脂組成物を加熱して架橋構造を形成する際に化合物（Ｂ）が揮発してしまい、離型性が不充分になるおそれがある。
　化合物（Ｂ）の沸点の下限はＴＤ＋１０℃が好ましく、ＴＤ＋３０℃が特に好ましい。化合物（Ｂ）の沸点の上限は、３００℃が好ましく、２５０℃が特に好ましい。 The boiling point of the compound (B) is T D to 400 ° C. If the boiling point of a compound (B) is in the said range, the mold release property of the film | membrane formed will be more excellent. If the boiling point of the compound (B) is less than T D, compounds in forming a crosslinked structure by heating the resin composition (B) ends up volatilize, there is a possibility that the releasing property becomes insufficient.
The lower limit of the boiling point of the compound (B) is preferably T D + 10 ° C., particularly preferably T D + 30 ° C. The upper limit of the boiling point of the compound (B) is preferably 300 ° C, particularly preferably 250 ° C.
　化合物（Ｂ）は、芳香環を有する芳香族化合物であってもよく、芳香環を有しない非芳香族化合物であってもよい。
　芳香環としては、例えばベンゼン環、ナフタレン環、アントラセン環等が挙げられる。
　非芳香族化合物は、直鎖または分岐鎖状の脂肪族化合物であってもよく、脂環式基を有する脂環式化合物であってもよい。
　化合物（Ｂ）は、フッ素原子を有しないことが好ましい。 The compound (B) may be an aromatic compound having an aromatic ring or a non-aromatic compound having no aromatic ring.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.
The non-aromatic compound may be a linear or branched aliphatic compound or an alicyclic compound having an alicyclic group.
It is preferable that a compound (B) does not have a fluorine atom.
　化合物（Ｂ）の具体例としては、下記の化合物が挙げられる。
　フロログルシノール、ヒドロキノン、レゾルシノール、２，７－ジヒドロキシナフタレン、１，５－ジヒドロキシナフタレン、１，４－フェニレンジアミン等の芳香族化合物、
　トリメチロールプロパン、エチレングリコール、プロピレングリコール等の非芳香族化合物。 Specific examples of the compound (B) include the following compounds.
Aromatic compounds such as phloroglucinol, hydroquinone, resorcinol, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,4-phenylenediamine,
Non-aromatic compounds such as trimethylolpropane, ethylene glycol, and propylene glycol.
　化合物（Ｂ）は、離型性がより優れる点では、芳香環を有することが好ましい。
　化合物（Ｂ）としては、フロログルシノール、ヒドロキノン、レゾルシノール、２，７－ジヒドロキシナフタレン、１，５－ジヒドロキシナフタレン、１，４－フェニレンジアミン等の、芳香環と、該芳香環に結合した２以上の官能基（Ｉ）とを有する化合物が特に好ましい。
　化合物（Ｂ）は、１種を単独で用いてもよく、２種以上を併用してもよい。 The compound (B) preferably has an aromatic ring in terms of more excellent releasability.
Compound (B) includes phloroglucinol, hydroquinone, resorcinol, 2,7-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,4-phenylenediamine and the like, and two or more bonded to the aromatic ring A compound having the functional group (I) is particularly preferred.
A compound (B) may be used individually by 1 type, and may use 2 or more types together.
（他の成分）
　他の成分としては、例えば界面活性剤、基材（金型等）との密着性改良剤、ウレタン化触媒（スズ触媒等）、ブロックイソシアナート基のブロック解離触媒等が挙げられる。
　樹脂組成物（１）の場合には、共重合体（Ａ２）または共重合体（Ａ３）、樹脂組成物（２）の場合には共重合体（Ａ１）を他の成分として含んでいてもよいが、含まなくてもよい。
　なお、本発明における樹脂組成物は、溶剤を含まないものをいう。 (Other ingredients)
Examples of other components include a surfactant, an adhesion improver with a base material (such as a mold), a urethanization catalyst (such as a tin catalyst), and a block dissociation catalyst for a block isocyanate group.
In the case of the resin composition (1), the copolymer (A2) or the copolymer (A3), and in the case of the resin composition (2), the copolymer (A1) may be included as another component. Yes, but not necessarily.
In addition, the resin composition in this invention says what does not contain a solvent.
（各成分の含有量）
　樹脂組成物中、樹脂組成物（１）の場合は共重合体（Ａ１）と化合物（Ｂ）との合計の含有量、樹脂組成物（２）の場合は共重合体（Ａ２）と共重合体（Ａ３）と化合物（Ｂ）との合計の含有量は、樹脂組成物の総質量に対し、５～１００質量％が好ましく、１０～１００質量％がより好ましく、２０～１００質量％が特に好ましい。この合計の含有量が前記範囲の下限値以上であれば、形成される膜の離型性がより優れ、耐久性がより優れたものとなる。 (Content of each component)
In the resin composition, in the case of the resin composition (1), the total content of the copolymer (A1) and the compound (B), and in the case of the resin composition (2), the copolymer (A2) and the copolymer weight. The total content of the union (A3) and the compound (B) is preferably 5 to 100% by mass, more preferably 10 to 100% by mass, and particularly preferably 20 to 100% by mass with respect to the total mass of the resin composition. preferable. If this total content is equal to or greater than the lower limit of the above range, the formed film is more releasable and more durable.
　樹脂組成物中、化合物（Ｂ）の含有量は、樹脂組成物（１）の場合は共重合体（Ａ１）の１００質量部に対して、樹脂組成物（２）の場合は共重合体（Ａ２）および共重合体（Ａ３）の合計の１００質量部に対して、５～１００質量部が好ましく、１０～８０質量部がより好ましく、２０～６０質量部が特に好ましい。化合物（Ｂ）の含有量が前記範囲の下限値以上であれば、化合物（Ｂ）による効果が充分に発揮され、形成される膜の離型性がより優れる。化合物（Ｂ）の含有量が前記範囲の上限値以下であれば、フッ素原子を１つ以上有する有機基の含有量が充分に多くなり、形成される膜の離型性がより優れる。 In the resin composition, the content of the compound (B) is 100 parts by mass of the copolymer (A1) in the case of the resin composition (1), and the copolymer (2) in the case of the resin composition (2). The amount is preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight, and particularly preferably 20 to 60 parts by weight with respect to 100 parts by weight of the total of A2) and the copolymer (A3). If content of a compound (B) is more than the lower limit of the said range, the effect by a compound (B) will fully be exhibited, and the mold release property of the film | membrane formed will be more excellent. If the content of the compound (B) is not more than the upper limit of the above range, the content of the organic group having one or more fluorine atoms will be sufficiently increased, and the releasability of the formed film will be more excellent.
　樹脂組成物（１）は、共重合体（Ａ１）および化合物（Ｂ）以外の他の成分を含まないことが好ましい。
　樹脂組成物（２）は、共重合体（Ａ２）～（Ａ３）および化合物（Ｂ）以外の他の成分を含まないことが好ましい。 It is preferable that the resin composition (1) does not contain other components other than the copolymer (A1) and the compound (B).
The resin composition (2) preferably contains no other components than the copolymers (A2) to (A3) and the compound (B).
　樹脂組成物（２）中、共重合体（Ａ２）および共重合体（Ａ３）それぞれの含有量は、単位（ｕ２）と単位（ｕ３）とのモル比（単位（ｕ２）／単位（ｕ３））が３０／７０～７０／３０となる量であることが好ましく、４０／６０～６０／４０となる量であることがより好ましい。単位（ｕ２）／単位（ｕ３）が前記範囲内であれば、より優れた離型性とより優れた耐久性とを両立できる。 The content of each of the copolymer (A2) and the copolymer (A3) in the resin composition (2) is the molar ratio of the unit (u2) to the unit (u3) (unit (u2) / unit (u3)). ) Is preferably 30/70 to 70/30, more preferably 40/60 to 60/40. When the unit (u2) / unit (u3) is within the above range, it is possible to achieve both better release properties and better durability.
　共重合体（Ａ２）および共重合体（Ａ３）それぞれの全単位の合計中、単位（ｕ１）の割合は、５～４０モル％が好ましく、１０～３０モル％が特に好ましい。単位（ｕ１）の割合が前記範囲の下限値以上であれば、形成される膜の離型性がより優れる。単位（ｕ１）の割合が前記範囲の上限値以下であれば、形成される膜の耐久性がより優れる。 In the total of all the units of the copolymer (A2) and the copolymer (A3), the ratio of the unit (u1) is preferably 5 to 40 mol%, particularly preferably 10 to 30 mol%. If the ratio of the unit (u1) is not less than the lower limit of the above range, the mold release property of the formed film is more excellent. When the ratio of the unit (u1) is not more than the upper limit of the above range, the durability of the formed film is more excellent.
　共重合体（Ａ２）および共重合体（Ａ３）それぞれの全単位の合計中、単位（ｕ２）の割合は、３０～４８モル％が好ましく、３５～４５モル％が特に好ましい。単位（ｕ２）の割合が前記範囲の下限値以上であれば、形成される膜の耐久性がより優れる。単位（ｕ２）の割合が前記範囲の上限値以下であれば、形成される膜の離型性がより優れる。 In the total of all units of the copolymer (A2) and the copolymer (A3), the proportion of the unit (u2) is preferably 30 to 48 mol%, particularly preferably 35 to 45 mol%. When the ratio of the unit (u2) is not less than the lower limit of the above range, the durability of the formed film is more excellent. If the ratio of the unit (u2) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
　共重合体（Ａ２）および共重合体（Ａ３）それぞれの全単位の合計中、単位（ｕ３）の割合は、３０～４８モル％が好ましく、３５～４５モル％が特に好ましい。単位（ｕ３）の割合が前記範囲の下限値以上であれば、形成される膜の耐久性がより優れる。単位（ｕ３）の割合が前記範囲の上限値以下であれば、形成される膜の離型性がより優れる。 In the total of all units of the copolymer (A2) and the copolymer (A3), the proportion of the unit (u3) is preferably 30 to 48 mol%, particularly preferably 35 to 45 mol%. When the ratio of the unit (u3) is not less than the lower limit of the above range, the durability of the formed film is more excellent. When the ratio of the unit (u3) is not more than the upper limit of the above range, the mold release property of the formed film is more excellent.
（作用効果）
　樹脂組成物にあっては、共重合体（Ａ１）、または共重合体（Ａ２）および共重合体（Ａ３）と、化合物（Ｂ）とを含むため、離型性に優れかつ耐久性に優れた硬化膜（本発明における離型膜に同じ。）を形成できる。
　共重合体（Ａ１）、または共重合体（Ａ２）および共重合体（Ａ３）を含むことで、樹脂組成物中には単位（ｕ１）～（ｕ３）が全て存在する。
　単位（ｕ１）のフッ素原子を１つ以上有する有機基は、樹脂組成物から形成される硬化膜の表面エネルギーを低くして、離型性の向上に寄与する。
　単位（ｕ２）および単位（ｕ３）の存在は、樹脂組成物から形成される硬化膜の耐久性の向上に寄与する。樹脂組成物からなる未硬化膜を、単位（ｕ２）中のブロックイソシアナート基が脱ブロック化してイソシアナート基になる温度（すなわち、ＴＤ）以上に加熱すると、生じたイソシアナート基と単位（ｕ３）中の活性水素原子含有官能基とが反応し、架橋構造が形成される。また、脱ブロック化したイソシアナート基は化合物（Ｂ）の官能基とも反応して架橋構造が形成される。これら架橋構造の形成により、樹脂組成物は架橋硬化し、これにより膜の耐久性が高まる。
　さらに、樹脂組成物が化合物（Ｂ）を含むことで、化合物（Ｂ）を含まない場合に比べて、離型性が優れる。これは、化合物（Ｂ）が有する官能基（Ｉ）の極性が高いため、化合物（Ｂ）と単位（ｕ１）中の前記有機基との親和性が低く、金型表面に未硬化の膜が形成される際に、未硬化膜中に存在する化合物（Ｂ）によって前記有機基が膜の自由表面側表面へ偏在しやすくなり、次いでその状態で未硬化膜が硬化されることにより、硬化膜の自由表面側表面に前記有機基が偏在しやすくなるためと考えられる。
　化合物（Ｂ）による上記の効果は、樹脂組成物中に単位（ｕ１）～（ｕ３）が全て存在することで充分に発揮される。例えば樹脂組成物中に単位（ｕ２）が存在しない場合には、離型性の向上効果は見られないおそれがある。 (Function and effect)
In the resin composition, since it contains the copolymer (A1), the copolymer (A2) and the copolymer (A3), and the compound (B), it has excellent releasability and durability. A cured film (same as the release film in the present invention) can be formed.
By including the copolymer (A1), or the copolymer (A2) and the copolymer (A3), all the units (u1) to (u3) are present in the resin composition.
The organic group having one or more fluorine atoms in the unit (u1) lowers the surface energy of the cured film formed from the resin composition and contributes to the improvement of the release property.
The presence of the unit (u2) and the unit (u3) contributes to improvement in durability of the cured film formed from the resin composition. When the uncured film made of the resin composition is heated to a temperature at which the block isocyanate group in the unit (u2) is deblocked to become an isocyanate group (ie, T D ) or higher, the resulting isocyanate group and unit ( The active hydrogen atom-containing functional group in u3) reacts to form a crosslinked structure. The deblocked isocyanate group also reacts with the functional group of the compound (B) to form a crosslinked structure. By forming these cross-linked structures, the resin composition is cross-linked and cured, thereby increasing the durability of the film.
Furthermore, when a resin composition contains a compound (B), compared with the case where a compound (B) is not included, mold release property is excellent. This is because the functional group (I) of the compound (B) has a high polarity, so the affinity between the compound (B) and the organic group in the unit (u1) is low, and an uncured film is formed on the mold surface. When formed, the organic group tends to be unevenly distributed on the free surface side surface of the film by the compound (B) present in the uncured film, and then the uncured film is cured in that state, whereby the cured film This is thought to be because the organic group tends to be unevenly distributed on the surface of the free surface.
The above-mentioned effect by the compound (B) is sufficiently exhibited when all the units (u1) to (u3) are present in the resin composition. For example, when the unit (u2) is not present in the resin composition, there is a possibility that the effect of improving the releasability is not observed.
〔コーティング液〕
　本発明のコーティング液（以下、「本コーティング液」とも記す。）は、前記樹脂組成物と、溶剤とを含む液状の組成物である。 [Coating solution]
The coating liquid of the present invention (hereinafter also referred to as “the present coating liquid”) is a liquid composition containing the resin composition and a solvent.
（溶剤）
　溶剤としては、例えば、含フッ素溶剤、炭化水素系溶剤等が挙げられる。溶剤は１種を単独で用いてもよく、２種以上を併用してもよい。これら溶剤の沸点は、溶媒除去の際に化合物（Ｂ）が除去されないように、化合物（Ｂ）の沸点未満であることが好ましい。その沸点は化合物（Ｂ）の沸点よりも２０℃以上低いことが好ましい。また、その沸点の下限値は塗布後の表面の平坦性が優れる点から、８０℃が好ましく、１００℃が特に好ましい。溶剤の沸点の上限値は、加熱による除去の容易性の点から、３００℃が好ましい。
　活性水素原子含有官能基を有しない化合物からなる溶剤の場合は、イソシアナート基に対して不活性であるので、その沸点はＴＤ以上の温度であってもよい。ただし、ＴＤ以上の温度であっても、イソシアナート基生成後溶剤の存在する状態が長く続くと架橋反応が進み、平坦性の良好な膜が生成し難いことより、乾燥温度（溶剤を加熱除去するための温度）から硬化温度へは速やかに移行させることが好ましい。活性水素原子含有官能基を有しない化合物からなる溶剤の沸点は、ＴＤ＋５０℃以下が好ましく、ＴＤ＋３０℃以下がより好ましい。
　アルコール類等の活性水素原子含有官能基を有する化合物からなる溶剤の場合は、その沸点が高いと溶剤除去の際に共重合体のブロックイソシアナート基が脱ブロックして反応するおそれがあるので、活性水素原子含有化合物からなる溶剤の沸点はＴＤよりも充分低いことが好ましい。その沸点は、ＴＤ－３０℃以下が好ましく、ＴＤ－５０℃以下がより好ましい。 (solvent)
Examples of the solvent include a fluorine-containing solvent and a hydrocarbon solvent. A solvent may be used individually by 1 type and may use 2 or more types together. The boiling point of these solvents is preferably less than the boiling point of the compound (B) so that the compound (B) is not removed during the solvent removal. The boiling point is preferably 20 ° C. or more lower than the boiling point of the compound (B). Further, the lower limit of the boiling point is preferably 80 ° C., particularly preferably 100 ° C., from the viewpoint of excellent surface flatness after coating. The upper limit of the boiling point of the solvent is preferably 300 ° C. from the viewpoint of easy removal by heating.
For solvent comprising a compound having no active hydrogen atom-containing functional group, since it is inert to isocyanate groups, the boiling point may be a temperature above T D. However, even T D temperature above state continues for a long time and the cross-linking reaction in the presence of a solvent after the isocyanate group generation advances, than it is difficult to produce a good film flatness, the drying temperature (solvent heating It is preferable to quickly shift from the temperature for removal to the curing temperature. The boiling point of the solvent composed of the compound having no active hydrogen atom-containing functional group is preferably T D + 50 ° C. or less, and more preferably T D + 30 ° C. or less.
In the case of a solvent consisting of a compound having an active hydrogen atom-containing functional group such as alcohols, if the boiling point is high, the block isocyanate group of the copolymer may deblock and react when the solvent is removed. boiling point of the solvent composed of the active hydrogen atom-containing compound is preferably sufficiently lower than T D. Its boiling point is preferably T D −30 ° C. or lower, and more preferably T D −50 ° C. or lower.
　含フッ素溶剤の具体例としては、下記の化合物が挙げられる。
　旭硝子社製のアサヒクリン（商標）として、１Ｈ－トリデカフルオロヘキサン（ＡＣ２０００、沸点：７１℃）；１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロオクタン（ＡＣ６０００、沸点：１１５℃）；１，１，２，２－テトラフルオロ－１－（２，２，２－トリフルオロエトキシ）エタン（ＡＥ３０００、沸点：５６℃）；ジクロロペンタフルオロプロパン（ＡＫ－２２５、沸点：５４℃）等が挙げられる。その他として、サイトップ（商標）ＣＴ－ｓｏｌｖ１００Ｅ（旭硝子社製、沸点：９８℃）；１－メトキシノナフルオロブタン（スリーエムジャパン社製、Ｎｏｖｅｃ（商標）７１００、沸点：６１℃）；１－エトキシノナフルオロブタン（スリーエムジャパン社製、Ｎｏｖｅｃ（商標）７２００、沸点：７６℃）；１，１，１，２，３，３－ヘキサフルオロ－４－（１，１，２，３，３，３－ヘキサフルオロプロポキシ）ペンタン（スリーエムジャパン社製、Ｎｏｖｅｃ（商標）７６００、沸点：１３１℃）；２Ｈ，３Ｈ－ペルフルオロペンタン（三井・デュポンフロロケミカル社製、Ｖｅｒｔｒｅｌ（商標）ＸＦ、沸点：５５℃）；３，３，４，４，５，５，６，６，７，７，８，８，８－トリデカフルオロ－１－オクタノール（沸点：８０℃）；４，４，５，５，６，６，７，７，８，８，９，９，９－トリデカフルオロ－１－ノナノール；ヘキサフルオロベンゼン（沸点：８１℃）；ヘキサフルオロ－２－プロパノール（沸点：５９℃）；２，２，３，３，４，４，５，５－オクタフルオロ－１－ペンタノール（沸点：１４０℃）；１Ｈ，１Ｈ，７Ｈ－ドデカフルオロ－１－ヘプタノール（沸点：１７０℃）；１Ｈ，１Ｈ，２Ｈ，２Ｈ－トリデカフルオロ－１－オクタノール（沸点：８０℃）等。 Specific examples of the fluorine-containing solvent include the following compounds.
Asahiclin (trademark) manufactured by Asahi Glass Co., Ltd., 1H-tridecafluorohexane (AC2000, boiling point: 71 ° C.); 1,1,1,2,2,3,3,4,4,5,5,6 6-tridecafluorooctane (AC6000, boiling point: 115 ° C.); 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (AE3000, boiling point: 56 ° C.); dichloro And pentafluoropropane (AK-225, boiling point: 54 ° C.). In addition, Cytop (trademark) CT-solv 100E (Asahi Glass Co., Ltd., boiling point: 98 ° C.); 1-methoxynonafluorobutane (manufactured by 3M Japan, Novec (trademark) 7100, boiling point: 61 ° C.); 1-ethoxynona Fluorobutane (manufactured by 3M Japan, Novec ™ 7200, boiling point: 76 ° C.); 1,1,1,2,3,3-hexafluoro-4- (1,1,2,3,3,3- Hexafluoropropoxy) pentane (manufactured by 3M Japan, Novec (trademark) 7600, boiling point: 131 ° C); 2H, 3H-perfluoropentane (manufactured by Mitsui DuPont Fluorochemicals, Vertrel (trademark) XF, boiling point: 55 ° C); 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-octanol (boiling point: 0,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-nonanol; hexafluorobenzene (boiling point: 81 ° C); hexafluoro -2-propanol (boiling point: 59 ° C.); 2,2,3,3,4,4,5,5-octafluoro-1-pentanol (boiling point: 140 ° C.); 1H, 1H, 7H-dodecafluoro- 1-heptanol (boiling point: 170 ° C.); 1H, 1H, 2H, 2H-tridecafluoro-1-octanol (boiling point: 80 ° C.), etc.
　炭化水素系溶剤の具体例としては、下記の化合物が挙げられる。
　シクロペンタノン、シクロヘキサノン、メチルアミルケトン、２－ブタノン等のケトン類；乳酸エチル、安息香酸メチル、安息香酸エチル、安息香酸ベンジル、メチルセルソルブアセテート、エチルセルソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のエステル類；テトラヒドロフラン、ジオキサン、ジメトキシエタン、ジエトキシエタン、アニソール、ジグライム、トリグライム等のエーテル類、ジメチルカーボネート、ジエチルカーボネート、エチルメチルカーボネート、エチレンカーボネート、プロピレンカーボネート等のカーボネート類、１－ブタノール、１－ペンタノール、１－ヘキサノール、１－ヘプタノール、２－プロパノール、２－ブタノール、２－ペンタノール、３－ペンタノール、２-ヘキサノール、３－ヘキサノール、２－ヘプタノール、３－ヘプタノール、４－ヘプタノール、２－オクタノール、３－オクタノール、４－オクタノール等のアルコール類等。 Specific examples of the hydrocarbon solvent include the following compounds.
Ketones such as cyclopentanone, cyclohexanone, methyl amyl ketone, 2-butanone; ethyl lactate, methyl benzoate, ethyl benzoate, benzyl benzoate, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene Esters such as glycol monoethyl ether acetate; ethers such as tetrahydrofuran, dioxane, dimethoxyethane, diethoxyethane, anisole, diglyme, triglyme, carbonates such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 2-propanol, 2-butano Le, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-octanol, 3-octanol, 4-octanol alcohols such like.
（本コーティング液の組成）
　本コーティング液において、前記樹脂組成物の割合は、本コーティング液の総質量に対し、０．１～３０質量％が好ましく、１～３０質量％が特に好ましい。
　溶剤の割合は、本コーティング液の総質量に対し、７０～９９．９質量％が好ましく、７０～９９質量％が特に好ましい。 (Composition of this coating solution)
In the present coating liquid, the ratio of the resin composition is preferably 0.1 to 30% by mass, particularly preferably 1 to 30% by mass, based on the total mass of the present coating liquid.
The ratio of the solvent is preferably from 70 to 99.9% by mass, particularly preferably from 70 to 99% by mass, based on the total mass of the present coating liquid.
（作用効果）
　本コーティング液にあっては、前記樹脂組成物を含むため、離型性が優れ、かつ耐久性に優れた膜を形成できる。 (Function and effect)
Since the present coating liquid contains the resin composition, a film having excellent releasability and excellent durability can be formed.
〔離型膜付き金型〕
　本発明の離型膜付き金型は、金型の表面に、前記樹脂組成物から形成された離型膜を備える。
　金型の材質は、典型的には金属であり、例えば鉄、ニッケル、アルミ、ステンレス鋼、ニッケル合金、ジュラルミン等が挙げられる。
　離型膜の厚さは、特に制限されないが、０．０５～５μｍが好ましく、０．１～２μｍが特に好ましい。
　離型膜付き金型は、例えば以下に示す離型膜付き金型の製造方法により製造できる。 [Mold with release film]
The mold with a release film of the present invention includes a release film formed from the resin composition on the surface of the mold.
The material of the mold is typically a metal, and examples thereof include iron, nickel, aluminum, stainless steel, nickel alloy, and duralumin.
The thickness of the release film is not particularly limited, but is preferably 0.05 to 5 μm, particularly preferably 0.1 to 2 μm.
The mold with a release film can be produced by, for example, the following method for producing a mold with a release film.
（離型膜付き金型の製造方法）
　本発明の離型膜付き金型の製造方法としては、金型の表面に、本コーティング液を塗布し、溶剤の沸点以上（ただし、化合物（Ｂ）の沸点未満）かつＴＤ以上の温度で加熱して離型膜を形成し、離型膜付き金型を得る方法が好ましい。加熱温度は、溶剤の沸点＋１０℃以上（ただし、化合物（Ｂ）の沸点未満）かつＴＤ＋３０℃以上が好ましく、溶剤の沸点＋２０℃以上（ただし、化合物（Ｂ）の沸点未満）かつＴＤ＋５０℃以上がより好ましい。加熱温度の上限値は３００℃が好ましい。
　本コーティング液を塗布し、上記加熱温度以上の温度で加熱すると、溶剤が除去されて前記樹脂組成物からなる膜が形成され、単位（ｕ２）中のブロックイソシアナート基からイソシアナート基が生成し、このイソシアナート基と単位（ｕ３）や化合物（Ｂ）中の活性水素原子含有官能基とが反応して架橋構造が形成される。これにより、前記樹脂組成物の硬化物からなる離型膜が形成される。
　本コーティング液の塗布後、加熱の前に、塗布した本コーティング液を１５０℃未満の温度で乾燥（溶剤を除去）し、前記樹脂組成物からなる乾燥膜を形成してもよい。 (Manufacturing method of mold with release film)
As a method for producing the release film-coated mold of the present invention, the surface of the mold, this coating solution was applied, the solvent of higher boiling point (but below the boiling point of the compound (B)) and at T D a temperature above A method of forming a release film by heating to obtain a mold with a release film is preferred. The heating temperature is preferably the boiling point of the solvent + 10 ° C. or more (however, less than the boiling point of the compound (B)) and T D + 30 ° C. or more, the boiling point of the solvent + 20 ° C. or more (however, less than the boiling point of the compound (B)) and T D + 50 ° C. or more is more preferable. The upper limit of the heating temperature is preferably 300 ° C.
When this coating solution is applied and heated at a temperature equal to or higher than the above heating temperature, the solvent is removed to form a film made of the resin composition, and an isocyanate group is generated from the block isocyanate group in the unit (u2). The isocyanate group reacts with the active hydrogen atom-containing functional group in the unit (u3) or compound (B) to form a crosslinked structure. Thereby, the release film which consists of hardened | cured material of the said resin composition is formed.
After the application of the present coating liquid and before heating, the applied main coating liquid may be dried (removed from the solvent) at a temperature of less than 150 ° C. to form a dry film made of the resin composition.
　本コーティング液の塗布方法は特に制限されず、噴霧、浸漬、刷毛塗り、スピンコート等の公知の湿式塗布法を用いることができる。
　離型膜を形成する際の加熱温度は１５０℃以上が好ましい。加熱温度は４００℃以下が好ましい。加熱温度は金型の表面温度とする。加熱時間は、例えば５～６０分間とすることができる。 The coating method of this coating liquid is not particularly limited, and a known wet coating method such as spraying, dipping, brush coating, spin coating or the like can be used.
The heating temperature for forming the release film is preferably 150 ° C. or higher. The heating temperature is preferably 400 ° C. or lower. The heating temperature is the mold surface temperature. The heating time can be, for example, 5 to 60 minutes.
（用途）
　前記離型膜付き金型は、各種成形材料の成形品の製造に用いることができる。
　離型膜付き金型で成形され、成形品とされる成形材料としては、特に限定されず、例えば金属、樹脂、ゴム等の各種の公知の成形材料であってよい。
　本発明に係る金型が用いられる加工方法はプレス加工あるいは射出成型が好ましい。加工圧力は１～５０ＭＰａが好ましい。１ＭＰａ以上であれば加工性に優れ、５０ＭＰａ以下であれば金型の耐久性に優れる。また加工温度は１５０～２５０℃が好ましい。１５０℃以上であれば成形性に優れ、２５０℃以下であれば離型膜の熱分解による劣化を防げる。加工対象は特に制限されないが、ポリエチレン、ポリプロピレン、ポリスチレン、ポリエチレンテレフタレート、ポリ塩化ビニル、ポリカーボネート、ポリアミド、ポリエステル、フェノール樹脂、アクリル樹脂、エポキシ樹脂、ＡＢＳ樹脂等の樹脂素材、天然ゴム、スチレンブタジエンゴム，イソプレンゴム、ブタジエンゴム、アクリロニトリルブタジエンゴム、ウレタンゴム、アクリルゴム、シリコーンゴム、フッ素ゴム等のゴム素材、鉄、ニッケル、アルミ、チタン、ステンレス鋼、ニッケル合金、ジュラルミン等の金属等が例示できる。 (Use)
The mold with a release film can be used for manufacturing molded articles of various molding materials.
The molding material that is molded by the mold with a release film to form a molded product is not particularly limited, and may be various known molding materials such as metal, resin, and rubber.
The processing method using the mold according to the present invention is preferably press processing or injection molding. The processing pressure is preferably 1 to 50 MPa. If it is 1 MPa or more, it will be excellent in workability, and if it is 50 MPa or less, it will be excellent in the durability of a metal mold | die. The processing temperature is preferably 150 to 250 ° C. If it is 150 degreeC or more, it is excellent in a moldability, and if it is 250 degrees C or less, deterioration by the thermal decomposition of a release film can be prevented. The processing object is not particularly limited, but resin materials such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, polycarbonate, polyamide, polyester, phenol resin, acrylic resin, epoxy resin, ABS resin, natural rubber, styrene butadiene rubber, Examples include rubber materials such as isoprene rubber, butadiene rubber, acrylonitrile butadiene rubber, urethane rubber, acrylic rubber, silicone rubber, and fluorine rubber, and metals such as iron, nickel, aluminum, titanium, stainless steel, nickel alloy, and duralumin.
（作用効果）
　前記離型膜は、離型性に優れる。また、耐久性に優れており、摩擦等による削れや剥がれが生じにくい。
　そのため、前記離型膜付き金型を用いることで、成形した成形品を容易に離型できる。
　また、従来金型に用いられている離型剤では、成形を繰り返したときに、成形材料との接触等により離型膜の削れや剥がれが生じやすく、頻繁に離型膜を形成しなおす必要があった。前記離型膜付き金型にあっては、離型膜の耐久性が優れるため、従来に比べ、離型膜を形成しなおす頻度を低減できる。
　また、前記離型膜付き金型にあっては、離型膜の離型性および耐久性が優れることから、離型膜が成形品の表面に移行することを抑制できる。この移行は、得られる成形品の表面における水の接触角で測定できる。例えば加工前の金属の表面での水の接触角よりも、加工後の金属（成形品）の表面での水の接触角が大きければ、離型膜の移行が生じている。 (Function and effect)
The release film is excellent in releasability. Moreover, it is excellent in durability and is less likely to be scraped or peeled off due to friction or the like.
Therefore, by using the mold with a release film, the molded product can be easily released.
In addition, with mold release agents used in conventional molds, when the molding is repeated, the release film tends to be scraped or peeled off due to contact with the molding material, etc., and it is necessary to re-form the release film frequently. was there. In the mold with a release film, since the durability of the release film is excellent, the frequency of re-forming the release film can be reduced as compared with the related art.
Moreover, in the said mold with a release film, since the release property and durability of a release film are excellent, it can suppress that a release film transfers to the surface of a molded article. This transition can be measured by the contact angle of water on the surface of the resulting molded product. For example, if the contact angle of water on the surface of the metal (molded product) after processing is larger than the contact angle of water on the surface of the metal before processing, the release film is transferred.
　以下、実施例を示して本発明を詳細に説明する。ただし、本発明は以下の記載によっては限定されない。
　後述する例１～２１のうち例１～１４は実施例であり、例１５～２１は比較例である。
　各例で使用した測定方法を以下に示す。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description.
Of examples 1 to 21 described later, examples 1 to 14 are examples, and examples 15 to 21 are comparative examples.
The measurement method used in each example is shown below.
〔測定方法〕
（ＮＭＲ測定）
　１Ｈ－ＮＭＲは、日本電子社製ＪＮＭ－ＡＬ３００を用いて測定した。 〔Measuring method〕
(NMR measurement)
1 H-NMR was measured using JNM-AL300 manufactured by JEOL.
（共重合体の組成比）
　上述のＮＭＲ測定を行い、３．６ｐｐｍ、３．８ｐｐｍ、４．３ｐｐｍの積分比から算出した。 (Composition ratio of copolymer)
The above-mentioned NMR measurement was performed and calculated from the integration ratio of 3.6 ppm, 3.8 ppm, and 4.3 ppm.
（分子量測定）
　質量平均分子量（Ｍｗ）は、東ソー社製、ＨＬＣ－８２２０を用いて、分子量既知の標準ポリメチルメタクリレート試料を用いて作成した検量線を用い、ゲルパーミエーションクロマトグラフィで測定した（ポリメチルメタクリレート換算）。 (Molecular weight measurement)
The mass average molecular weight (Mw) was measured by gel permeation chromatography using a calibration curve prepared using a standard polymethyl methacrylate sample with a known molecular weight using HLC-8220 manufactured by Tosoh Corporation (in terms of polymethyl methacrylate). .
〔原料等〕
　以下の各例で用いた略号はそれぞれ以下の化合物を示す。
　Ｃ６ＦＭＡ：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ－Ｃ２Ｈ４－Ｃ６Ｆ１３（Ｃ６ＦＭＡは、特開２００４－３５９６１６号公報の例１に記載の方法で製造した。）。
　単量体（ｍ１－１）：ＣＨ２＝Ｃ（ＣＨ３）ＣＯＯ－ＣＨ２－ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＯＣＦ３（単量体（ｍ１－１）は、後述する製造例１で製造した。）。
　ＭＯＩ－ＢＭ：下式（ｉ）で表される化合物（メタクリル酸２－（Ｏ－［１’－メチルプロピリデンアミノ］カルボキシアミノ）エチル。ＴＤは１５０℃。商品名「カレンズＭＯＩ－ＢＭ」（昭和電工社製））。 [Raw materials]
The abbreviations used in the following examples represent the following compounds, respectively.
C6FMA: CH 2 ═C (CH 3 ) COO—C 2 H 4 —C 6 F 13 (C6FMA was produced by the method described in Example 1 of JP-A No. 2004-359616).
Monomer (m1-1): CH 2 ═C (CH 3 ) COO—CH 2 —CF 2 OCF 2 CF 2 OCF 2 CF 2 OCF 3 (Monomer (m1-1) is Production Example 1 described below. Manufactured by.)
MOI-BM:. A compound represented by the following formula (i) (2-methacrylate (O-[1'-methyl propylidene amino] carboxyamino) ethyl .T D is 0.99 ° C. trade name "Karenz MOI-BM" (Made by Showa Denko).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　ＨＥＭＡ：２－ヒドロキシエチルメタクリレート（純正化学社製）。
　ＭＥＫ：２－ブタノン（関東化学社製）。
　化合物（Ｂ－１）：フロログルシノール（東京化成社製、沸点２２０℃、分子量１２６）。
　化合物（Ｂ－２）：ヒドロキノン（東京化成社製、沸点２８７℃、分子量１１０）。
　化合物（Ｂ－３）：レゾルシノール（東京化成社製、沸点２７７℃、分子量１１０）。
　化合物（Ｂ－４）：２，７－ジヒドロキシナフタレン（東京化成社製、沸点３７５℃、分子量１６０）。
　化合物（Ｂ－５）：１，５－ジヒドロキシナフタレン（東京化成社製、沸点３７５℃、分子量１６０）。
　化合物（Ｂ－６）：１，４－フェニレンジアミン（東京化成社製、沸点２６７℃、分子量１０８）。
　化合物（Ｂ－７）：トリメチロールプロパン（東京化成社製、沸点１６０℃、分子量１３４）。
　化合物（Ｂ－８）：エチレングリコール（東京化成社製、沸点１９７℃、分子量６２）。
　化合物（Ｘ－１）：イソプロパノール（関東化学社製、沸点８３℃、分子量７４）。 HEMA: 2-hydroxyethyl methacrylate (manufactured by Junsei Co., Ltd.).
MEK: 2-butanone (manufactured by Kanto Chemical Co., Inc.).
Compound (B-1): Phloroglucinol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 220 ° C., molecular weight 126).
Compound (B-2): Hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 287 ° C., molecular weight 110).
Compound (B-3): Resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 277 ° C., molecular weight 110).
Compound (B-4): 2,7-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 375 ° C., molecular weight 160).
Compound (B-5): 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 375 ° C., molecular weight 160).
Compound (B-6): 1,4-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 267 ° C., molecular weight 108).
Compound (B-7): Trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 160 ° C., molecular weight 134).
Compound (B-8): Ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 197 ° C., molecular weight 62).
Compound (X-1): Isopropanol (manufactured by Kanto Chemical Co., Inc., boiling point 83 ° C., molecular weight 74).
〔製造例１：単量体（ｍ１－１）の合成〕
　下式（ｉｉ）で表される化合物（１Ｈ，１Ｈ－パーフルオロ－３，６，９－トリオキサデカン－１－オール）の３０．０ｇ、およびトリエチルアミンの１２．０ｇをテトラヒドロフランの５０ｍＬに溶解した。そこに、氷冷下、メタクリル酸クロリドの１２．０ｇを滴下し、２時間室温で攪拌した後、酢酸エチルの１５０ｍＬを加え、１規定の塩酸の１５０ｍＬ、飽和食塩水の１５０ｍＬの順で抽出した。その後、酸酸エチル層を硫酸マグネシウムで乾燥し、酢酸エチルを留去した。得られた液体を減圧蒸留により精製して目的の化合物（単量体（ｍ１－１））を得た。得られた化合物の１Ｈ－ＮＭＲ測定結果を以下に示す。
　１Ｈ－ＮＭＲ（３００．４ＭＨｚ、溶媒：ｄ－アセトン、基準：テトラメチルシラン（以下「ＴＭＳ」とも記す））δ（ｐｐｍ）：２．０（ｓ、３Ｈ）、４．８（ｔ、２Ｈ）、６．０（ｓ、１Ｈ）、６．２（ｓ、１Ｈ）。 [Production Example 1: Synthesis of monomer (m1-1)]
30.0 g of the compound represented by the following formula (ii) (1H, 1H-perfluoro-3,6,9-trioxadecan-1-ol) and 12.0 g of triethylamine were dissolved in 50 mL of tetrahydrofuran. . Thereto, 12.0 g of methacrylic acid chloride was added dropwise under ice-cooling, and the mixture was stirred for 2 hours at room temperature. Then, 150 mL of ethyl acetate was added, and extracted with 150 mL of 1N hydrochloric acid and 150 mL of saturated saline in this order. . Then, the ethyl acid acid layer was dried with magnesium sulfate, and ethyl acetate was distilled off. The obtained liquid was purified by distillation under reduced pressure to obtain the target compound (monomer (m1-1)). The results of 1 H-NMR measurement of the obtained compound are shown below.
1 H-NMR (300.4 MHz, solvent: d-acetone, standard: tetramethylsilane (hereinafter also referred to as “TMS”)) δ (ppm): 2.0 (s, 3H), 4.8 (t, 2H ), 6.0 (s, 1H), 6.2 (s, 1H).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
〔製造例２〕
　Ｃ６ＦＭＡの１．２ｇ、ＨＥＭＡの０．７ｇ、ＭＯＩ－ＢＭの１．３ｇ、および開始剤Ｖ６５（和光純薬社製）の０．０５ｇをＭＥＫの２９ｇに溶解し、雰囲気を窒素置換した後、５０℃で２４時間振とうした。得られた反応液をヘキサンの５００ｍＬに入れ、析出した固体を公称孔径３μｍのポリテトラフルオロエチレン（ＰＴＦＥ）製フィルタで濾過し、白色固体状の質量平均分子量（Ｍｗ）２３，０００の共重合体（Ａ１－１）を得た。
　共重合体（Ａ１－１）におけるＴＤは約１５０℃であった。
　反応に用いた原料等の量（ｇ）、得られた共重合体の組成比と質量平均分子量（Ｍｗ）を表１に示す。 [Production Example 2]
After dissolving 1.2 g of C6FMA, 0.7 g of HEMA, 1.3 g of MOI-BM, and 0.05 g of initiator V65 (manufactured by Wako Pure Chemical Industries, Ltd.) in 29 g of MEK, the atmosphere was replaced with nitrogen. Shake for 24 hours at 50 ° C. The obtained reaction liquid was put into 500 mL of hexane, and the precipitated solid was filtered through a polytetrafluoroethylene (PTFE) filter having a nominal pore size of 3 μm, and a white solid-state copolymer having a mass average molecular weight (Mw) of 23,000. (A1-1) was obtained.
T D in the copolymer (A1-1) was approximately 0.99 ° C..
Table 1 shows the amount (g) of the raw material used for the reaction, the composition ratio of the obtained copolymer, and the mass average molecular weight (Mw).
〔製造例３～５〕
　反応に用いた原料等の量（ｇ）を表１に示すようにした以外は製造例２と同様に重合を行って共重合体（Ａ１－２）、（Ａ２－１）、（Ａ３－１）を得た。各共重合体におけるＴＤはいずれも約１５０℃であった。得られた共重合体の組成比と質量平均分子量（Ｍｗ）を表１に示す。 [Production Examples 3 to 5]
Polymerization was carried out in the same manner as in Production Example 2 except that the amount (g) of the raw material used in the reaction was as shown in Table 1, and the copolymers (A1-2), (A2-1), (A3-1) ) Both T D is in each copolymer was about 0.99 ° C.. Table 1 shows the composition ratio and mass average molecular weight (Mw) of the obtained copolymer.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
〔例１〕
　共重合体（Ａ１－１）の１．０ｇ、フロログルシノールの０．３ｇ、溶剤のシクロヘキサノンの４．０ｇをガラスバイアル（２０ｍＬ）に入れ、充分に撹拌し均一の溶液とした。得られた溶液を公称孔径０．２０μｍのＰＴＦＥ製フィルタで濾過して、コーティング液を調製した。 [Example 1]
1.0 g of the copolymer (A1-1), 0.3 g of phloroglucinol, and 4.0 g of cyclohexanone as a solvent were placed in a glass vial (20 mL) and sufficiently stirred to obtain a homogeneous solution. The obtained solution was filtered through a PTFE filter having a nominal pore size of 0.20 μm to prepare a coating solution.
〔例２〕
　共重合体（Ａ１－１）の１．０ｇ、フロログルシノールの０．５ｇ、溶剤のシクロヘキサノンの４．０ｇをガラスバイアル（２０ｍＬ）に入れ、充分に撹拌し均一の溶液とした。得られた溶液を公称孔径０．２０μｍのＰＴＦＥ製フィルタで濾過して、コーティング液を調製した。 [Example 2]
1.0 g of copolymer (A1-1), 0.5 g of phloroglucinol, and 4.0 g of cyclohexanone as a solvent were placed in a glass vial (20 mL) and stirred well to obtain a homogeneous solution. The obtained solution was filtered through a PTFE filter having a nominal pore size of 0.20 μm to prepare a coating solution.
〔例３～１２、１５～２１〕
　表２～４に示す共重合体、化合物を用いた以外は、例１と同様の方法でコーティング液を調製した。 [Examples 3 to 12, 15 to 21]
A coating solution was prepared in the same manner as in Example 1 except that the copolymers and compounds shown in Tables 2 to 4 were used.
〔例１３〕
　共重合体（Ａ２－１）の０．５ｇ、共重合体（Ａ３－１）の０．５ｇ、フロログルシノールの０．３ｇ、溶剤のシクロヘキサノンの４．０ｇをガラスバイアル（２０ｍＬ）に入れ、充分に撹拌し均一の溶液とした。得られた溶液を公称孔径０．２０μｍのＰＴＦＥ製フィルタで濾過して、コーティング液を調製した。 [Example 13]
0.5 g of copolymer (A2-1), 0.5 g of copolymer (A3-1), 0.3 g of phloroglucinol, and 4.0 g of cyclohexanone as a solvent were placed in a glass vial (20 mL). The solution was sufficiently stirred to obtain a uniform solution. The obtained solution was filtered through a PTFE filter having a nominal pore size of 0.20 μm to prepare a coating solution.
〔例１４〕
　表３に示す化合物を用いた以外は、例１３と同様の方法でコーティング液を調製した。 [Example 14]
A coating solution was prepared in the same manner as in Example 13 except that the compounds shown in Table 3 were used.
〔評価〕
　例１～２１で得たコーティング液について、以下の評価を行った。結果を表２～４に示す。 [Evaluation]
The coating liquids obtained in Examples 1 to 21 were evaluated as follows. The results are shown in Tables 2-4.
（離型性の評価）
　洗浄した５ｃｍ角のステンレス鋼（ＳＵＳ）板上に、スピンコート法によりコーティング液を塗布し、ホットプレートを用いて２００℃で３０分間加熱することにより厚さ１μｍの離型膜を有する金型モデルを作製した。
　この金型モデルの離型膜表面に、Ｓｃоｔｃｈ透明粘着テープ(ＣＣ１８２０-Ｂｘ-Ｊ)
　幅１９ｍｍを貼りつけ、９０°剥離試験機（日新科学社製）を用いて剥離速度：１５ｍｍ／分で剥離強度（Ｎ）を測定した。剥離強度が１．２Ｎ以下であれば、離型性に優れる。 (Evaluation of releasability)
A mold model having a release film with a thickness of 1 μm by applying a coating solution on a washed 5 cm square stainless steel (SUS) plate by spin coating and heating at 200 ° C. for 30 minutes using a hot plate. Was made.
On the mold release film surface of this mold model, Scott transparent transparent adhesive tape (CC1820-Bx-J)
A width of 19 mm was applied, and the peel strength (N) was measured at a peel rate of 15 mm / min using a 90 ° peel tester (manufactured by Nisshin Kagaku). When the peel strength is 1.2 N or less, the release property is excellent.
（膜硬度）
　前記金型モデルの離型膜を形成した面に対して鉛筆硬度試験（ＪＩＳ５６００－５－４）を行った。鉛筆硬度がＦ以上であれば、膜硬度に優れる。 (Film hardness)
A pencil hardness test (JIS 5600-5-4) was performed on the surface of the mold model on which the release film was formed. If the pencil hardness is F or more, the film hardness is excellent.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　例１～１４のコーティング液から形成された離型膜は、粘着テープの剥離強度が小さく、離型性に優れていた。また、膜硬度がＦ以上であり、耐久性に優れていた。
　単位（ｕ１）～（ｕ３）を含み、化合物（Ｂ）を含まない例１５、２１のコーティング液や、化合物（Ｂ）の代わりに官能基（Ｉ）を１しか有さず沸点が１００℃未満の化合物を用いた例１６のコーティング液から形成された離型膜は、剥離強度が大きく、離型性に劣っていた。
　単位（ｕ２）を含まない例１７～２０のコーティング液から形成された離型膜は、膜硬度が低く、耐久性に劣っていた。 The release films formed from the coating liquids of Examples 1 to 14 had a low peel strength of the adhesive tape and excellent mold release properties. Further, the film hardness was F or more, and the durability was excellent.
The coating solutions of Examples 15 and 21 containing units (u1) to (u3) and no compound (B), or having only one functional group (I) instead of compound (B) and a boiling point of less than 100 ° C. The release film formed from the coating solution of Example 16 using the above compound had high peel strength and was inferior in release properties.
The release films formed from the coating liquids of Examples 17 to 20 containing no unit (u2) had low film hardness and poor durability.
　例１～９と例１５との対比から、または例１０～１４と例２１との対比から、化合物（Ｂ）の添加により、離型膜の剥離強度が小さくなったことがわかる。
　一方、例１７～２０の対比から、単位（ｕ２）を含まない場合には、化合物を添加しても離型性の向上効果は見られないことがわかる。 From the comparison between Examples 1 to 9 and Example 15 or from the comparison between Examples 10 to 14 and Example 21, it can be seen that the peel strength of the release film was reduced by the addition of the compound (B).
On the other hand, from the comparison of Examples 17 to 20, it can be seen that when the unit (u2) is not included, the effect of improving the releasability is not observed even when the compound is added.
　本発明の樹脂組成物およびコーティング液は、例えば、離型膜付き金型、防汚コート付き物品、撥液コート付き物品等の製造に有用である。
　なお、２０１６年０６月２７日に出願された日本特許出願２０１６－１２６６９０号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The resin composition and coating liquid of the present invention are useful for producing, for example, a mold with a release film, an article with an antifouling coat, an article with a liquid repellent coat, and the like.
The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2016-126690 filed on June 27, 2016 are incorporated herein as the disclosure of the specification of the present invention. It is.

Claims (15)

  1. 　下記単位（ｕ１）と下記単位（ｕ２）と下記単位（ｕ３）とを有する共重合体（Ａ１）と、下記化合物（Ｂ）とを含むことを特徴とする樹脂組成物。
    　単位（ｕ１）：フッ素原子を１つ以上有する有機基を有する（ただしブロックイソシアナート基および活性水素原子含有官能基を有しない。）単量体に由来する単位。
    　単位（ｕ２）：ブロックイソシアナート基を有する（ただし活性水素原子含有官能基を有しない。）単量体に由来する単位。
    　単位（ｕ３）：活性水素原子含有官能基を有する（ただしブロックイソシアナート基を有しない。）単量体に由来する単位。
    　化合物（Ｂ）：水酸基、アミノ基およびカルボキシ基からなる群から選ばれる少なくとも１種の官能基を２以上有し、その沸点が共重合体（Ａ１）におけるブロックイソシアナート基のブロック解離温度以上かつ４００℃以下である、化合物。     A resin composition comprising a copolymer (A1) having the following unit (u1), the following unit (u2) and the following unit (u3), and the following compound (B).
    Unit (u1): A unit derived from a monomer having an organic group having one or more fluorine atoms (but not having a block isocyanate group and an active hydrogen atom-containing functional group).
    Unit (u2): A unit derived from a monomer having a block isocyanate group (but not having an active hydrogen atom-containing functional group).
    Unit (u3): A unit derived from a monomer having an active hydrogen atom-containing functional group (but not having a block isocyanate group).
    Compound (B): having at least two functional groups selected from the group consisting of a hydroxyl group, an amino group and a carboxy group, the boiling point of which is not less than the block dissociation temperature of the block isocyanate group in the copolymer (A1); A compound that is 400 ° C. or lower.
  2. 　前記共重合体（Ａ１）が、共重合体（Ａ１）中の全単位に対して、単位（ｕ１）を５～４０モル％、単位（ｕ２）を３０～４８モル％および単位（ｕ３）を３０～４８モル％の割合で含む共重合体である、請求項１に記載の樹脂組成物。 In the copolymer (A1), the unit (u1) is 5 to 40 mol%, the unit (u2) is 30 to 48 mol%, and the unit (u3) is the total unit in the copolymer (A1). The resin composition according to claim 1, which is a copolymer containing 30 to 48 mol%.
  3. 　前記共重合体（Ａ１）の質量平均分子量が５，０００～２００，０００である、請求項１または２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the copolymer (A1) has a mass average molecular weight of 5,000 to 200,000.
  4. 　前記化合物（Ｂ）の含有量が、前記共重合体（Ａ１）の１００質量部に対して２０～６０質量部である、請求項１～３のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the content of the compound (B) is 20 to 60 parts by mass with respect to 100 parts by mass of the copolymer (A1).
  5. 　下記単位（ｕ１）と下記単位（ｕ２）とを有し、下記単位（ｕ３）を有しない共重合体（Ａ２）と、前記単位（ｕ１）と前記単位（ｕ３）とを有し、前記単位（ｕ２）を有しない共重合体（Ａ３）と、下記化合物（Ｂ）とを含むことを特徴とする樹脂組成物。
    　単位（ｕ１）：フッ素原子を１つ以上有する有機基を有する（ただしブロックイソシアナート基および活性水素原子含有官能基を有しない。）単量体に由来する単位。
    　単位（ｕ２）：ブロックイソシアナート基を有する（ただし活性水素原子含有官能基を有しない。）単量体に由来する単位。
    　単位（ｕ３）：活性水素原子含有官能基を有する（ただしブロックイソシアナート基を有しない。）単量体に由来する単位。
    　化合物（Ｂ）：水酸基、アミノ基およびカルボキシ基からなる群から選ばれる少なくとも１種の官能基を２以上有し、その沸点が共重合体（Ａ２）におけるブロックイソシアナート基のブロック解離温度以上かつ４００℃以下である、化合物。     A copolymer (A2) having the following unit (u1) and the following unit (u2) and not having the following unit (u3); the unit (u1) and the unit (u3); The resin composition characterized by including the copolymer (A3) which does not have (u2), and the following compound (B).
    Unit (u1): A unit derived from a monomer having an organic group having one or more fluorine atoms (but not having a block isocyanate group and an active hydrogen atom-containing functional group).
    Unit (u2): A unit derived from a monomer having a block isocyanate group (but not having an active hydrogen atom-containing functional group).
    Unit (u3): A unit derived from a monomer having an active hydrogen atom-containing functional group (but not having a block isocyanate group).
    Compound (B): having at least two functional groups selected from the group consisting of a hydroxyl group, an amino group and a carboxy group, the boiling point of which is not less than the block dissociation temperature of the block isocyanate group in the copolymer (A2); A compound that is 400 ° C. or lower.
  6. 　前記共重合体（Ａ２）が、共重合体（Ａ２）中の全単位に対して、単位（ｕ１）を５～４０モル％および単位（ｕ２）を６０～９５モル％の割合で含む共重合体であり、
    　前記共重合体（Ａ３）が、共重合体（Ａ３）中の全単位に対して、単位（ｕ１）を５～４０モル％および単位（ｕ３）を６０～９５モル％の割合で含む共重合体である、
    請求項５に記載の樹脂組成物。     The copolymer (A2) is a copolymer comprising 5 to 40 mol% of units (u1) and 60 to 95 mol% of units (u2) with respect to all units in the copolymer (A2). Coalesced,
    The copolymer (A3) contains 5-40 mol% of units (u1) and 60-95 mol% of units (u3) with respect to all units in the copolymer (A3). United,
    The resin composition according to claim 5.
  7. 　前記共重合体（Ａ２）の質量平均分子量が５，０００～２００，０００であり、前記共重合体（Ａ３）の質量平均分子量が５，０００～２００，０００である、請求項５または６に記載の樹脂組成物。 The mass average molecular weight of the copolymer (A2) is 5,000 to 200,000, and the mass average molecular weight of the copolymer (A3) is 5,000 to 200,000. The resin composition as described.
  8. 　前記化合物（Ｂ）の含有量が、前記共重合体（Ａ２）と前記共重合体（Ａ３）との合計１００質量部に対して２０～６０質量部である、請求項５～７のいずれか一項に記載の樹脂組成物。 The content of the compound (B) is 20 to 60 parts by mass with respect to a total of 100 parts by mass of the copolymer (A2) and the copolymer (A3). The resin composition according to one item.
  9. 　前記単位（ｕ１）が、フッ素原子を１つ以上有する有機基として、炭素数４～６の直鎖のペルフルオロアルキル基、または炭素数４～６の直鎖のペルフルオロアルキル基の炭素原子間に１～３個のエーテル性酸素原子を有する基を有する、請求項１～８のいずれか一項に記載の樹脂組成物。 The unit (u1) is an organic group having one or more fluorine atoms, and 1 to 5 carbon atoms of a linear perfluoroalkyl group having 4 to 6 carbon atoms or a linear perfluoroalkyl group having 4 to 6 carbon atoms. The resin composition according to any one of claims 1 to 8, which has a group having -3 etheric oxygen atoms.
  10. 　前記共重合体におけるブロックイソシアナート基のブロック解離温度が１２０～２００℃である、請求項１～９のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 9, wherein a block dissociation temperature of the block isocyanate group in the copolymer is 120 to 200 ° C.
  11. 　前記化合物（Ｂ）が芳香環を有する、請求項１～１０のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 10, wherein the compound (B) has an aromatic ring.
  12. 　請求項１～１１のいずれか一項に記載の樹脂組成物と、溶剤とを含むことを特徴とするコーティング液。 A coating liquid comprising the resin composition according to any one of claims 1 to 11 and a solvent.
  13. 　前記溶剤の含有割合が、コーティング液の総質量に対して、７０～９９．９質量％である、請求項１２に記載のコーティング液。 The coating liquid according to claim 12, wherein the content ratio of the solvent is 70 to 99.9 mass% with respect to the total mass of the coating liquid.
  14. 　金型の表面に、請求項１～１０のいずれか一項に記載の樹脂組成物から形成された離型膜を備えることを特徴とする離型膜付き金型。 A mold with a release film, comprising a release film formed from the resin composition according to any one of claims 1 to 10 on the surface of the mold.
  15. 　金型の表面に、請求項１２に記載のコーティング液を塗布し、ブロックイソシアナート基のブロック解離温度以上の温度で加熱して離型膜を形成し、離型膜付き金型を得ることを特徴とする離型膜付き金型の製造方法。 Applying the coating liquid according to claim 12 to the surface of the mold and heating at a temperature equal to or higher than the block dissociation temperature of the block isocyanate group to form a release film, thereby obtaining a mold with a release film A method for producing a mold with a release film.
PCT/JP2017/021023 2016-06-27 2017-06-06 Resin composition, coating liquid, release film-equipped mold, and method for producing same WO2018003432A1 (en)

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