CN109415550A - Resin combination, coating fluid, the mold with mold release film and its manufacturing method - Google Patents
Resin combination, coating fluid, the mold with mold release film and its manufacturing method Download PDFInfo
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- CN109415550A CN109415550A CN201780039821.8A CN201780039821A CN109415550A CN 109415550 A CN109415550 A CN 109415550A CN 201780039821 A CN201780039821 A CN 201780039821A CN 109415550 A CN109415550 A CN 109415550A
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- 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
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- 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
- 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
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention, which provides, can form excellent release property and the resin combination and coating fluid of the film of excellent in te pins of durability and have that release property is excellent and the mold and its manufacturing method with mold release film of the mold release film of excellent in te pins of durability.Resin combination includes copolymer (A1) and compound (B), and the unit of monomer of the above-mentioned copolymer (A1) with the organic group (but without blocked isocyanate base and containing the functional group of active hydrogen atom) derived from the fluorine atom for having 1 or more derives from the unit of the monomer with blocked isocyanate base (but not having functional group containing active hydrogen atom) and the unit of the monomer from the functional group's (but without blocked isocyanate base) having containing active hydrogen atom；Above compound (B) with 2 or more selected from hydroxyl, at least one kind of functional group of amino and carboxyl and its boiling point more than the sealing end dissociation temperature of the blocked isocyanate base in copolymer (A1) and at 400 DEG C or less.
Description
Technical field
The present invention relates to resin combination, coating fluid, the mold with mold release film and its manufacturing methods.
Background technique
In the past, the release agent excellent as release property uses fluorochemical (such as patent document 1).The release agent example
Such as in the surface filming for the mold that resin, rubber, metal are formed.Whereby, release property of the formed products from mold releasability
It improves.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2010-18038 bulletin
Summary of the invention
The technical problems to be solved by the invention
But the durability of the film for the release agent recorded in patent document 1 (being also denoted as " mold release film " below) is not enough,
It is repeated in the forming of formed products, resin or rubber due to flowing occurs and mold release film is cut in or mold release film is to forming
The problem of product migration, mold release film is damaged.
The purpose of the present invention is to provide can form that release property is excellent and the resin combination of the film of excellent in te pins of durability and painting
Cloth liquid and have that release property is excellent and the mold and its manufacturing method with mold release film of the mold release film of excellent in te pins of durability.
Technical scheme applied to solve the technical problem
The present invention provide the resin combination of composition with following [1]~[15], coating fluid, the mold with mold release film and
Its manufacturing method.
[1] a kind of resin combination, characterized in that comprising with following units (u1), following units (u2) and following lists
The copolymer (A1) and following compounds (B) of first (u3),
Unit (u1): from the fluorine atom for having 1 or more organic group (but do not have blocked isocyanate base
With the functional group containing active hydrogen atom) monomer unit；
Unit (u2): from the monomer with blocked isocyanate base (but not having the functional group containing active hydrogen atom)
Unit；
Unit (u3): from the monomer for the functional group's (but not having blocked isocyanate base) having containing active hydrogen atom
Unit；
Compound (B): with 2 or more exist selected from hydroxyl, at least one kind of functional group of amino and carboxyl, its boiling point
More than the sealing end dissociation temperature of the blocked isocyanate base in copolymer (A1) and in 400 DEG C of compounds below.
[2] resin combination as described in [1], wherein above-mentioned copolymer (A1) is relative to complete in copolymer (A1)
Portion's unit is with the ratio of 5~40 moles of % comprising unit (u1), with the ratio of 30~48 moles of % comprising unit (u2) and with 30
The ratio of~48 moles of % includes the copolymer of unit (u3).
[3] resin combination as described in [1] or [2], wherein the matter average molecular weight of above-mentioned copolymer (A1) be 5000~
200000。
[4] resin combination as described in any one of [1]~[3], wherein the content of above compound (B) relative to
The above-mentioned copolymer (A1) of 100 mass parts is 20~60 mass parts.
[5] a kind of resin combination, characterized in that comprising there is following units (u1) and following units (u2) but do not have
The copolymer (A2) of following units (u3) has said units (u1) and said units (u3) but does not have said units (u2)
Copolymer (A3) and following compounds (B),
Unit (u1): from the fluorine atom for having 1 or more organic group (but do not have blocked isocyanate base
With the functional group containing active hydrogen atom) monomer unit；
Unit (u2): from the monomer with blocked isocyanate base (but not having the functional group containing active hydrogen atom)
Unit；
Unit (u3): from the monomer for the functional group's (but not having blocked isocyanate base) having containing active hydrogen atom
Unit；
Compound (B): with 2 or more exist selected from hydroxyl, at least one kind of functional group of amino and carboxyl, its boiling point
More than the sealing end dissociation temperature of the blocked isocyanate base in copolymer (A2) and in 400 DEG C of compounds below.
[6] resin combination as described in [5], wherein above-mentioned copolymer (A2) is relative to complete in copolymer (A2)
Copolymerization of portion's unit with the ratio of 5~40 moles of % comprising unit (u1) and with the ratio of 60~95 moles of % comprising unit (u2)
Object；Above-mentioned copolymer (A3) is to include unit relative to whole units in copolymer (A3) with the ratio of 5~40 moles of %
It (u1) and with the ratio of 60~95 moles of % include the copolymer of unit (u3).
[7] resin combination as described in [5] or [6], wherein the matter average molecular weight of above-mentioned copolymer (A2) be 5000~
200000, the matter average molecular weight of above-mentioned copolymer (A3) is 5000~200000.
[8] resin combination as described in any one of [5]~[7], wherein the content of above compound (B) relative to
Total 100 mass parts of above-mentioned copolymer (A2) and above-mentioned copolymer (A3) are 20~60 mass parts.
[9] resin combination as described in any one of [1]~[8], wherein said units (u1) have carbon number 4~6
The perfluoroalkyl of straight chain or the group for having 1~3 etheric oxygen atom between the carbon atom of the perfluoroalkyl of the straight chain of carbon number 4~6
Organic group as the fluorine atom for having 1 or more.
[10] resin combination as described in any one of [1]~[9], wherein the sealing end isocyanic acid in above-mentioned copolymer
The sealing end dissociation temperature of ester group is 120~200 DEG C.
[11] resin combination as described in any one of [1]~[10], wherein above compound (B) has aromatic ring.
[12] a kind of coating fluid, characterized in that comprising resin combination described in any one of above-mentioned [1]~[11] and molten
Agent.
[13] coating fluid as described in [12], wherein the content ratio of above-mentioned solvent is relative to the gross mass of coating fluid
70~99.9 mass %.
[14] a kind of mold with mold release film, characterized in that have on the surface of mold by any one of [1]~[10] institute
The mold release film that the resin combination stated is formed.
[15] a kind of manufacturing method of the mold with mold release film, characterized in that described in the surface of mold coating [12]
Coating fluid is heated with temperature more than the sealing end dissociation temperature of blocked isocyanate base to form mold release film, and it is de- to obtain band
The mold of mould film.
Invention effect
Resin combination and coating fluid according to the present invention, can form that release property is excellent and the film of excellent in te pins of durability.
Mold with mold release film of the invention has that release property is excellent and the mold release film of excellent in te pins of durability.
The manufacturing method of mold according to the present invention with mold release film can manufacture and have that release property is excellent and durability is excellent
The mold with mold release film of different mold release film.
Specific embodiment
The meaning of following term in this specification is as described below.
" unit " in polymer refers to the part from the monomer formed by monomer polymerization.Unit either
The unit directly formed by polymerization reaction is also possible to convert a part of the unit and handling polymer
At the unit of other structures.
" (methyl) acryloxy " is the general designation of acryloxy and methacryloxy.
" (methyl) acrylate " is the general designation of acrylate and methacrylate.
" mold release film " refers to that the release property for the film surface that substrate etc. is formed in compared with the part for not being formed with the film is excellent
Different film, specifically, the peel strength for being attached to the substance of film surface is lesser compared with the part for not forming the film
Film.
(resin combination)
Resin combination of the invention is that the composition comprising aftermentioned copolymer (A1) and compound (B) (is also remembered below
For " resin combination (1) ") or composition comprising copolymer (A2), copolymer (A3) and compound (B) (also remember below
For " resin combination (2) ").In addition, referring to resin combination (1) and resin in the case where only referring to " resin combination "
Both compositions (2).
Resin combination can also include other compositions as needed.
Copolymer (A1), copolymer (A2), copolymer (A3) matter average molecular weight (Mw) be respectively preferably 5000~
200000, particularly preferred 10000~150000.Copolymer (A1), copolymer (A2), copolymer (A3) if Mw in above-mentioned model
More than the lower limit value enclosed, then the durability of the film of release agent is more excellent, if in the upper limit value of above range hereinafter, if in solvent
In dissolubility it is more excellent.
Matter average molecular weight (Mw) is converted by the polymethyl methacrylate of gel permeation chromatography (GPC) measurement
Value.
Copolymer (A1), copolymer (A2), each unit is as described below contained in copolymer (A3).
(unit (u1))
Unit (u1) be derived from 1 or more fluorine atom organic group (but do not have blocked isocyanate
Base and functional group containing active hydrogen atom) monomer (being also denoted as " monomer (m1) " below) unit.
The release property for the film that copolymer (A1)~(A3) is formed by with unit (u1), by resin combination is excellent.
As the organic group with 1 or more fluorine atom, from release property it is more excellent from the viewpoint of, preferred polyfluoro alkane
Base or between the carbon atom of Polyfluoroalkyl with the group of etheric oxygen atom, particularly preferred perfluoroalkyl or in perfluoroalkyl
With the group of etheric oxygen atom between carbon atom.
From the point of view of release property, Polyfluoroalkyl and the group between the carbon atom of Polyfluoroalkyl with etheric oxygen atom
Carbon number be preferably 4 or more.From the influence to environment it is small from the point of view of, preferably 6 or less.Therefore, above-mentioned carbon number is more preferable
It is 4~6, particularly preferably 6.The quantity of etheric oxygen atom is preferably 1~3, and particularly preferably 1~2.
Polyfluoroalkyl can be straight chain, or branch, preferably straight chain.
I.e., as the organic group with 1 or more fluorine atom, preferably the perfluoroalkyl of the straight chain of carbon number 4~6 or
With the group of 1~3 etheric oxygen atom, particularly preferred carbon number 6 between the carbon atom of the perfluoroalkyl of the straight chain of carbon number 4~6
Straight chain perfluoroalkyl or between the carbon atom of the perfluoroalkyl of the straight chain of carbon number 6 with 1~2 etheric oxygen atom base
Group.
Monomer (m1) is preferably the group with polymeric double bond and the organic group with 1 or more fluorine atom is direct
Or structure made of being combined by linking group.
The organic group of the polymeric double bond and the fluorine atom with 1 or more that are combined directly or by linking group
Quantity be respectively preferably 1.
As the group with polymeric double bond, such as vinyl, allyl, (methyl) acryloxy, α-can be enumerated
Propylene halide acyloxy etc..Among them, from the point of view of being easy to control the molecular weight of copolymer, preferred (methyl) acryloyl
Oxygroup.
As linking group, such as divalent alkyl can be enumerated.As divalent alkyl, can enumerate such as alkylidene, arlydene.
As the linking group, considered from the perspective of durability, preferred alkylidene, the alkylidene of particularly preferred carbon number 1~6.Alkylidene
It can be linear chain or branched chain, preferably straight chain.
As monomer (m1), from the angle that the release property that is formed by film is more excellent, influence to environment is small, is easy to get
Consider, preferably with CH2=C (R11) C (O) O-R12- RfThe monomer of expression.Wherein, R11It is hydrogen atom, methyl or halogen atom (fluorine
Atom, chlorine atom etc.), R12It is alkylidene, RfIt is the perfluoroalkyl of carbon number 4~6 or the carbon original of the perfluoroalkyl in carbon number 4~6
With the group of etheric oxygen atom between son.
As R11, preferably hydrogen atom or methyl, particularly preferred methyl.
As R12, the preferred alkylidene of carbon number 1~6, particularly preferred-CH2,-C2H4?.
As Rf, preferably-(CF2)3CF3、-(CF2)4CF3、-(CF2)5CF3、-CF(CF3)OCF2CF2CF3、-
CF2OCF2CF2OCF3、-CF2OCF2CF2OCF2CF3、-CF2OCF2CF2OCF2CF2OCF3。
As with CH2=C (R11)C(O)O-R12-RfThe monomer of expression can enumerate following compounds.
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)5CF3Deng.
As monomer (m1), particularly preferably following compounds.
CH2=C (CH3)C(O)O-C2H4-(CF2)5CF3、
CH2=C (CH3)C(O)O-CH2-CF2OCF2CF2OCF2CF2OCF3。
Monomer (m1) can be used alone, and can also be used in combination with two or more.
(unit (u2))
Unit (u2) is derived from the list with blocked isocyanate base (but not having the functional group containing active hydrogen atom)
The unit of body (being also denoted as " monomer (m2) " below).
Blocked isocyanate base be with end-capping reagent will be isocyanate-terminated after group.As will be isocyanate-terminated
End-capping reagent, can enumerate such as oximes, pyrazoles.
Monomer (m2) is preferably the group with polymeric double bond and blocked isocyanate base directly or by linking group
Structure made of being combined.
The quantity difference of the polymeric double bond and blocked isocyanate base that are combined directly or by linking group is preferred
It is 1.
As group and linking group with polymeric double bond, can enumerate has polymerism with monomer (m1) respectively
The identical group of group and linking group of double bond, preferred configuration are also identical.
As monomer (m2), from the point of view of the easiness of cross-linking reaction, preferably with CH2=C (R13)C(O)O-R14-
NHC(O)R15The monomer of expression.Wherein, R13It is hydrogen atom, methyl or halogen atom (fluorine atom, chlorine atom etc.), R14It is alkylidene,
R15It is the organic group of 1 valence.
-NHC(O)R15It is equivalent to blocked isocyanate base.
As R13, preferably hydrogen atom or methyl, particularly preferred methyl.
As R14, the preferred alkylidene of carbon number 1~6, particularly preferred-CH2-、-C2H4-。
As R15, preferably following groups indicated with formula (5a), following groups indicated with formula (5b) or following with formula
The group that (5c) is indicated.Wherein, R51、R52、R53And R54It is separately the alkyl of carbon number 1~4.
Monomer (m2) can be used alone 2 kinds, can also be used in combination with two or more.
[changing 1]
(unit (u3))
Unit (u3) is derived from the list with functional group's (but not having blocked isocyanate base) containing active hydrogen atom
The unit of body (being also denoted as " monomer (m3) " below).
As the functional group containing active hydrogen atom, preferably hydroxyl (OH) or amino (NH2), particularly preferred hydroxyl.
Monomer (m3) is preferably the group with polymeric double bond and the functional group containing active hydrogen atom directly or by even
Connect structure made of group is combined.
As group and linking group with polymeric double bond, can enumerate has polymerism with monomer (m1) respectively
The identical group of group and linking group of double bond, preferred configuration are also identical.
As monomer (m3), from the point of view of the easiness of cross-linking reaction, preferably with CH2=C (R16)C(O)O-R17-OH
The monomer of expression.Wherein, R16For hydrogen atom, methyl or halogen atom (fluorine atom, chlorine atom etc.), R17For alkylidene.
As R16, preferably hydrogen atom or methyl, particularly preferred methyl.
As R17, the preferred alkylidene of carbon number 1~6, particularly preferred-CH2-、-C2H4-。
Monomer (m3) can be used alone, and can also be used in combination with two or more.
(other units)
Copolymer (A1), copolymer (A2) and copolymer (A3) can have unit (u1), unit (u2) and unit respectively
(u3) unit (being denoted as " other units " below) other than.
The monomer that other units are derived from other than monomer (m1), monomer (m2) and monomer (m3) (is also denoted as " monomer below
(m4) " unit).
As monomer (m4), such as (methyl) alkyl acrylate, alkyl vinyl ether, vinyl chloride etc. can be enumerated.
Monomer (m4) can be used alone, and can also be used in combination with two or more.
(copolymer (A1))
Copolymer (A1) has unit (u1), unit (u2) and unit (u3).
Copolymer (A1) can also have other units as needed.
In copolymer (A1), the ratio of unit (u1) preferably accounts for 5~40 in whole units of copolymer (A1) and rubs
You are %, particularly preferably accounts for 10~30 moles of %.If the ratio of unit (u1) is formed more than the lower limit value of above range
Film release property it is more excellent.If the ratio of unit (u1) in the upper limit value of above range hereinafter, if be formed by the resistance to of film
Long property is more excellent.
The ratio of unit (u2) preferably accounts for 30~48 moles of % in whole units of copolymer (A1), particularly preferably accounts for 35
~45 moles of %.If the ratio of unit (u2) is more than the lower limit value of above range, the durability for being formed by film is more excellent
It is different.If the ratio of unit (u2) in the upper limit value of above range hereinafter, if be formed by film release property it is more excellent.
The ratio of unit (u3) preferably accounts for 30~48 moles of % in whole units of copolymer (A1), particularly preferably accounts for 35
~45 moles of %.If the ratio of unit (u3) is more than the lower limit value of above range, the durability for being formed by film is more excellent
It is different.If the ratio of unit (u3) in the upper limit value of above range hereinafter, if be formed by film release property it is more excellent.
Therefore, as copolymer (A1), preferably in whole units of copolymer (A1), with the ratio of 5~40 moles of %
Include unit comprising unit (u2), with the ratio of 30~48 moles of % comprising unit (u1), with the ratio of 30~48 moles of %
(u3), unit is particularly preferably included comprising unit (u1), with the ratio of 35~45 moles of % with the ratio of 10~30 moles of %
It (u2), include unit (u3) with the ratio of 35~45 moles of %.
The molar ratio (unit (u2)/unit (u3)) of unit (u2) and unit (u3) are preferably 30/70~70/30, especially
It is preferred that 40/60~60/40.If unit (u2)/unit (u3) is within the above range, superior demoulding can be achieved at the same time
Property and superior durability.
The sealing end dissociation temperature of blocked isocyanate base in copolymer (A1) and the blocked isocyanate in monomer (m2)
The sealing end dissociation temperature of base is roughly equal.Therefore, by the selection of the blocked isocyanate base in monomer (m2), it can adjust copolymerization
The sealing end dissociation temperature of blocked isocyanate base in object (A1).It is also the same in following copolymers (A2).
In addition, sealing end dissociation temperature not instead of 1 point in monomer and copolymer, has certain range, therefore this
In invention, the sealing end dissociation temperature in copolymer (A1) and copolymer (A2) is will to block isocyanic acid by heating in 30 minutes
" sealing end dissociation temperature " of the temperature of the de- sealing end of the 50% of ester group as copolymer.
Hereinafter, by the sealing end dissociation temperature T of the blocked isocyanate base in copolymer (A1) and copolymer (A2)D(℃)
It indicates.
(copolymer (A2))
Copolymer (A2) is the copolymer with unit (u1) and unit (u2), but without unit (u3).
Copolymer (A2) can also have other units as needed.
In copolymer (A2), the ratio of unit (u1) preferably accounts for 5~40 in whole units of copolymer (A2) and rubs
You are %, particularly preferably accounts for 5~30 moles of %.If the ratio of unit (u1) is formed more than the lower limit value of above range
Film release property it is more excellent.If the ratio of unit (u1) in the upper limit value of above range hereinafter, if be formed by the resistance to of film
Long property is more excellent.
The ratio of unit (u2) preferably accounts for 60~95 moles of % in whole units of copolymer (A2), particularly preferably accounts for 70
~95 moles of %.If the ratio of unit (u2) is more than the lower limit value of above range, the durability for being formed by film is more excellent
It is different.If the ratio of unit (u2) in the upper limit value of above range hereinafter, if be formed by film release property it is more excellent.
Therefore, as copolymer (A2), preferably in whole units of copolymer (A2), with the ratio of 5~40 moles of %
It include the copolymer of unit (u2) comprising unit (u1), with the ratio of 60~95 moles of %, particularly preferably with 5~30 moles of %'s
Ratio includes unit (u1), the copolymer with the ratio of 70~95 moles of % comprising unit (u2).
(copolymer (A3))
Copolymer (A3) is the copolymer with unit (u1) and unit (u3), but without unit (u2).
Because all having unit (u1), miscibility is good for copolymer (A2) and copolymer (A3).In copolymer (A2)
Unit (u1) can be identical or different with the unit (u1) in copolymer (A3).
Copolymer (A3) can also have other units as needed.
In copolymer (A3), the ratio of unit (u1) preferably accounts for 5~40 in whole units of copolymer (A3) and rubs
You are %, particularly preferably accounts for 10~40 moles of %%.If the ratio of unit (u1) is more than the lower limit value of above range, institute's shape
At film release property it is more excellent.If the ratio of unit (u1) in the upper limit value of above range hereinafter, if be formed by film
Durability is more excellent.
The ratio of unit (u3) preferably accounts for 60~95 moles of % in whole units of copolymer (A3), particularly preferably accounts for 60
~90 moles of %.If the ratio of unit (u3) is more than the lower limit value of above range, the durability for being formed by film is more excellent
It is different.If the ratio of unit (u3) in the upper limit value of above range hereinafter, if be formed by film release property it is more excellent.
Therefore, as copolymer (A3), preferably in whole units of copolymer (A3), with the ratio of 5~40 moles of %
It include the copolymer of unit (u3) comprising unit (u1), with the ratio of 60~95 moles of %, particularly preferably with 10~40 moles of %
Ratio include unit (u1), with the ratio of 60~90 moles of % include unit (u3) copolymer.
(compound (B))
Compound (B) is that there is 2 or more at least one kind of functional groups selected from hydroxyl, amino and carboxyl (also to remember below
For the compound of " functional group (I) ").
The quantity of functional group (I) is preferably 2~10 possessed by compound (B), and more preferable 2~8, particularly preferred 2 or 3.
If the quantity of functional group (I) is within the above range, the release property for being formed by film is more excellent.
As functional group (I), preferably hydroxyl or amino, particularly preferred hydroxyl.
The boiling point of compound (B) is TD~400 DEG C.If the boiling point of compound (B) is within the above range, it is formed by
The release property of film is more excellent.If the boiling point of compound (B) is lower than TD, then made when heated resin composition forms cross-linked structure
It volatilizees at compound (B), release property is possible to become not enough.
The lower limit of the boiling point of compound (B) is preferably TD+ 10 DEG C, particularly preferred TD+30℃.The boiling point of compound (B) it is upper
Preferably 300 DEG C, particularly preferred 250 DEG C of limit.
Compound (B) can be the aromatic compound with aromatic ring, be also possible to the non-aromatic without aromatic ring
Close object.
As aromatic ring, can enumerate such as phenyl ring, naphthalene nucleus, anthracene nucleus.
Non-aromatic compounds can be the aliphatic compound of straight or branched, be also possible to have ester ring type base
Ester ring type compound.
Compound (B) does not preferably have fluorine atom.
As the concrete example of compound (B), following compounds can be enumerated.
The fragrance such as phloroglucin, hydroquinone, resorcinol, 2,7 dihydroxy naphthalene, 1,5- dihydroxy naphthlene, 1,4- phenylenediamine
Compounds of group,
The non-aromatic compounds such as trimethylolpropane, ethylene glycol, propylene glycol.
In the superior viewpoint of release property, compound (B) preferably has aromatic ring.
As compound (B), particularly preferred phloroglucin, hydroquinone, resorcinol, 2,7- dihydroxy naphthlene, 1,5- bis-
The compound with aromatic ring and 2 or more the functional groups (I) in conjunction with the aromatic ring of hydroxyl naphthalene, 1,4- phenylenediamine etc..
Compound (B) can be used alone, and two or more can also be used in combination.
(other compositions)
As other compositions, can enumerate such as the adaptation modifying agent of surfactant and substrate (mold), amino first
Acid esterification catalyst (tin catalyst etc.), sealing end dissociation catalyst of blocked isocyanate base etc..
It may include copolymer (A2) or copolymer (A3) as other compositions in the case where resin combination (1), it can also not
Include；In the case where resin combination (2), it may include copolymer (A1) as other compositions, can also not include.
In addition, the resin combination in the present invention refers to not solvent-laden resin combination.
(content of each ingredient)
In resin combination, in the case where resin combination (1), the total content of copolymer (A1) and compound (B) is opposite
In the gross mass of resin combination, preferably 5~100 mass %, more preferable 10~100 mass %, particularly preferred 20~100 matter
Measure %；In the case where resin combination (2), the total content of copolymer (A2), copolymer (A3) and compound (B) is relative to resin
The gross mass of composition, preferably 5~100 mass %, more preferable 10~100 mass %, particularly preferred 20~100 mass %.
If the total content, more than the lower limit value of above range, the release property for being formed by film is more excellent, it is more excellent to form durability
Different resin combination.
In resin combination, in the case where resin combination (1), the content of compound (B) is relative to copolymer (A1)
100 mass parts are preferably 5~100 mass parts, more preferable 10~80 mass parts, particularly preferred 20~60 mass parts；Resin combination
In the case where object (2), the content of compound (B) is preferred relative to total 100 mass parts of copolymer (A2) and copolymer (A3)
For 5~100 mass parts, more preferable 10~80 mass parts, particularly preferred 20~60 mass parts.If the content of compound (B) exists
More than the lower limit value of above range, then the effect of compound (B) can be given full play to, the release property for being formed by film is more excellent.Such as
The content of fruit compound (B) above range upper limit value hereinafter, the then content of the organic group with 1 or more fluorine atom
Become enough, the release property for being formed by film is more excellent.
Resin combination (1) is preferably without the other compositions other than copolymer (A1) and compound (B).
Resin combination (2) is preferably without the other compositions other than copolymer (A2)~(A3) and compound (B).
In resin combination (2), copolymer (A2) and copolymer (A3) respective content are preferably unit (u2) and unit
(u3) amount that molar ratio (unit (u2)/unit (u3)) reaches 30/70~70/30, more preferably reaches 40/60~60/40
Amount.If unit (u2)/unit (u3) is within the above range, superior release property and superior can be achieved at the same time
Durability.
The respective whole units of copolymer (A2) and copolymer (A3) it is total in, the ratio of unit (u1) preferably accounts for 5
~40 moles of % particularly preferably account for 10~30 moles of %.If the ratio of unit (u1) more than the lower limit value of above range,
The release property for being formed by film is more excellent.If the ratio of unit (u1) in the upper limit value of above range hereinafter, if be formed by
The durability of film is more excellent.
The respective whole units of copolymer (A2) and copolymer (A3) it is total in, the ratio of unit (u2) preferably accounts for 30
~48 moles of % particularly preferably account for 35~45 moles of %.If the ratio of unit (u2) more than the lower limit value of above range,
The durability for being formed by film is more excellent.If the ratio of unit (u2) in the upper limit value of above range hereinafter, if be formed by
The release property of film is more excellent.
The respective whole units of copolymer (A2) and copolymer (A3) it is total in, the ratio of unit (u3) preferably accounts for 30
~48 moles of % particularly preferably account for 35~45 moles of %.If the ratio of unit (u3) more than the lower limit value of above range,
The durability for being formed by film is more excellent.If the ratio of unit (u3) in the upper limit value of above range hereinafter, if be formed by
The release property of film is more excellent.
(function and effect)
Resin combination, can shape because comprising copolymer (A1) or copolymer (A2) and copolymer (A3) and compound (B)
Excellent and excellent in te pins of durability the cured film (identical as mold release film of the invention) at release property.
By the inclusion of copolymer (A1) or copolymer (A2) and copolymer (A3), in resin combination unit (u1)~
(u3) all exist.
The organic group with 1 or more fluorine atom of unit (u1) reduces the cured film formed by resin combination
Surface energy, is conducive to the raising of release property.
The presence of unit (u2) and unit (u3) has the raising for the durability for being conducive to the cured film formed by resin combination.
If by the blocked isocyanate base deblocking being heated in unit (u2) from the cured films that resin combination is formed and becoming
Temperature (the i.e., T of isocyanate groupD) more than, then the official containing active hydrogen atom in isocyanate group and unit (u3) that generates
Reaction can be rolled into a ball, cross-linked structure is formed.In addition, functional group reactions of the isocyanate group of deblocking also with compound (B), form
Cross-linked structure.By the formation of these cross-linked structures, resin combination crosslinking curing, the durability of film is improved as a result,.
In addition, resin combination is by the inclusion of compound (B), compared with the case where being free of compound (B), release property is more excellent
It is different.Think the reason is that: the polarity of functional group (I) possessed by compound (B) is high, so in compound (B) and unit (u1)
Above-mentioned organic group compatibility it is low, when die surface forms uncured film, as present in cured films change
It closes object (B), above-mentioned organic group is easy to concentrate the Free Surface side surface for being present in film, and then cured films are sent out in this state
Raw solidification, so that above-mentioned organic group is easy to concentrate the Free Surface side surface for being present in cured film.
The said effect of compound (B) obtains sufficiently because unit (u1)~(u3) is all present in resin combination
It plays.For example, in the case where unit (u2) is not present in resin combination, it is possible to can not observe the raising effect of release property
Fruit.
(coating fluid)
Coating fluid (being also denoted as " this coating fluid " below) of the invention is the liquid comprising above-mentioned resin combination and solvent
Composition.
(solvent)
As solvent, can enumerate such as fluoride solvent, hydrocarbon solvent.Solvent can be used alone a kind, can also with 2 kinds with
On be used in combination.The boiling point of these solvents is preferably shorter than the boiling point of compound (B), will not remove compound (B) when removing solvent
It goes.Its boiling point is preferably than 20 DEG C of low boiling point or more of compound (B).In addition, the sight that flatness from the surface after coating is excellent
Point considers that the lower limit value of boiling point is preferably 80 DEG C, particularly preferred 100 DEG C.From the viewpoint of the easiness of the removing based on heating
Consider, the upper limit value of the boiling point of solvent is preferably 300 DEG C.
In the case where the solvent that compound by not having the functional group containing active hydrogen atom is formed, because to isocyanates
Base is inert, so its boiling point is also possible to TDAbove temperature.But even TDAbove temperature, if isocyanate group is raw
At it is rear there are the state for extended periods of solvent continue, then cross-linking reaction carry out, it is difficult to generate the good film of flatness, it is advantageous to from
Drying temperature (for heating the temperature for removing solvent) is fast moved to solidification temperature.By not having the function containing active hydrogen atom
The boiling point for the solvent that the compound of group is formed is preferably in TD+ 50 DEG C hereinafter, more preferably in TD+ 30 DEG C or less.
In the case where the solvent formed by the compound with the functional group containing active hydrogen atom of alcohols etc., if it is boiled
Point is high, it is likely that when removing solvent, the blocked isocyanate base of copolymer takes off sealing end and reacted, and it is advantageous to by having
The boiling point ratio T for the solvent that the compound of active hydrogen atom is formedDIt is sufficiently low.Its boiling point is preferably in TD- 30 DEG C hereinafter, more preferably
In TD- 50 DEG C or less.
As the concrete example of fluoride solvent, following compounds can be enumerated.
As the ASAHIKLIN (ア サ ヒ Network リ Application) (trade mark) of Asahi Glass Co., Ltd, can enumerate ten trifluoro of 1H- oneself
Alkane (AC2000, boiling point: 71 DEG C)；1,1,1,2,2,3,3,4,4,5,5,6,6- ten three fluoro-octane (AC6000, boiling point: 115 DEG C)；
1,1,2,2- tetra- fluoro- 1- (2,2,2- trifluoro ethoxy) ethane (AE3000, boiling point: 56 DEG C)；Dichloro pentafluoropropane (AK-225,
Boiling point: 54 DEG C) etc..As other, there is CYTOP (trade mark) CT-solv100E (Asahi Glass Co., Ltd's system, boiling point: 98 DEG C)；1-
MSX 4518 (Co., Ltd, 3M Japan system, Novec (trade mark) 7100, boiling point: 61 DEG C)；1- ethoxy nonafluorobutane
(Co., Ltd, 3M Japan system, Novec (trade mark) 7200, boiling point: 76 DEG C)；1,1,1,2,3,3- hexafluoro -4- (1,1,2,3,3,3-
Hexafluoro propoxyl group) pentane (Co., Ltd, 3M Japan system, Novec (trade mark) 7600, boiling point: 131 DEG C)；2H, 3H- perflenapent
(three well Du Pont fluorine chemistry Co. Ltd. systems, Vertrel (trade mark) XF, boiling point: 55 DEG C)；3,3,4,4,5,5,6,6,7,7,8,
The fluoro- 1- octanol of 8,8- 13 (boiling point: 80 DEG C)；The fluoro- 1 nonyl alcohol of 4,4,5,5,6,6,7,7,8,8,9,9,9- 13；Phenyl-hexafluoride
(boiling point: 81 DEG C)；Hexafluoro -2- propyl alcohol (boiling point: 59 DEG C)；2,2,3,3,4,4,5,5- octafluoro -1- amylalcohol (boiling point: 140 DEG C)；
The fluoro- 1-heptanol of 1H, 1H, 7H- 12 (boiling point: 170 DEG C)；Fluoro- 1- octanol of 1H, 1H, 2H, 2H- 13 (boiling point: 80 DEG C) etc..
As the concrete example of hydrocarbon solvent, following compounds can be enumerated.
The ketones such as cyclopentanone, cyclohexanone, methyl amyl ketone, 2- butanone；Ethyl lactate, methyl benzoate, ethyl benzoate,
Ergol, methylcellosolve acetate, ethyl cellosolve acetate, propylene glycol methyl ether acetate, propylene glycol ester list second
The esters such as ether acetic acid ester；Tetrahydrofuran, dioxanes, dimethoxy-ethane, diethoxyethane, methyl phenyl ethers anisole, diethylene glycol dimethyl ether,
The ethers such as triglyme；The carbon such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate
Esters of gallic acid；N-butyl alcohol, 1- amylalcohol, 1- hexanol, 1-heptanol, 2- propyl alcohol, 2- butanol, 2- amylalcohol, 3- amylalcohol, 2- hexanol, 3- hexanol,
Alcohols such as 2- enanthol, 3- enanthol, 4- enanthol, sec-n-octyl alcohol, 3- octanol, 4- octanol etc..
(composition of this coating fluid)
In this coating fluid, the ratio of above-mentioned resin combination is 0.1~30 matter preferably with respect to the gross mass of this coating fluid
Measure %, particularly preferred 1~30 mass %.
The ratio of solvent is 70~99.9 mass %, particularly preferred 70~99 matter preferably with respect to the gross mass of this coating fluid
Measure %.
(function and effect)
This coating fluid can form that release property is excellent and the film of excellent in te pins of durability because comprising above-mentioned resin combination.
(mold with mold release film)
Mold with mold release film of the invention has the mold release film formed by above-mentioned resin combination on the surface of mold.
The material of mold is typically metal, can enumerate such as iron, nickel, aluminium, stainless steel, nickel alloy, duralumin.
The thickness of mold release film is not particularly limited, but preferably 0.05~5 μm, and particularly preferred 0.1~2 μm.
Mold with mold release film can be manufactured for example, by the manufacturing method of the mold as shown below with mold release film.
(manufacturing method of the mold with mold release film)
As the manufacturing method of the mold of the invention with mold release film, it preferably is coated with this coating fluid on the surface of mold, with
More than the boiling point of solvent (but the boiling point for being lower than compound (B)) and TDAbove temperature is heated, and mold release film is formed, and obtains band
The method of the mold of mold release film.Heating temperature preferably+10 DEG C of the boiling point of solvent or more the boiling points of (but be lower than compound (B)) and
In TD+ 30 DEG C or more, more preferably at+20 DEG C of the boiling point of solvent or more (but the boiling points for being lower than compound (B)) and in TD+ 50 DEG C with
On.The upper limit value of heating temperature is preferably 300 DEG C.
It is coated with this coating fluid, if being heated with temperature more than above-mentioned heating temperature, solvent can be removed, formed by upper
The film for stating resin combination composition generates isocyanate group, the isocyanate group by the blocked isocyanate base in unit (u2)
With the functional group reactions containing active hydrogen atom in unit (u3) or compound (B), cross-linked structure is formed.Whereby, it is formed by upper
State the mold release film that the solidfied material of resin combination is constituted.
After the coating of this coating fluid, before heating, by this coating fluid of coating in the at a temperature of drying lower than 150 DEG C
(removing solvent), can form the desciccator diaphragm being made of above-mentioned resin combination.
The coating method of this coating fluid is not particularly limited, and wet type well known to spraying, dipping, brushing, spin coating etc. can be used
Rubbing method.
Heating temperature when formation mold release film is preferably at 150 DEG C or more.Heating temperature is preferably at 400 DEG C or less.Heating temperature
Degree is set as the surface temperature of mold.Heating time can be set as such as 5~60 minutes.
(purposes)
The above-mentioned mold with mold release film can be used for the manufacture of the formed products of various moulding materials.
As with the die forming with mold release film, be made into the moulding materials of formed products, be not particularly limited, can be example
The various well known moulding materials of such as metal, resin, rubber.
Processing method using mold of the invention is preferably pressure processing or injection molding.Tonnage is preferably 1~
50MPa.If in 1MPa or more, excellent in workability, if in 50MPa hereinafter, if mold excellent in te pins of durability.In addition, plus
Work temperature is preferably 150~250 DEG C.If had excellent formability at 150 DEG C or more, if at 250 DEG C hereinafter, if can prevent
Mold release film because thermal decomposition caused by deteriorate.Processing object is not particularly limited, polyethylene, polypropylene, polyphenyl can be illustrated
Ethylene, polyethylene terephthalate, polyvinyl chloride, polycarbonate, polyamide, polyester, phenolic resin, acrylic resin,
The resin materials such as epoxy resin, ABS resin, natural rubber, butadiene-styrene rubber, isoprene rubber, butadiene rubber, acrylonitrile fourth
The rubber materials such as diene rubber, polyurethane rubber, acrylic rubber, silicon rubber, fluorubber, iron, nickel, aluminium, titanium, stainless steel, nickel
Metals such as alloy, duralumin etc..
(function and effect)
The release property of above-mentioned mold release film is excellent.And excellent in te pins of durability, it is not easy to occur because friction etc. caused by be ground or
Removing.
Therefore, by using the above-mentioned mold with mold release film, the formed products of forming can easily be demoulded.
In addition, in the case where release agent used in previous mold, in Iteratively forming, due to the contact with moulding material
Deng being easy to happen the grinding or removing of mold release film, need continually to re-form mold release film.In the above-mentioned mold with mold release film
In the case of, because the excellent in te pins of durability of mold release film, compared with the past, the frequency for re-forming mold release film can be reduced.
In addition, in the case where the above-mentioned mold with mold release film, because of the release property and excellent in te pins of durability of mold release film,
It can inhibit surface migration of the mold release film to formed products.The migration can by the contact angle of the water on the surface of resulting formed products come
Measurement.For example, if the contact angle of the water on the surface of the metal (formed products) after processing is than on the metallic surface before processing
Water contact angle it is big, then the migration of mold release film has occurred.
Embodiment
The present invention is described in detail for embodiment described below.But the present invention is not limited to records below.
In aftermentioned example 1~21, example 1~14 is embodiment, and example 15~21 is comparative example.
Measuring method used in each example is described below.
(measuring method)
(NMR measurement)
It is carried out using the JNM-AL300 that Jeol Ltd. (Japan Electronics society) makes1The measurement of H-NMR.
(ratio of components of copolymer)
Above-mentioned NMR measurement is carried out, according to the integral of 3.6ppm, 3.8ppm, 4.3ppm than calculating.
(molecular weight determination)
Matter average molecular weight (Mw) is by using (Dong ソ ー society, TOSOH Co., Ltd) HLC-8220 of system, using using molecular weight
Lubber-line made of known standard polymethyl methacrylate sample is determined (poly- first with gel permeation chromatography device
Base methyl acrylate conversion).
(raw material etc.)
Dummy suffix notation used in each example below respectively indicates compound below.
C6FMA:CH2=C (CH3)COO-C2H4-C6F13(C6FMA is by Japanese Patent Laid-Open 2004-359616 public affairs
The method manufacture recorded in the example 1 of report).
Monomer (m1-1): CH2=C (CH3)COO-CH2-CF2OCF2CF2OCF2CF2OCF3(monomer (m1-1) is by following
Production Example 1 manufacture).
MOI-BM: (methacrylic acid 2- (O- [1 '-methyl propylene amino] the carboxyl ammonia of compound represented by following formula (i)
Base) ethyl ester；TD is 150 DEG C；Trade name " カ レ Application ズ MOI-BM " (Showa Denko K. K's system)).
[changing 2]
HEMA: 2-hydroxyethyl methacrylate (Junsei Chemical Co., Ltd.'s system).
MEK:2- butanol (Kanto Kagaku K. K.'s system).
Compound (B-1): phloroglucin (Tokyo is melted into Co. Ltd. system, 220 DEG C of boiling point, molecular weight 126).
Compound (B-2): hydroquinone (Tokyo is melted into Co. Ltd. system, 287 DEG C of boiling point, molecular weight 110).
Compound (B-3): resorcinol (Tokyo is melted into Co. Ltd. system, 277 DEG C of boiling point, molecular weight 110).
Compound (B-4): 2,7- dihydroxy naphthlenes (Tokyo is melted into Co. Ltd. system, 375 DEG C of boiling point, molecular weight 160).
Compound (B-5): 1,5- dihydroxy naphthlene (Tokyo is melted into Co. Ltd. system, 375 DEG C of boiling point, molecular weight 160).
Compound (B-6): Isosorbide-5-Nitrae-phenylenediamine (Tokyo is melted into Co. Ltd. system, 267 DEG C of boiling point, molecular weight 108).
Compound (B-7): trimethylolpropane (Tokyo is melted into Co. Ltd. system, 160 DEG C of boiling point, molecular weight 134).
Compound (B-8): ethylene glycol (Tokyo is melted into Co. Ltd. system, 197 DEG C of boiling point, molecular weight 62).
Compound (X-1): isopropanol (Kanto Kagaku K. K.'s system, 83 DEG C of boiling point, molecular weight 74).
(Production Example 1: the synthesis of monomer (m1-1))
By compound represented by 30.0g following formula (ii) (1H, 1H- perfluor -3,6,9- trioxa decyl- 1- alcohol) and 12.0g
Triethylamine be dissolved in the tetrahydrofuran of 50mL.Under ice-cooling, the methacrylic chloride of 12.0g is added dropwise thereto, in room
After the lower stirring of temperature 2 hours, add the ethyl acetate of 150mL, successively with the hydrochloric acid 150mL of 1 equivalent, saturated salt solution 150mL into
Extraction is gone.Then, with the dry ethyl acetate layer of magnesium sulfate, ethyl acetate is distilled off.It is resulting by vacuum distillation purifying
Liquid has obtained target compound (monomer (m1-1)).Resulting compound1The measurement result of H-NMR is as follows.
1H-NMR (300.4MHz, solvent: d- acetone, benchmark: tetramethylsilane (being also denoted as " TMS " below)) δ (ppm):
2.0(s、3H)、4.8(t、2H)、6.0(s、1H)、6.2(s、1H)。
[changing 3]
(Production Example 2)
By initiator V65 (the He Guangchun medicine strain formula of the MOI-BM of HEMA, 1.3g of C6FMA, 0.7g of 1.2g and 0.05g
Commercial firm's system) it is dissolved in the MEK of 29g, after atmosphere is replaced into nitrogen, vibrated at 50 DEG C 24 hours.It will be resulting anti-
In the hexane for answering liquid investment 500mL, the filter of polytetrafluoroethylene (PTFE) (PTFE) system of 3 μm of normal pore size of the solid of precipitation is carried out
Filtering, has obtained the copolymer (A1-1) of the matter average molecular weight (Mw) 23000 of white solid.
The T of copolymer (A1-1)DAbout 150 DEG C.
The amount (g) of raw material used in reaction etc., the ratio of components of resulting copolymer and matter average molecular weight (Mw) are shown in table 1
In.
(Production Example 3~5)
Other than being changed to shown in table 1 by the amount (g) of raw material used in reaction etc., it is carried out similarly with Production Example 2
Polymerization, has obtained copolymer (A1-2), (A2-1), (A3-1).The T of each copolymerDIt is each about 150 DEG C.By resulting copolymer
Ratio of components and matter average molecular weight (Mw) be shown in Table 1.
[table 1]
(example 1)
The cyclohexanone addition glass as solvent of the copolymer (A1-1) of 1.0g, the phloroglucin of 0.3g, 4.0g is small
In bottle (20mL), it is sufficiently stirred, uniform solution has been made.By the filter of the PTFE of 0.20 μm of normal pore size of resulting solution
Device is filtered, and is prepared for coating fluid.
(example 2)
The cyclohexanone addition glass as solvent of the copolymer (A1-1) of 1.0g, the phloroglucin of 0.5g, 4.0g is small
In bottle (20mL), it is sufficiently stirred, uniform solution has been made.By the filter of the PTFE of 0.20 μm of normal pore size of resulting solution
Device is filtered, and is prepared for coating fluid.
(example 3~12,15~21)
Other than using copolymer shown in table 2~4, compound, it is prepared for being coated with by method same as example 1
Liquid.
(example 13)
By the copolymer (A2-1) of 0.5g, the copolymer (A3-1) of 0.5g, the phloroglucin of 0.3g, 4.0g be used as solvent
Cyclohexanone be added vial (20mL) in, be sufficiently stirred, uniform solution be made.By resulting solution normal pore size
The filter of 0.20 μm of PTFE is filtered, and is prepared for coating fluid.
(example 14)
Other than using compound shown in table 3, coating fluid is prepared for by method same as example 13.
[evaluation]
Evaluation below has been carried out to coating fluid obtained in example 1~21.As a result it is shown in table 2~4.
(evaluation of release property)
On stainless steel (SUS) plate of 5cm square after cleaning, by spin-coating method applied coating solution, using heating plate with
200 DEG C are heated 30 minutes, to make the mold former with 1 μm of thickness of mold release film.
In the transparent adhesive tape of Scotch (CC1820-Bx-J) of the mold release film surface mount width 19mm of the mold former,
Using 90 ° of electronic stripping testers (day new science Co. Ltd. system), with peeling rate: determining within 15mm/ minutes peel strength (N).
If peel strength in 1.2N hereinafter, if release property it is excellent.
(film hardness)
Pencil hardness test (JIS5600-5-4) is carried out to the face for foring mold release film of above-mentioned mold former.If lead
Hardness is in F or more, then film hardness is excellent.
[table 2]
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Copolymer | A1-1 | A1-1 | A1-1 | A1-1 | A1-1 | A1-1 | A1-1 |
| Compound | B-1 | B-1 | B-2 | B-3 | B-4 | B-5 | B-6 |
| Peel strength (N) | 1 | 0.8 | 1 | 1 | 0.8 | 0.9 | 1 |
| Film hardness | 6H | 6H | 6H | 6H | 6H | 6H | 6H |
[table 3]
| Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 | |
| Copolymer | A1-1 | A1-1 | A1-2 | A1-2 | A1-2 | A2-1, A3-1 | A2-1, A3-1 |
| Compound | B-7 | B-8 | B-1 | B-2 | B-4 | B-4 | B-1 |
| Peel strength (N) | 1.2 | 1.2 | 0.6 | 1 | 0.8 | 0.7 | 0.8 |
| Film hardness | 4H | H | 4H | 4H | 4H | 2H | F |
[table 4]
| Example 15 | Example 16 | Example 17 | Example 18 | Example 19 | Example 20 | Example 21 | |
| Copolymer | A1-1 | A1-1 | A3-1 | A3-1 | A3-1 | A3-1 | A1-2 |
| Compound | Nothing | X-1 | Nothing | B-1 | B-4 | B-8 | Nothing |
| Peel strength (N) | 1.6 | 1.5 | 0.6 | 0.6 | 0.7 | 0.7 | 1.4 |
| Film hardness | 6H | 4H | 2B | 2B | 2B | 2B | 4H |
The peel strength that the adhesive tape of mold release film is formed by by the coating fluid of example 1~14 is small, release property is excellent.In addition,
Film hardness is in F or more, excellent in te pins of durability.
Only have by the coating fluid of the example 15,21 comprising unit (u1)~(u3) but not comprising compound (B), or by using
There is 1 functional group (I) and boiling point is lower than the mold release film that 100 DEG C of compound is formed instead of the coating fluid of the example 16 of compound (B)
Peel strength is big, release property is poor.
The film hardness for the mold release film that coating fluid by being free of the example 17~20 of unit (u2) is formed is low, durability is poor.
The comparison of comparison or example 10~14 and example 21 from example 1~9 and example 15 takes off it is found that by addition compound (B)
The peel strength of mould film becomes smaller.
On the other hand, from the comparison of example 17~20 it is found that do not include unit (u2) in the case where, even if addition chemical combination
Object does not observe the improvement effect of release property yet.
A possibility that being utilized in industry
Resin combination and coating fluid of the invention is anti-in the mold for example with mold release film, the article with nonpolluting coating, band
It is useful in the manufacture of the article of liquid coating etc..
Japanese patent application 2016-126690 specification filing an application 27 days June in 2016 incorporated herein, right
Announcement of the full content of claim and abstract as specification of the invention.
Claims (15)
1. a kind of resin combination, which is characterized in that comprising with following units (u1), following units (u2) and following units
(u3) copolymer (A1) and following compounds (B),
Unit (u1): from the unit of the monomer of the organic group for the fluorine atom for having 1 or more, wherein the monomer
Without blocked isocyanate base and containing the functional group of active hydrogen atom；
Unit (u2): from the unit of the monomer with blocked isocyanate base, wherein the monomer, which does not have, contains reactive hydrogen
The functional group of atom；
Unit (u3): from the unit of the monomer with the functional group containing active hydrogen atom, wherein the monomer does not have envelope
Terminal isocyanate group；
Compound (B): with 2 or more be total to selected from hydroxyl, at least one kind of functional group of amino and carboxyl and its boiling point
More than the sealing end dissociation temperature of the blocked isocyanate base in polymers (A1) and in 400 DEG C of compounds below.
2. resin combination as described in claim 1, which is characterized in that the copolymer (A1) is relative to copolymer (A1)
In whole units with the ratio of 5~40 moles of % include unit (u1), with the ratio of 30~48 moles of % include unit (u2)
With the copolymer for the ratio of 30~48 moles of % including unit (u3).
3. resin combination as claimed in claim 1 or 2, which is characterized in that the matter average molecular weight of the copolymer (A1) is
5000~200000.
4. resin combination according to any one of claims 1 to 3, which is characterized in that the content phase of the compound (B)
The copolymer (A1) for 100 mass parts is 20~60 mass parts.
5. a kind of resin combination, which is characterized in that comprising with following units (u1) and following units (u2) but under not having
State the copolymer (A2) of unit (u3), with the unit (u1) and the unit (u3) but being total to without the unit (u2)
Polymers (A3) and following compounds (B),
Unit (u1): from the unit of the monomer of the organic group for the fluorine atom for having 1 or more, wherein the monomer
Without blocked isocyanate base and containing the functional group of active hydrogen atom；
Unit (u2): from the unit of the monomer with blocked isocyanate base, wherein the monomer, which does not have, contains reactive hydrogen
The functional group of atom；
Unit (u3): from the unit of the monomer with the functional group containing active hydrogen atom, wherein the monomer does not have envelope
Terminal isocyanate group；
Compound (B): with 2 or more be total to selected from hydroxyl, at least one kind of functional group of amino and carboxyl and its boiling point
More than the sealing end dissociation temperature of the blocked isocyanate base in polymers (A2) and in 400 DEG C of compounds below.
6. resin combination as claimed in claim 5, which is characterized in that
The copolymer (A2) is to include unit relative to whole units in copolymer (A2) with the ratio of 5~40 moles of %
It (u1) and with the ratio of 60~95 moles of % include the copolymer of unit (u2)；
The copolymer (A3) is to include unit relative to whole units in copolymer (A3) with the ratio of 5~40 moles of %
It (u1) and with the ratio of 60~95 moles of % include the copolymer of unit (u3).
7. such as resin combination described in claim 5 or 6, which is characterized in that the matter average molecular weight of the copolymer (A2) is
5000~200000, the matter average molecular weight of the copolymer (A3) is 5000~200000.
8. the resin combination as described in any one of claim 5~7, which is characterized in that the content phase of the compound (B)
Total 100 mass parts for the copolymer (A2) and the copolymer (A3) are 20~60 mass parts.
9. such as resin combination according to any one of claims 1 to 8, which is characterized in that the unit (u1) has carbon number 4
The perfluoroalkyl of~6 straight chain has 1~3 etheric oxygen atom between the carbon atom of the perfluoroalkyl of the straight chain of carbon number 4~6
Organic group of the group as the fluorine atom for having 1 or more.
10. such as resin combination according to any one of claims 1 to 9, which is characterized in that the sealing end in the copolymer is different
The sealing end dissociation temperature of cyanic acid ester group is 120~200 DEG C.
11. such as resin combination according to any one of claims 1 to 10, which is characterized in that the compound (B) has virtue
Ring.
12. a kind of coating fluid, which is characterized in that include resin combination and solvent described in any one of claim 1~11.
13. coating fluid as claimed in claim 12, which is characterized in that the content ratio of the solvent is relative to the total of coating fluid
Quality is 70~99.9 mass %.
14. a kind of mold with mold release film, which is characterized in that have on the surface of mold by any one of claim 1~10
The mold release film that the resin combination is formed.
15. a kind of manufacturing method of the mold with mold release film, which is characterized in that described in the surface of mold coating claim 12
Coating fluid, heated with temperature more than the sealing end dissociation temperature of blocked isocyanate base to form mold release film, obtain band
The mold of mold release film.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016126690 | 2016-06-27 | ||
| JP2016-126690 | 2016-06-27 | ||
| PCT/JP2017/021023 WO2018003432A1 (en) | 2016-06-27 | 2017-06-06 | Resin composition, coating liquid, release film-equipped mold, and method for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109415550A true CN109415550A (en) | 2019-03-01 |
Family
ID=60786861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780039821.8A Pending CN109415550A (en) | 2016-06-27 | 2017-06-06 | Resin combination, coating fluid, the mold with mold release film and its manufacturing method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2018003432A1 (en) |
| KR (1) | KR20190022459A (en) |
| CN (1) | CN109415550A (en) |
| WO (1) | WO2018003432A1 (en) |
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|---|---|---|---|---|
| JP7345477B2 (en) * | 2018-08-23 | 2023-09-15 | 株式会社ネオス | Heat-resistant mold release agent composition |
| CN116829643A (en) * | 2021-06-21 | 2023-09-29 | 积水化学工业株式会社 | (meth) acrylic resin composition, inorganic fine particle dispersion slurry composition, and inorganic fine particle dispersion molded article |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06279687A (en) * | 1993-03-24 | 1994-10-04 | Asahi Glass Co Ltd | Antifouling processing agent |
| CN1149326A (en) * | 1994-05-26 | 1997-05-07 | 美国3M公司 | Fluorine containing oil- and water-repellent compositions |
| JP2002256130A (en) * | 2001-03-02 | 2002-09-11 | Asahi Glass Co Ltd | Water- and oil-repellent agent composition |
| WO2010061964A1 (en) * | 2008-11-28 | 2010-06-03 | 新日本製鐵株式会社 | Chromate-free surface-treated metal material |
| WO2011062093A1 (en) * | 2009-11-17 | 2011-05-26 | 住友化学株式会社 | Optical and thermal energy crosslinkable insulating layer material for organic thin film transistor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5023133B2 (en) | 2009-10-27 | 2012-09-12 | Ａｇｃセイミケミカル株式会社 | Release agent composition |
-
2017
- 2017-06-06 JP JP2018524996A patent/JPWO2018003432A1/en not_active Withdrawn
- 2017-06-06 CN CN201780039821.8A patent/CN109415550A/en active Pending
- 2017-06-06 WO PCT/JP2017/021023 patent/WO2018003432A1/en active Application Filing
- 2017-06-06 KR KR1020187031063A patent/KR20190022459A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06279687A (en) * | 1993-03-24 | 1994-10-04 | Asahi Glass Co Ltd | Antifouling processing agent |
| CN1149326A (en) * | 1994-05-26 | 1997-05-07 | 美国3M公司 | Fluorine containing oil- and water-repellent compositions |
| JP2002256130A (en) * | 2001-03-02 | 2002-09-11 | Asahi Glass Co Ltd | Water- and oil-repellent agent composition |
| WO2010061964A1 (en) * | 2008-11-28 | 2010-06-03 | 新日本製鐵株式会社 | Chromate-free surface-treated metal material |
| CN102227517B (en) * | 2008-11-28 | 2014-04-02 | 新日铁住金株式会社 | Chromate-free surface-treated metal material |
| WO2011062093A1 (en) * | 2009-11-17 | 2011-05-26 | 住友化学株式会社 | Optical and thermal energy crosslinkable insulating layer material for organic thin film transistor |
| CN102612752A (en) * | 2009-11-17 | 2012-07-25 | 住友化学株式会社 | Optical and thermal energy crosslinkable insulating layer material for organic thin film transistor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2018003432A1 (en) | 2019-05-16 |
| KR20190022459A (en) | 2019-03-06 |
| WO2018003432A1 (en) | 2018-01-04 |
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