CN119487082A - Method for producing fluorinated copolymer, method for producing powder coating, and method for producing coated article - Google Patents
Method for producing fluorinated copolymer, method for producing powder coating, and method for producing coated article Download PDFInfo
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- CN119487082A CN119487082A CN202380051214.9A CN202380051214A CN119487082A CN 119487082 A CN119487082 A CN 119487082A CN 202380051214 A CN202380051214 A CN 202380051214A CN 119487082 A CN119487082 A CN 119487082A
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- China
- Prior art keywords
- fluorocopolymer
- producing
- vinyl ether
- amount
- polymerization
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- 238000000576 coating method Methods 0.000 title claims abstract description 115
- 239000011248 coating agent Substances 0.000 title claims abstract description 114
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 99
- 239000000843 powder Substances 0.000 title claims abstract description 40
- 229920001577 copolymer Polymers 0.000 title claims abstract description 17
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000000178 monomer Substances 0.000 claims abstract description 96
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 90
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 78
- 150000001875 compounds Chemical class 0.000 claims abstract description 67
- 125000003386 piperidinyl group Chemical group 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 41
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 41
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 41
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 21
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 40
- 125000005936 piperidyl group Chemical group 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 4
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- 239000000203 mixture Substances 0.000 description 33
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- 239000008096 xylene Substances 0.000 description 24
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 19
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 17
- DQNSRQYYCSXZDF-UHFFFAOYSA-N 1,4-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1CCC(COC=C)CC1 DQNSRQYYCSXZDF-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
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- 238000009826 distribution Methods 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
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- 230000008859 change Effects 0.000 description 6
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- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 3
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 2
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
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- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 2
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- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
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- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
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- 239000004033 plastic Substances 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- 229940036248 turpentine Drugs 0.000 description 1
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Classifications
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/24—Trifluorochloroethene
-
- 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
-
- 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
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
提供：能制造热稳定性优异、用于形成涂膜时涂膜的光泽性优异、且涂膜的着色被进一步抑制的含氟共聚物的、含氟共聚物的制造方法、粉体涂料的制造方法和涂装物品的制造方法。本发明的含氟共聚物的制造方法制造包含基于氯三氟乙烯的单元和基于乙烯基醚的单元的含氟共聚物，所述制造方法中，使用自由基聚合引发剂、含哌啶基化合物和水滑石，使包含氯三氟乙烯和乙烯基醚的单体进行聚合来制造含氟共聚物，含哌啶基化合物中的哌啶基的摩尔量相对于单体的全部用量的摩尔量的比为0.0032～0.010，水滑石的用量相对于含哌啶基化合物的用量的质量比为0.3以上且低于4.6，使聚合开始后，向反应体系内连续地或间断地供给氯三氟乙烯和乙烯基醚。Provided are a method for producing a fluorinated copolymer which is excellent in thermal stability, excellent in glossiness of a coating film when used to form a coating film, and further suppresses coloring of the coating film, a method for producing a fluorinated copolymer, a method for producing a powder coating, and a method for producing a coated article. The method for producing a fluorinated copolymer of the present invention produces a fluorinated copolymer containing units based on chlorotrifluoroethylene and units based on vinyl ether, wherein the fluorinated copolymer is produced by polymerizing monomers containing chlorotrifluoroethylene and vinyl ether using a radical polymerization initiator, a piperidinyl-containing compound, and hydrotalcite, wherein the molar amount of the piperidinyl group in the piperidinyl-containing compound relative to the molar amount of the total amount of the monomers used is 0.0032 to 0.010, and the mass ratio of the amount of the hydrotalcite used relative to the amount of the piperidinyl-containing compound used is 0.3 or more and less than 4.6, and after the start of polymerization, chlorotrifluoroethylene and vinyl ether are continuously or intermittently supplied to the reaction system.
Description
Technical Field
The present invention relates to a method for producing a fluorocopolymer, a method for producing a powder coating material, and a method for producing a coated article.
Background
The coating material containing the fluorocopolymer can form a coating film excellent in weather resistance. As a method for producing such a fluorocopolymer, patent document 1 discloses a method in which a fluoroolefin, a monomer having a crosslinkable group, and a monomer having no fluorine atom or crosslinkable group are used in the presence of a piperidyl-containing compound and an organic solvent to obtain a fluorocopolymer.
Prior art literature
Patent literature
Patent document 1 International publication No. 2014/054545
Disclosure of Invention
Problems to be solved by the invention
Further improvement of thermal stability, in which the molecular weight is not increased by heat, is demanded for the fluorocopolymer to be used as a coating material. Further, further improvement is also required for the glossiness and coloring of the formed coating film.
The present inventors have evaluated the fluorocopolymer described in patent document 1, and as a result, have found that there is room for improvement in the thermal stability of the fluorocopolymer, and in the gloss and coloration of the formed coating film.
The present invention provides a method for producing a fluorocopolymer which can produce a fluorocopolymer which is excellent in heat stability, excellent in gloss of a coating film when used for forming a coating film, and further suppressed in coloring of the coating film. The present invention also provides a method for producing a powder coating material comprising the fluorocopolymer and a method for producing a coated article using the powder coating material.
Solution for solving the problem
The present inventors have conducted intensive studies with respect to the above-mentioned problems, and as a result, have found that in a method for producing a fluorocopolymer comprising chlorotrifluoroethylene units and vinyl ether units by polymerizing monomers comprising chlorotrifluoroethylene and vinyl ether using a radical polymerization initiator, a piperidyl-containing compound and hydrotalcite, a fluorocopolymer having a molar ratio of the molar amount of piperidyl groups in the piperidyl-containing compound to the molar amount of the entire amount of monomers of 0.0032 to 0.010 and a mass ratio of the amount of hydrotalcite to the amount of the piperidyl-containing compound of 0.3 or more and less than 4.6 is obtained by continuously or intermittently supplying chlorotrifluoroethylene and vinyl ether into a reaction system after the start of polymerization, whereby a fluorocopolymer having excellent thermal stability, excellent gloss of a coating film when used for forming a coating film and further suppressed coloring of the coating film when used for forming a coating film is obtained.
That is, the inventors have found that the above problems can be solved by the following configuration.
[1] A process for producing a fluorocopolymer comprising chlorotrifluoroethylene units and vinyl ether units, wherein the fluorocopolymer is produced by polymerizing monomers comprising chlorotrifluoroethylene and vinyl ether using a radical polymerization initiator, a piperidyl-containing compound and hydrotalcite, wherein the ratio of the molar amount of piperidyl groups in the piperidyl-containing compound to the molar amount of the total amount of the monomers is from 0.0032 to 0.010, and the mass ratio of the amount of hydrotalcite to the amount of the piperidyl-containing compound is from 0.30 to less than 4.60, and wherein the chlorotrifluoroethylene and the vinyl ether are continuously or intermittently supplied into a reaction system after the initiation of the polymerization.
[2] The method for producing a fluorocopolymer according to [1], wherein the fluorocopolymer is produced by conducting the polymerization in a reactor, and a solvent and the monomer are present in the reactor before the initiation of the polymerization, and a ratio of a total molar amount of the monomers to a molar amount of the solvent in the reactor before the initiation of the polymerization is 0.30 or more.
[3] The method for producing a fluorocopolymer according to [1] or [2], wherein the vinyl ether contains at least a vinyl ether having a crosslinkable group.
[4] The method for producing a fluorocopolymer according to [3], wherein the crosslinkable group is a hydroxyl group or a carboxyl group.
[5] The method for producing a fluorocopolymer according to [3], wherein the amount of the vinyl ether having a crosslinkable group is 1 to 20 mol% based on the total amount of the monomers.
[6] The method for producing a fluorocopolymer as described in [1] or [2], wherein the vinyl ether comprises a vinyl ether having a crosslinkable group and a vinyl ether having no crosslinkable group, and the amount of the vinyl ether having no crosslinkable group is 1 to 70 mol% based on the total amount of the monomers.
[7] The method for producing a fluorocopolymer as described in [1] or [2], wherein the molar ratio of the amount of chlorotrifluoroethylene to the total amount of the monomers is 30 to 70 mol%.
[8] The method for producing a fluorocopolymer as described in [1] or [2], wherein the fluorocopolymer has a weight average molecular weight of 10000 to 60000.
[9] A method for producing a powder coating material, wherein the fluorocopolymer produced by the method for producing a fluorocopolymer as described in [1] or [2] is used for producing a powder coating material.
[10] A method for producing a coated article, characterized by applying the powder coating produced by the method for producing a powder coating according to [9] to a surface of a substrate to form a coating layer, and melt-curing the coating layer to form a coating film.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a method for producing a fluorocopolymer which can produce a fluorocopolymer which is excellent in heat stability, excellent in gloss of a coating film when used for forming a coating film, and further suppressed in coloring of the coating film. The present invention also provides a method for producing a powder coating material comprising the fluorocopolymer and a method for producing a coated article using the powder coating material.
Detailed Description
The meaning of terms in the present invention is as follows.
The numerical range indicated by "-" means a range including the numerical values described before and after "-" as the lower limit value and the upper limit value. In the numerical ranges described in stages in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in other stages. In the numerical ranges described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
In the present specification, 1 kind of substance belonging to each component may be used alone, or 2 or more kinds may be used in combination. Here, when 2 or more kinds of substances are used in combination for each component, the content of the component is not particularly limited as long as it is the total content of the substances used in combination.
In the present specification, a combination of 2 or more preferred embodiments is a more preferred embodiment.
The unit refers to a generic term of an atomic group based on the 1 molecule of the monomer directly formed by polymerization of the monomer and an atomic group obtained by chemically converting a part of the atomic group. The content (mol%) of each unit relative to all units contained in the polymer is determined by analyzing the polymer by nuclear magnetic resonance spectroscopy, and may be determined by the amount of the component to be added when the polymer is produced.
(Meth) acrylic acid is a generic term for acrylic acid and methacrylic acid.
The hydrolyzable silyl group is a group capable of undergoing a hydrolysis reaction to form a silanol group.
The acid value and the hydroxyl value were measured according to the method of JIS K0070-3 (1992), respectively.
The glass transition temperature (Tg) is the mid-point glass transition temperature of a polymer as determined by Differential Scanning Calorimetry (DSC).
The melt viscosity is a value of the melt viscosity at 170℃of the sample when the temperature is raised from 130℃to 200℃at a temperature rise rate of 10℃per minute by using a rotary rheometer.
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by size exclusion chromatography (gel permeation chromatography) using polystyrene as a standard substance. In addition, the ratio of Mw to Mn represents the molecular weight distribution, also referred to as Mw/Mn.
The average particle diameter of the particles is a value of 50% of the particle diameter obtained by calculating the volume average from the particle size distribution measured by using a known particle size distribution measuring apparatus (trade name Helos-Rodos, etc. of Sympatec corporation) using a laser diffraction method as a measurement principle.
The film thickness was measured using an eddy current film thickness meter (SANKO ELECTRONIC LABORATORY co., ltd. Trade name EDY-5000, etc.).
The method for producing a fluorocopolymer comprises polymerizing a monomer comprising chlorotrifluoroethylene and a vinyl ether, using a radical polymerization initiator, a piperidyl-containing compound and hydrotalcite, wherein the ratio of the molar amount of the piperidyl groups in the piperidyl-containing compound to the molar amount of the total amount of the monomers is 0.0032 to 0.010, and the mass ratio of the amount of the hydrotalcite to the amount of the piperidyl-containing compound is 0.30 or more and less than 4.60, and the chlorotrifluoroethylene and the vinyl ether are continuously or intermittently supplied into the reaction system after the start of the polymerization.
In the present specification, the monomer means both a system comprising only 1 monomer and a system comprising 2 or more monomers.
Hereinafter, the fluorocopolymer produced by the production method will be described, and the production method will be described.
The fluorocopolymer produced by the present production method (hereinafter, also referred to as a specific fluorocopolymer) comprises units based on chlorotrifluoroethylene (CF 2 =cfcl) and units based on vinyl ether.
The content of the chlorotrifluoroethylene-based unit is preferably 30 to 70 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol% based on the total repeating units of the specific fluorocopolymer, from the viewpoint that the weather resistance of a coating film obtained by using the specific fluorocopolymer is more excellent.
The vinyl ether may be a vinyl ether having a crosslinkable group or a vinyl ether having no crosslinkable group.
The vinyl ether preferably has a crosslinkable group, from the viewpoint of further improving the hardness of a coating film obtained by using a specific fluorocopolymer.
Specific examples of the crosslinkable group include at least 1 group selected from the group consisting of a hydroxyl group, an amino group, an epoxy group, an oxetanyl group, a hydrolyzable silyl group, a sulfo group and a carboxyl group, and from the viewpoint that the hardness of a coating film obtained by using a specific fluorocopolymer can be further improved, hydroxyl groups or carboxyl groups are preferable, and hydroxyl groups are more preferable. The sulfo group and the carboxyl group may be ionized to form-SO 3 - or-COO -, or may be salified with a cation to form-SO 3 -Na+ or-COO -Na+, or the like.
The number of crosslinkable groups may be 1 or 2 or more. The crosslinkable group may be used in combination of 2 or more kinds.
The vinyl ether may be used in combination of 2 or more, and among them, a vinyl ether having a crosslinkable group and a vinyl ether having no crosslinkable group are preferably used in combination.
The vinyl ether may or may not have a fluorine atom, but preferably does not have a fluorine atom.
The vinyl ether having a crosslinkable group may be used in combination of 2 or more.
The vinyl ether having a crosslinkable group is preferably a vinyl ether having a hydroxyl group or a vinyl ether having a carboxyl group, and more preferably a vinyl ether having a hydroxyl group, from the viewpoint that the hardness of a coating film obtained by using a specific fluorocopolymer can be further improved.
The vinyl ether having no crosslinkable group may be used in combination of 2 or more.
Specific examples of the vinyl ether having a hydroxyl group include CH2＝CHO-CH2-cycloC6H10-CH2OH、CH2＝CHOCH2CH2OH、CH2＝CHOCH2CH2CH2CH2OH.
The bonding site of "-cycloC 6H10 -" means cyclohexylene and "-cycloC 6H10 -" is usually 1,4-.
The vinyl ether having a hydroxyl group may be used in combination of 2 or more.
Specific examples of the vinyl ether having a carboxyl group include monomers represented by CH 2＝CHO(CH2)n12OC(O)CH2CH2 COOH (wherein n12 represents an integer of 1 to 10).
The vinyl ether having a carboxyl group may be used in combination of 2 or more.
Specific examples of vinyl ethers having no crosslinkable group include ethyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, and cyclohexylmethyl vinyl ether.
The content of the vinyl ether-based unit is preferably 1 to 80 mol%, more preferably 10 to 70 mol%, still more preferably 20 to 60 mol% based on the total repeating units of the specific fluorocopolymer.
When the vinyl ether-based unit includes a unit based on a vinyl ether having a crosslinkable group, the content of the unit based on a vinyl ether having a crosslinkable group is preferably 1 to 20 mol%, more preferably 3 to 20 mol%, and even more preferably 5 to 15 mol% with respect to the total of the repeating units of the specific fluorocopolymer, from the viewpoint that the hardness of the coating film obtained by using the specific fluorocopolymer can be further improved.
When the vinyl ether-based unit contains a unit based on a vinyl ether having no crosslinkable group, the content of the unit based on a vinyl ether having no crosslinkable group is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, and even more preferably 10 to 50 mol% with respect to the total repeating units of the specific fluorocopolymer, from the viewpoint that the smoothness of a coating film obtained by using the specific fluorocopolymer can be further improved.
The specific fluorocopolymer may contain units other than chlorotrifluoroethylene units and vinyl ether units (hereinafter also referred to as other units), and it is preferable that the coating film obtained by using the specific fluorocopolymer contains substantially no other units, because the coating film is more excellent in weatherability.
Here, the substantial absence of other units means that the content of other units is 0.1 mol% or less with respect to the total of the repeating units of the specific fluorocopolymer.
Specific examples of the other units include units based on fluoroolefins other than chlorotrifluoroethylene and units based on vinyl esters.
The specific fluorocopolymer preferably has no carboxyl group, from the viewpoint that the hardness of a coating film obtained by using the specific fluorocopolymer can be further improved. In this case, the specific fluorocopolymer preferably has hydroxyl groups.
The specific fluorocopolymer preferably comprises units based on chlorotrifluoroethylene, units based on vinyl ethers having crosslinkable groups and units based on vinyl ethers having no crosslinkable groups, and more preferably is a fluorocopolymer formed from only units based on chlorotrifluoroethylene, units based on vinyl ethers having crosslinkable groups and units based on vinyl ethers having no crosslinkable groups.
The specific fluorocopolymer preferably contains 30 to 70 mol%, 1 to 20 mol%, 1 to 70 mol%, more preferably 45 to 55 mol%, 5 to 15 mol%, and 10 to 50 mol% of units based on chlorotrifluoroethylene, units based on vinyl ether having a crosslinkable group, and units based on vinyl ether having no crosslinkable group, in this order, relative to all units contained in the specific fluorocopolymer.
The Tg of the specific fluorocopolymer is preferably 30 to 60 ℃, more preferably 35 to 60 ℃, and even more preferably 40 to 55 ℃ in view of further improvement in blocking resistance of a powder coating material containing the specific fluorocopolymer and surface smoothness of a coating film obtained by using the powder coating material.
The melt viscosity of the specific fluorocopolymer at 170℃is preferably 10 to 450 Pa.s, more preferably 30 to 450 Pa.s, still more preferably 40 to 400 Pa.s.
When the specific fluorocopolymer has a hydroxyl value, the hydroxyl value of the specific fluorocopolymer is preferably more than 0mgKOH/g and less than 150mgKOH/g, more preferably 5 to 100mgKOH/g, still more preferably 15 to 70mgKOH/g, particularly preferably 30 to 60mgKOH/g.
When the specific fluorocopolymer has an acid value, the acid value of the specific fluorocopolymer preferably exceeds 0mgKOH/g and is lower than 10mgKOH/g, more preferably 2 to 8mgKOH/g, still more preferably 3 to 7mgKOH/g.
In view of the more excellent effect of the present invention, the Mw of the specific fluorocopolymer is preferably 10000 to 60000, more preferably 15000 to 55000, and even more preferably 20000 to 50000.
In view of the more excellent effect of the present invention, the Mn of the specific fluorocopolymer is preferably 5000 to 20000, more preferably 6000 to 18000, and still more preferably 7000 to 16000.
In view of the more excellent effect of the present invention, the Mw/Mn (molecular weight distribution) of the specific fluorocopolymer is preferably 2.0 to 3.5, more preferably 2.3 to 3.3, still more preferably 2.5 to 3.2.
As an example of the method for adjusting Mw/Mn of the specific fluorocopolymer, there can be mentioned a method for adjusting the amounts of the piperidyl group-containing compound, hydrotalcite and the like, and a method for continuously or intermittently supplying chlorotrifluoroethylene and vinyl ether into the reaction system after the start of polymerization of the monomer containing chlorotrifluoroethylene and vinyl ether.
The specific fluorocopolymer may be used as a component of a coating material. The coating material prepared from the specific fluorocopolymer may be any of a solvent-based coating material obtained by dissolving the specific fluorocopolymer in an organic solvent, an aqueous coating material obtained by dispersing the specific fluorocopolymer in water, and a powder coating material containing a powder of the specific fluorocopolymer, and a powder coating material is preferable.
As described above, the present production method is a production method of a fluorine-containing copolymer, in which a monomer containing chlorotrifluoroethylene and a vinyl ether is polymerized using a radical polymerization initiator, a piperidyl-containing compound, and hydrotalcite to produce a fluorine-containing copolymer containing a chlorotrifluoroethylene-based unit and a vinyl ether-based unit.
In the present production method, a ratio of the molar amount of the piperidinyl groups in the piperidinyl group-containing compound to the molar amount of the entire amount of the monomers (hereinafter, also referred to as a ratio Pg/m.) is 0.0032 to 0.010, and a mass ratio of the hydrotalcite to the amount of the piperidinyl group-containing compound (hereinafter, also referred to as a ratio H/Pc.) is 0.30 or more and less than 4.60, and chlorotrifluoroethylene and vinyl ether are continuously or intermittently supplied into the reaction system after the start of polymerization, whereby a fluorine-containing copolymer having excellent thermal stability, excellent gloss of a coating film when used for forming a coating film, and further suppressed coloring of the coating film when used for forming a coating film can be produced. The reason for this is not necessarily clear, but is considered as follows.
It is presumed that by setting the ratio Pg/M to the lower limit value or more, the change (the increase in the molecular weight) of the fluorocopolymer, which may be one of factors causing gelation of the fluorocopolymer, can be suppressed even in a high-temperature environment, and the thermal stability of the fluorocopolymer is improved.
It is presumed that coloring derived from the piperidinyl-containing compound in a coating film formed using the fluorocopolymer is suppressed by setting the ratio Pg/M to the upper limit or less.
It is presumed that by setting the ratio H/Pc to be within the above range, unwanted side reactions in the polymerization of the monomer are suppressed, the molecular weight of the fluorocopolymer becomes more uniform, and the fluorocopolymer with suppressed generation of foreign matters when the fluorocopolymer is used for forming a coating film is produced, and as a result, the glossiness of the coating film is improved.
It is also presumed that the molecular weight of the fluorocopolymer becomes more uniform by continuous or intermittent supply of chlorotrifluoroethylene and vinyl ether into the reaction system after the start of polymerization of the monomer containing chlorotrifluoroethylene and vinyl ether, and the gloss of the coating film formed by using the fluorocopolymer is improved.
The components used in the production of the specific fluorocopolymer in the present production method will be described.
In the present production method, at least a monomer containing chlorotrifluoroethylene and a vinyl ether, a radical polymerization initiator, a piperidyl group-containing compound, and hydrotalcite are used.
The chlorotrifluoroethylene and vinyl ether used in the present production method are each as described for the above specific fluorocopolymer, and the same applies to the above specific fluorocopolymer.
The suitable manner of the amount of chlorotrifluoroethylene to be used in the entire amount of the monomer in the present production method is the same as the suitable manner of the content of chlorotrifluoroethylene based on the entire repeating units of the above-mentioned specific fluorocopolymer. That is, the amount of chlorotrifluoroethylene to be used is preferably 30 to 70 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol% based on the total amount of the monomers.
In the present production method, the suitable modes of the amount of vinyl ether, the amount of vinyl ether having a crosslinkable group, and the amount of vinyl ether having no crosslinkable group with respect to the total amount of monomers are the same as the suitable modes of the content of vinyl ether-based units, the content of vinyl ether-based units having a crosslinkable group, and the content of vinyl ether-based units having no crosslinkable group with respect to the total repeating units of the specific fluorocopolymer.
In the present production method, monomers other than chlorotrifluoroethylene and vinyl ether may be used, but from the viewpoint of further excellent effects of the present invention, it is preferable to use only chlorotrifluoroethylene and vinyl ether as monomers.
In the present production method, a monomer containing chlorotrifluoroethylene, a vinyl ether having a crosslinkable group, and a vinyl ether having no crosslinkable group is preferably used, and a monomer containing chlorotrifluoroethylene, a vinyl ether having a crosslinkable group, and a vinyl ether having no crosslinkable group alone is more preferably used.
The suitable manner of the respective amounts of chlorotrifluoroethylene, vinyl ether having a crosslinkable group, and vinyl ether having no crosslinkable group relative to the total amount of monomers is the same as the suitable manner of the respective contents of chlorotrifluoroethylene-based units, vinyl ether having a crosslinkable group, and vinyl ether having no crosslinkable group relative to the total units contained in the above-mentioned specific fluorocopolymer.
In the present production method, a piperidinyl group-containing compound is used. The piperidinyl group-containing compound is a compound having a piperidinyl group or a piperidinyl group having a substituent. As the piperidinyl group-containing compound, a compound having a piperidinyl group having a substituent is preferable.
The substituted piperidinyl group is preferably a tetrasubstituted piperidinyl group, and more preferably a 2, 6-tetrasubstituted piperidinyl group.
The piperidinyl group-containing compound is preferably a piperidinyl group-containing compound having 2 or more piperidinyl groups or piperidinyl groups having substituents in 1 molecule.
The piperidyl group-containing compound may be used in an amount of 2 or more, preferably 2 or more.
The piperidyl-containing compound is preferably a compound represented by the following formula (a compound having a 2, 6-tetrasubstituted piperidyl group).
[ Chemical 1]
R 11～R14 is independently an alkyl group (methyl, ethyl, propyl, dodecyl, stearyl, etc.), a cycloalkyl group (cyclopentyl, cyclohexyl, etc.), a substituted alkyl group (2-hydroxyethyl, 2-methoxycarbonylethyl, 3-hydroxypropyl, etc.), an aryl group (phenyl, naphthyl, etc.), or an aralkyl group (phenethyl, benzyl, etc.), R 11 and R 12, or R 13 and R 14 may form an aliphatic ring having 3 to 6 carbon atoms. R 11～R14 is preferably an alkyl group having 1 to 18 carbon atoms, more preferably a methyl group, from the viewpoints of price and ease of acquisition.
R 15 is a hydrogen atom, an alkyl group (methyl, ethyl, propyl, butyl, dodecyl, stearyl, etc.), a substituted alkyl group (2-hydroxyethyl, 2-methoxycarbonylethyl, 2-acetoxyethyl, 2- (3-methoxycarbonylpropionyloxy) ethyl, 3-hydroxypropyl, etc.), an aryl group (phenyl, naphthyl, hydroxyphenyl, etc.), an aralkyl group (phenethyl, benzyl, hydroxyphenylalkyl, etc.), or a cycloalkyl group (cyclohexyl, etc.).
R 16 is a hydrogen atom, a hydroxyl group, an alkyl group (methyl, ethyl, propyl, butyl, dodecyl, stearyl, etc.), a substituted alkyl group (2-hydroxyethyl, 2-methoxycarbonylethyl, 2-acetoxyethyl, 2- (3-methoxycarbonylpropionyloxy) ethyl, 3-hydroxypropyl, etc.), an aryl group (phenyl, naphthyl, etc.), an aralkyl group (phenethyl, benzyl, etc.), a group containing an ester bond (acetoxy, propionyloxy, butyryloxy, lauryloxy, substituted alkylcarbonyloxy, benzoyloxy, substituted benzoyloxy, etc.), an amino-containing group (alkoxycarbonylamino, N-monoalkylcarbamoylamino, N-dialkylcarbamoylamino, etc.), or a group containing a2, 6-tetrasubstituted piperidinyl group. For R 16, more than 2 of these groups may be combined.
As a specific example of the piperidinyl-containing compound, examples thereof include 2, 6-tetramethylpiperidine, 1,2, 6-pentamethylpiperidine, 4-hydroxy-2, 6-tetramethylpiperidine, 4-hydroxy-1, 2, 6-pentamethylpiperidine, 1-ethyl-2, 6-tetramethylpiperidine, 1-ethyl-4-hydroxy-2, 6-tetramethylpiperidine, 1-butyl-4-hydroxy-2, 6-tetramethylpiperidine 1-dodecyl-2, 6-tetramethylpiperidine, 1-phenyl-2, 6-tetramethylpiperidine, 1- (2-hydroxyethyl) -2, 6-tetramethylpiperidine, 1- (6-hydroxyethyl) -4-hydroxy-2, 6-tetramethylpiperidine, 4-acetoxy-2, 6-tetramethylpiperidine 1-dodecyl-2, 6-tetramethylpiperidine, 1-phenyl-2, 6-tetramethylpiperidine, 1- (2-hydroxyethyl) -2, 6-tetramethylpiperidine 1- (6-hydroxyethyl) -4-hydroxy-2, 6-tetramethylpiperidine, 4-acetoxy-2, 6-tetramethylpiperidine, methyl 1,2, 6-pentamethyl-4-piperidyl sebacate, bis (2, 6-tetramethyl-4-piperidyl) sebacate.
Examples of the piperidinyl group-containing compound in which R 16 is a group containing 2, 6-tetrasubstituted piperidinyl group include: 2, 6-tetramethylpiperidine (4-hydroxy-2, 6-tetramethylpiperidine, 4-hydroxy-1, 2, 6-pentamethylpiperidine, 1- (2-hydroxyethyl) -4-hydroxy-2, 6-tetramethylpiperidine, 1- (2-hydroxyethyl) -2, 6-tetramethylpiperidine, etc.) having a hydroxyl group is reacted with a polybasic acid (succinic acid, adipic acid, etc.) sebacic acid, azelaic acid, decane-1, 10-dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, malonic acid, substituted malonic acids, etc.), a piperidinyl group-containing compound containing 2 or more 2, 6-tetramethylpiperidinyl groups in 1 molecule, specifically, the compounds represented by the following formula are exemplified.
Wherein n3 is an integer of 1 to 20.
[ Chemical 2]
In the present production method, the ratio (ratio Pg/M) of the molar amount of the piperidinyl groups in the piperidinyl group-containing compound to the molar amount of the total amount of the monomers used (total molar amount of the total monomers used in polymerization) is 0.0032 to 0.010. In terms of the excellent effect of the present invention, the ratio Pg/M is preferably 0.0040 to 0.0090, more preferably 0.0050 to 0.0080.
In the present production method, hydrotalcite is used. Hydrotalcite refers to a layered composite hydroxide represented by the following formula.
[Mg2+ 1-xAl3+ x(OH)2]x+[CO3 2 -x/2·mH2O]x-
Wherein x is 0.2 to 0.33 and m is 0 to 2.
From the viewpoint of excellent adsorption of chloride ions and easy availability, hydrotalcite is preferably Mg 6Al2(OH)16CO3·4H2 O (in the formula indicating hydrotalcite, x=0.25 and m=0.5) or Mg 4.5Al2(OH)13CO3·3.5H2 O (in the formula indicating hydrotalcite, x=0.308 and m=0.538).
More than 2 kinds of hydrotalcite may be used.
The particle size of hydrotalcite is preferably 5 to 500. Mu.m, more preferably 5 to 110. Mu.m. If the particle size of hydrotalcite is 5 μm or more, removal by filtration becomes easy. If the particle diameter of hydrotalcite is 500 μm or less, the surface area per unit mass is large, and the effect of hydrotalcite is further exhibited.
The particle size of hydrotalcite was measured according to "method of screening test for chemicals" of JIS K0069.
In the present production method, the mass ratio of the amount of hydrotalcite to the total amount of monomers (total amount of all monomers used in polymerization) is preferably 0.001 to 0.050, more preferably 0.003 to 0.030. If the above ratio falls within the above range, the molecular weight distribution of the resulting fluorocopolymer can be further reduced.
In the present production method, the mass ratio (ratio H/Pc) of the amount of hydrotalcite to the amount of the piperidinyl-containing compound is 0.30 or more and less than 4.60. In terms of the excellent effect of the present invention, the ratio H/Pc is preferably 0.50 to 2.00, more preferably 0.80 to 1.50.
In the present production method, a radical polymerization initiator is used for polymerization of the monomer.
Examples of the radical polymerization initiator include peroxide initiators and azo initiators.
Specific examples of the peroxide initiator include cyclohexanone peroxide, t-butyl hydroperoxide, dibenzoyl peroxide, di-t-butyl peroxide, 2-di (t-butyl peroxy) butane, t-butyl peroxypivalate, and diisopropyl peroxydicarbonate.
Specific examples of azo initiators include 2,2 '-azobisisobutyronitrile, 1' -azobicyclohexane-1-carbonitrile, 2 '-azobis (2, 4-dimethylvaleronitrile), and 2,2' -azobis (2-methylbutyronitrile).
The radical polymerization initiator may be used in combination of 2 or more.
In the present production method, the ratio of the molar amount of the polymerization initiator to the molar amount of the entire amount of the monomer is preferably 0.05 to 1.5, more preferably 0.1 to 1.0.
The polymerization method of the monomer in the present production method includes solution polymerization, emulsion polymerization, suspension polymerization, and the like, and solution polymerization is preferable. Therefore, in the present production method, a solvent (polymerization solvent) is preferably used for polymerization of the monomer.
Examples of the solvent include an organic solvent, water and a mixed solvent thereof, and the organic solvent is preferable in view of ease of producing the fluorocopolymer.
The organic solvent is preferably 1 or more organic solvents selected from the group consisting of aromatic hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and ether ester solvents.
Specific examples of the aromatic hydrocarbon solvent include toluene, xylene, ethylbenzene, aromatic naphtha, tetrahydronaphthalene, and turpentine. As the aromatic hydrocarbon solvent, commercially available ones can be used, and SOLVESSO (registered trademark) #100 (Exxon Mobil Corporation), SOLVESSO (registered trademark) #150 (Exxon Mobil Corporation) and the like can be used.
Specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diisobutyl ketone, cyclohexanone and isophorone.
Specific examples of the ester-based solvent include methyl acetate, ethyl acetate, n-propyl acetate, isobutyl acetate and t-butyl acetate.
Specific examples of the alcohol solvent include ethanol, t-butanol, and isopropanol.
Specific examples of the ether ester solvents include ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, and methoxybutyl acetate.
The organic solvent may be used in combination of 2 or more.
In the present production method, after polymerization of a monomer containing chlorotrifluoroethylene and a vinyl ether is started, chlorotrifluoroethylene and a vinyl ether are continuously or intermittently supplied into a reaction system.
Thus, the concentration of chlorotrifluoroethylene and vinyl ether in the reaction system is easily kept constant during the polymerization reaction, and thus a fluorocopolymer having more uniform molecular weight and having more excellent effects of the present invention can be produced.
In the present production method, the kind of vinyl ether present before the start of polymerization is the same as the kind of vinyl ether added to the reaction system after the start of polymerization.
The reaction system is a system that contains chlorotrifluoroethylene and vinyl ether and that undergoes polymerization, and is present in a reactor, for example.
As the start time of the polymerization, a time at which the reactor in which chlorotrifluoroethylene, vinyl ether and a radical polymerization initiator are present is heated to reach the 10-hour half-life temperature of the radical polymerization initiator may be used as the start time of the polymerization, or a time at which the reactor in which chlorotrifluoroethylene, vinyl ether and no radical polymerization initiator are present is heated to reach the 10-hour half-life temperature of the radical polymerization initiator may be used as the start time of the polymerization, and then the radical polymerization initiator is added to the reactor in which the temperature is maintained.
In the present production method, after the polymerization of the monomer is started, a mixture of chlorotrifluoroethylene and vinyl ether may be supplied into the reaction system, or chlorotrifluoroethylene and vinyl ether may be supplied into the reaction system, respectively. After the polymerization of the monomer is started, the monomer other than chlorotrifluoroethylene and vinyl ether may be supplied into the reaction system as a mixture with at least one of chlorotrifluoroethylene and vinyl ether or separately from chlorotrifluoroethylene and vinyl ether.
In the present specification, monomers including chlorotrifluoroethylene and vinyl ether, which are continuously or intermittently supplied after the start of polymerization of the monomers, are also collectively referred to as "additional monomers".
In the present production method, the continuous supply of the additional monomer into the reaction system is a method in which the additional monomer is added continuously for a predetermined period, and the method is a method in which the additional monomer is not added outside the predetermined period.
In the present production method, the intermittent supply of the additional monomer is a method of adding the additional monomer intermittently in batches, and the method of adding the additional monomer is a method of adding 2 or more times during which the additional monomer is added and during which the additional monomer is not added are alternately repeated.
In the present production method, for example, after a monomer containing chlorotrifluoroethylene and a vinyl ether, a piperidyl group-containing compound, hydrotalcite, and a radical polymerization initiator are charged into a reactor, polymerization is started.
The amount of chlorotrifluoroethylene to be charged before the start of polymerization (hereinafter, also referred to as "initial") is a part of the total amount of chlorotrifluoroethylene to be used in the polymerization reaction, and the balance is used for continuous or intermittent supply (hereinafter, also referred to as "continuous addition") into the reaction system after the start of polymerization. Similarly, the amount of vinyl ether initially charged is a part of the total amount of vinyl ether used in the polymerization reaction, and the remainder is used for continuous addition after the polymerization is started.
In the present production method, the molar ratio (Mm/Ma) of the total molar amount Mm of chlorotrifluoroethylene and vinyl ether initially charged to the total amount Ma of chlorotrifluoroethylene and vinyl ether used in the production of the specific fluorocopolymer is preferably 0.30 or more, more preferably 0.45 or more, still more preferably 0.55 or more. When the molar ratio (Mm/Ma) is not less than the above lower limit, the blocking resistance of the coating material becomes good, and the gloss at the time of forming a coating film is improved.
The molar ratio (Mm/Ma) is preferably 1.00 or less, more preferably 0.90 or less, and still more preferably 0.85 or less. When the molar ratio (Mm/Ma) is equal to or less than the upper limit, the melt viscosity of the coating material becomes good, and the smoothness of the coating film becomes good, whereby the gloss of the coating film is improved.
In the present production method, the molar ratio A of the amount of vinyl ether initially charged to the amount of chlorotrifluoroethylene initially charged is preferably 0.5 to 1.5, more preferably 0.7 to 1.3, still more preferably 0.9 to 1.1.
The molar ratio B of the amount of vinyl ether in the additional monomer continuously added to the reaction system to the amount of chlorotrifluoroethylene is preferably 0.7 to 2.0, more preferably 0.8 to 1.4, and still more preferably 0.9 to 1.1.
Further, the ratio (A/B) of the molar ratio A to the molar ratio B is preferably 0.5 to 1.5, more preferably 0.7 to 1.3, still more preferably 0.9 to 1.1. If the ratio (A/B) falls within the above range, the amount of the low molecular weight component contained in the resulting fluorocopolymer becomes small. As a result, the molecular weight distribution of the fluorocopolymer can be narrowed, and the gloss of a coating film formed using the fluorocopolymer can be improved.
The piperidyl group-containing compound may be added to the total amount used in the present production method initially, or a part of the total amount used in the present production method may be added to the reaction system after the start of polymerization. The piperidinyl-containing compound is preferably initially charged in total. When the piperidinyl group-containing compound is added to the reaction system after the start of polymerization, the addition may be continuous or may be performed at one time.
The hydrotalcite may be initially charged in the total amount used in the present production method, or may be initially charged in a part of the total amount used in the present production method and the remainder may be added to the reaction system after the start of polymerization. The hydrotalcite is preferably initially charged in total. When hydrotalcite is added to the reaction system after the start of polymerization, it may be added continuously or at one time.
The radical polymerization initiator may be added to the total amount used for the polymerization of the monomer initially, or may be added to the reaction system after the polymerization is started by adding a part of the total amount used for the polymerization of the monomer initially. The radical polymerization initiator is preferably added to the reaction system after the start of the polymerization by initially charging a part of the total amount used in the polymerization of the monomer, and more preferably added to the reaction system after the start of the polymerization by continuously charging a part of the total amount used in the polymerization of the monomer.
In the case where a solvent is used for polymerization of the monomer in the present production method, the solvent is preferably fed into a reactor before the start of polymerization together with the monomer, and polymerization of the monomer is preferably performed in the reactor.
When a solvent is used for polymerization of the monomer, the ratio (Mm/Ms) of the total molar amount Mm of the monomer present in the reactor before the start of the polymerization to the molar amount Ms of the solvent present in the reactor before the start of the polymerization is preferably 0.30 or more, more preferably 0.50 or more, still more preferably 0.65 or more. When the ratio (Mm/Ms) is in the above range, polymerization starts while the concentration of the monomer in the reactor is kept high, and therefore the polymer chain is satisfactorily elongated, and the amount of the low-molecular-weight component contained in the obtained fluorocopolymer becomes small. As a result, the molecular weight distribution of the fluorocopolymer can be narrowed, and the gloss of a coating film formed using the fluorocopolymer can be improved.
The above ratio (Mm/Ms) is preferably 1.50 or less, more preferably 1.45 or less, and further preferably 1.00 or less, from the viewpoint of smoothness of the coating film.
In the production method, the temperature in the reactor (polymerization temperature) at the time of polymerizing the monomer is preferably 50 to 90 ℃, more preferably 60 to 80 ℃. The polymerization temperature is the temperature in the reaction system at the start of polymerization, and is the temperature in the reaction system at the start of polymerization by continuously adding an additional monomer after the start of polymerization.
The pressure in the reaction system when the additional monomer containing chlorotrifluoroethylene and vinyl ether is continuously added after the start of polymerization (hereinafter, also referred to as polymerization pressure.) is preferably 0.3 to 0.8mpa, more preferably 0.4 to 0.7mpa.
The polymerization time from the start of the polymerization of the monomer to the end of the polymerization of the monomer to which the additional monomer is continuously added is preferably 0.5 to 30 hours, more preferably 1 to 5 hours.
In the present production method, after the polymerization of the monomer is completed, a mixed solution containing insoluble components derived from hydrotalcite in addition to the specific fluorocopolymer is obtained. The present production method may further include a step of removing insoluble components from the mixed solution.
Specific examples of the method for removing the insoluble component include solid-liquid separation treatment such as filtration.
In the present production method, when a solvent is used for polymerization of the monomer, a mixed solution containing the fluorocopolymer and the solvent may be obtained after the polymerization of the monomer is completed. In this case, the present production method may further include a step of removing the solvent from the mixed solution.
Specific examples of the method for removing the solvent from the mixed solution include heating and distillation.
In the present production method, components such as chain transfer agent, polymerization inhibitor, stabilizer, and the like may be used as necessary.
In the present production method, after polymerizing the monomers in accordance with the above-described steps, a composition containing a specific fluorocopolymer and a piperidinyl-containing compound (hereinafter, also referred to as the present composition) is obtained.
The content of the specific fluorocopolymer contained in the present composition is preferably 5 to 99.5% by mass, more preferably 10 to 99% by mass, based on the total mass of the present composition.
The piperidinyl-containing compound contained in the present composition is preferably the piperidinyl-containing compound exemplified in the above-mentioned method for producing a fluorocopolymer.
The content of the piperidinyl-containing compound is preferably 0.3 to 2.6 mass%, more preferably 0.8 to 2.0 mass% relative to the total mass of the specific fluorocopolymer.
The present composition may comprise a solvent.
The solvent may be a polymerization solvent used for polymerization of the specific fluorocopolymer, a solvent other than the polymerization solvent, or a mixture of the polymerization solvent and a solvent other than the polymerization solvent.
Specific examples of the solvent include solvents listed in the above-mentioned method for producing a fluorocopolymer.
When the present composition contains a solvent, the content of the solvent is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, based on the total mass of the present composition.
The present composition may comprise insoluble ingredients derived from hydrotalcite, but is preferably substantially free of hydrotalcite.
Here, substantially free of hydrotalcite means that the content of hydrotalcite relative to the total mass of the present composition is 0.05 mass% or less.
The present composition may contain components other than those described above.
The specific fluorocopolymer is preferably used for producing powder coating.
When the composition containing the specific fluorocopolymer contains a solvent, the solvent may be removed and used to produce a powder coating material.
The powder coating material of the present invention (hereinafter, also referred to as the present coating material) contains a specific fluorocopolymer.
The content of the specific fluorocopolymer is preferably 30 to 100 mass%, more preferably 40 to 100 mass%, based on the total mass of the coating material.
The present coating may comprise a piperidinyl-containing compound. The piperidyl-containing compound is preferably the piperidyl-containing compound listed in the above-mentioned method for producing a fluorocopolymer.
When the present coating material contains a piperidinyl group-containing compound, the content of the piperidinyl group-containing compound is preferably 0.1 to 2.6 mass%, more preferably 0.15 to 2.0 mass% relative to the total mass of the present coating material.
The present coating may further comprise additives.
Specific examples of the additives include pigments, curing agents, catalysts (curing catalysts, etc.), polymers other than the above (for example, polyester resins, (meth) acrylic resins, epoxy resins), fillers (resin beads, etc.), light stabilizers, ultraviolet absorbers, matting agents, surface regulators, deaerators, flow agents, heat stabilizers, antistatic agents, rust inhibitors, silane coupling agents, pollution reducing agents, plasticizers, adhesives, and the like.
The present paint may contain a solvent (water, organic solvent, etc.) or may contain no solvent (water, organic solvent, etc.), and preferably contains no solvent. The content of the solvent is preferably less than 1 mass%, more preferably 1 mass ppm or less, and still more preferably 0 mass% based on the total mass of the present coating material.
The present coating can be produced by mixing a specific fluorocopolymer with additives as required. The particular fluorocopolymer and additives to be mixed may be in the form of powder or pellets, each independently.
One example of the method for producing the present paint is a method in which a specific fluorocopolymer and additives to be used if necessary are melt-kneaded, cooled, and then pulverized to obtain a powder paint. The temperature of the melt kneading is preferably 80 to 130 ℃.
In addition, as an embodiment of the method for producing the present paint, there is a method in which a powder containing a specific fluorocopolymer is mixed with a powder of an additive to be used as needed to obtain a powder paint. This method is also called dry blending, and is a method in which melt kneading is not performed during mixing.
The pulverization may be performed using a pulverizer such as a pin mill, a hammer mill, or a jet mill. The pulverized material is preferably classified after pulverization so that the particle size of the obtained powder coating material is uniform. The average particle diameter of the powder coating is preferably 1 to 100. Mu.m, more preferably 10 to 80. Mu.m.
The coating film of the present invention (hereinafter, also referred to as the present coating film) is formed by applying the present coating material to a substrate.
The coated article of the present invention comprises a substrate and a coating film formed from the present coating material disposed on the substrate.
Specific examples of the material of the base material include inorganic substances, organic substances, and organic-inorganic composite materials.
Concrete, natural stone, glass, metal (iron, stainless steel, aluminum, copper, brass, titanium, etc.) are examples of the inorganic substance.
Specific examples of the organic substance include plastics, rubbers, adhesives, and wood.
Specific examples of the organic-inorganic composite material include fiber-reinforced plastics, resin-reinforced concrete, and fiber-reinforced concrete.
The substrate may be subjected to a known surface treatment (chemical conversion treatment or the like). In addition, a resin layer (polyester resin layer, acrylic resin layer, silicone resin layer, etc.) formed by applying a primer or the like may be provided on the surface of the base material in advance.
The material of the base material is preferably metal, more preferably iron, an alloy containing iron (for example, carbon steel, stainless steel), or aluminum.
Specific examples of the shape of the substrate include a flat plate shape, a spherical shape, and a rod shape.
The film thickness of the coating film is preferably 20 to 1000 μm, more preferably 20 to 500 μm.
The coated article of the present invention is preferably produced by applying (coating) the present paint to the surface of a substrate to form a coating layer, heating the obtained coating layer, and then cooling.
Examples of the method for forming the coating layer include a coating method such as an electrostatic coating method, an electrostatic blowing method, an electrostatic dipping method, a flow dipping method, and a blowing method, and electrostatic coating using a powder coating gun is preferable.
Specific examples of the powder coating gun include a corona charging type coating gun and a friction charging type coating gun. The corona charging type coating gun is a coating gun that performs corona discharge treatment and blows a powder coating. The triboelectric type coating gun is a coating gun that performs triboelectric treatment on powder paint and blows the powder paint.
The heating temperature during the heating treatment is preferably 120 to 250 ℃. The heating maintenance time is usually 2 to 60 minutes. The heat treatment is preferably followed by cooling to 20 to 25 ℃. The coating layer is melted and solidified (melt-solidified) by heat treatment and cooling, and the present coating film is formed.
Examples
The present invention will be described in detail below by way of examples. Examples 1 to 9 are examples, and examples 10 to 14 are comparative examples. However, the present invention is not limited to these examples. The blending amounts of the components in the tables described below represent mass references unless otherwise specified.
Example 1
Into a stainless steel pressure-resistant reactor having an internal volume of 2500ml and equipped with a stirrer, 20g of a mixture (mass ratio 3:1) of a piperidinyl-containing compound (trade name "TINUVIN292" manufactured by BASF), bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate and methyl 1,2, 6-pentamethyl-4-piperidinyl sebacate), 20g of hydrotalcite (trade name "KW500" manufactured by KO Co., ltd., particle size of 45 μm or less: 38%, 45 to 75 μm:35%, 75 to 106 μm:21%, 106 to 500 μm: 6%), 679g of xylene, 118g of 4-hydroxybutyl vinyl ether (hereinafter also referred to as HBVE.) and 453g of cyclohexyl vinyl ether (hereinafter also referred to as CHVE.) were charged, and dissolved oxygen in the liquid was removed by nitrogen-based degassing. Further, 536g of chlorotrifluoroethylene (hereinafter, also referred to as ctfe.) was introduced into the reactor and heated. The pressure at the point when the temperature in the reactor reached 65 ℃ showed 0.59MPaG. Thereafter, 2ml of a 5% xylene solution of t-butyl peroxypivalate (hereinafter referred to as PBPV) was added to the reactor, and the reaction was started.
While maintaining the pressure with the decrease in pressure, additional monomers of CTFE110g, CHVE 93g and HBVE 24g were continuously added to the reactor, and a PBPV% xylene solution as a radical polymerization initiator was intermittently added to the reactor to allow polymerization to proceed. After the start of polymerization, the total amount of PBPV% xylene solution intermittently added to the reactor was 55ml. After 16 hours, the reactor was water cooled to stop the reaction.
After cooling the reaction solution to room temperature, the unreacted monomer was purged, insoluble components of the obtained reaction solution were removed by filtration, and an appropriate amount of xylene was added to obtain a fluorocopolymer solution (A-1) having a solid content of 65%. The fluorocopolymer solution (A-1) comprises fluorocopolymer, piperidyl-containing compound and xylene.
The composition of the fluorocopolymer contained in the fluorocopolymer solution (a-1) was CTFE/CHVE/HBVE (mol%) =50/39/11. In the case where CTFE/che/HBVE (mol%) is expressed as =xx/YY/ZZ, the values shown in XX, YY and ZZ refer to the molar ratios (percentages) of the structural units derived from CTFE, the structural units derived from che and the structural units derived from HBVE, respectively, with respect to the entire structural units of the fluorine-containing copolymer.
Example 2
22G of a piperidyl-containing compound (trade name "TINUVIN292", a mixture of bis (1, 2, 6-pentamethyl-4-piperidyl) sebacate and methyl 1,2, 6-pentamethyl-4-piperidyl sebacate (mass ratio 3:1)) was charged into a stainless steel pressure-resistant reactor having an internal volume of 2500ml equipped with a stirrer, 22g of hydrotalcite (trade name "KW500", grain size of 45 μm or less: 38%, 45 to 75 μm:35%, 75 to 106 μm:21%, 106 to 500 μm: 6%), 726g of xylene, 79g of HBVE, and 303g of CHVE were removed from the liquid by degassing with nitrogen. Furthermore, 357g of CTFE was introduced into the reactor and the temperature was raised. The pressure at the point when the temperature in the reactor reached 75 ℃ showed 0.55MPaG. Thereafter, 6ml of PBPV% xylene solution was added to the reactor to start the reaction.
While maintaining the pressure with the decrease in pressure, additional monomers of 350g CTFE, 297g CHVE and 78g HBVE were continuously added to the reactor, and a PBPV% xylene solution as a radical polymerization initiator was intermittently added to the reactor, thereby allowing polymerization to proceed. After the start of polymerization, the total amount of PBPV% xylene solution intermittently added to the reactor was 25ml. After 16 hours, the reactor was water cooled to stop the reaction.
After cooling the reaction solution to room temperature, the unreacted monomer was purged, insoluble components of the obtained reaction solution were removed by filtration, and an appropriate amount of xylene was added to obtain a fluorocopolymer solution (A-2) having a solid content of 65%. The fluorocopolymer solution (A-2) contains fluorocopolymer, piperidyl-containing compound and xylene.
The composition of the fluorocopolymer contained in the fluorocopolymer solution (a-2) was CTFE/CHVE/HBVE (mol%) =50/39/11.
(Examples 3 to 5)
A fluorocopolymer solution (A-3) to (A-5) was obtained in the same manner as in example 2, except that the amounts of the respective components and the polymerization temperatures were as shown in Table 1. The fluorine-containing copolymer solutions (A-3) to (A-5) comprise fluorine-containing copolymers, piperidyl-containing compounds and xylene. The compositions of the fluorocopolymers contained in the fluorocopolymer solutions (A-3) to (A-5) are CTFE/CHVE/HBVE (mol%) =50/39/11.
(Examples 6 to 9)
A fluorocopolymer solution (A-6) to (A-9) was obtained in the same manner as in example 1, except that the amounts of the respective components and the polymerization temperatures were as shown in Table 1. The fluorine-containing copolymer solutions (A-6) to (A-9) comprise fluorine-containing copolymers, piperidyl-containing compounds and xylene. The compositions of the fluorocopolymers contained in the fluorocopolymer solutions (A-6) to (A-9) are CTFE/CHVE/HBVE (mol%) =50/39/11.
Example 10
Into a stainless steel pressure-resistant reactor having an internal volume of 2500ml and equipped with a stirrer, 12.4g of a piperidyl-containing compound (trade name "TINUVIN144" manufactured by BASF), bis (1, 2, 6-pentamethyl-4-piperidyl) [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] butylmalonate), 929g of xylene, 212g of ethyl vinyl ether (hereinafter, also referred to as eve.), 132g of HBVE, and 214g of CHVE were charged, and dissolved oxygen in the liquid was removed by degassing based on nitrogen gas. In the reactor, 677g of CTFE was introduced and the temperature was raised. At the time when the temperature in the reactor reached 65 ℃, 2.5ml of PBPV 27.9.9% xylene solution was added to the reactor to start the polymerization.
After the polymerization was started, PBPV 27.9.9% xylene solution was intermittently added to the reactor, thereby allowing the polymerization to proceed. The total amount of PBPV 27.9.9% xylene solution intermittently added to the reactor after the start of polymerization was 50ml. After 10 hours, the reactor was water cooled to stop the reaction.
After cooling the reaction solution to room temperature, the unreacted monomer was purged, insoluble components of the obtained reaction solution were removed by filtration, and an appropriate amount of xylene was further added to the obtained filtrate to obtain a fluorocopolymer solution (A-10) having a solid content of 60.7%. The fluorocopolymer solution (A-10) comprises fluorocopolymer, piperidyl-containing compound and xylene.
The composition of the fluorocopolymer contained in the fluorocopolymer solution (a-10) was CTFE/EVE/che/HBVE (mol%) = 50/25/15/10.
(Examples 11 to 13)
A fluorocopolymer solution (A-11) to (A-13) was obtained in the same manner as in example 1, except that the amounts of the respective components and the polymerization temperatures were as shown in Table 1. The fluorine-containing copolymer solutions (A-11) - (A-13) comprise fluorine-containing copolymers, piperidyl-containing compounds and xylene. The compositions of the fluorocopolymers contained in the fluorocopolymer solutions (A-11) to (A-13) are CTFE/CHVE/HBVE (mol%) =50/39/11.
Example 14
A fluorocopolymer solution (A-14) was obtained in the same manner as in example 10, except that the amounts of the respective components and the polymerization temperatures were as shown in Table 1. The fluorocopolymer solution (A-14) contains fluorocopolymer, piperidyl-containing compound and xylene. The compositions of the fluorocopolymers contained in the fluorocopolymer solution (a-14) were CTFE/CHVE/HBVE (mol%) =50/39/11.
(Determination of molecular weight of fluorocopolymer)
Tetrahydrofuran (hereinafter also referred to as thf.) was added to each of the fluorocopolymer solutions to obtain solutions diluted to a concentration of 1% by mass of fluorocopolymer. After the obtained solution was filtered through a hydrophilic PTFE membrane filter having a pore size of 0.45. Mu.m, 1.5ml of the filtered solution (measurement solution) was filled into a transparent glass vial having a capacity of 2 ml.
Next, an elution curve (chromatogram) of the specific fluorocopolymer obtained from the elution time and the detection intensity based on RI (differential refractive index detector) was obtained by gel permeation chromatography. Next, mw, mn, mw/Mn of the fluorocopolymer was determined from the retention time of the obtained elution curve by using a standard curve of polystyrene. The results are shown in Table 1. The measurement conditions of the gel permeation chromatography are shown below.
< Conditions for measurement by gel permeation chromatography >
HLC-8320GPC (manufactured by Tosoh Co., ltd.)
The analytical column was used by connecting 2 Shodex GPC KF-806M (manufactured by Showa Denko Co., ltd.) with 1 Shodex GPC KF-802 (manufactured by Showa Denko Co., ltd.)
Column temperature box 40 DEG C
Pump case at 40 DEG C
Eluent tetrahydrofuran
Flow 1.0 ml/min
Detector RI
Standard Curve sample EASICAL PS-1 (polystyrene, agilent Co.)
Molecular weight range of standard curve is 580-570000
(Thermal stability)
50G of each example of the fluorocopolymer solution was placed in a heat-resistant container, and placed in an oven set at 70 ℃. After 14 days from the introduction into the oven, the heat-resistant container was taken out of the oven. THF was added to the fluorocopolymer solution after the heat test to prepare a solution diluted to a concentration of 1% by mass of fluorocopolymer, and the molecular weight of the fluorocopolymer was measured by the above-mentioned measurement method.
The ratio of the weight average molecular weight (Mw 2) of the fluorocopolymer after the heating test to the weight average molecular weight (Mw 1) of the fluorocopolymer before the heating test was calculated as Mw change rate (=Mw 2/Mw 1). From the calculated Mw change rate, the thermal stability of the fluorocopolymer was evaluated according to the following evaluation criteria. The evaluation results are shown in table 1.
Mw change ratio is less than 1.3.
Mw change ratio is 1.3 or more and less than 1.5.
Mw change ratio was 1.5 or more.
(Production of powder coating)
The fluorocopolymer solutions of each example were kept under reduced pressure heating at 65℃for 3 hours and then under reduced pressure heating at 130℃for 20 minutes by a vacuum dryer, and volatile components were removed to obtain fluorocopolymer compositions of each example. The obtained fluorocopolymer compositions of each example were prepared into powder by a pulverizer.
Next, a powdery mixture was prepared from each example of the powdery fluorocopolymer composition according to the following procedure. To 100 parts by mass of the powdery fluorocopolymer composition, 67 parts by mass of titanium oxide (manufactured by Dupont, ti-Pure (registered trademark) R960), 25 parts by mass of blocked isocyanate curing agent (manufactured by Evonik, VESTAGON (registered trademark) B1530), 0.012 part by mass of dibutyltin dilaurate as a curing catalyst in xylene (10000-fold dilution), 0.8 part by mass of benzoin as a degassing agent, 2 parts by mass of surface conditioner (manufactured by BYK, BYK (registered trademark) -360P) and the mixture was mixed for about 10 to 30 minutes by a high-speed mixer (manufactured by blewasaki limited).
Next, the powdery mixture was melt-kneaded by a twin-screw extruder (Thermo FISHER SCIENTIFIC Inc. 16mm extruder) at a barrel set temperature of 120℃to obtain pellets. The obtained pellets were pulverized at ordinary temperature by a pulverizer (manufactured by FRITSCH Co., ltd., rotor SPEED MILL P), and classified by a 150-mesh sieve to obtain a powder coating composition having an average particle diameter of about 40. Mu.m.
(Production of substrate with coating film)
Each powder coating composition was applied to one surface of a chromate-treated aluminum plate by electrostatic coating using an electrostatic coater (Onoda ceramic co., ltd., GX 3600C), and the resultant was kept at 200 ℃ for 20 minutes. After heating, the aluminum sheet with the coating layer corresponding to each example was left to cool to room temperature, and a coated (cured) film with a film thickness of 55 to 65 μm was obtained.
(Evaluation of gloss of coating film)
The 20℃gloss value of the surface of the coating film was measured after 24 hours of production of the aluminum sheet with the coating film by a gloss meter (PG-1M, manufactured by Nippon Denshoku Co., ltd.). The gloss of the coating film was evaluated from the obtained gloss value according to the following evaluation criteria. The evaluation results are shown in table 1.
20 DEG gloss value is 40 or more.
X20 gloss values are below 40.
(Evaluation of coloring of coating film)
The b-value of the surface of the coating film was measured after 24 hours of production of an aluminum plate with the coating film by a color difference meter (SE-7700, manufactured by japan electric color industry co., ltd.). The value of b is one of the color coordinates in the chromaticity system of l×a×b specified in JIS Z8729. The coloration of the coating film was evaluated from the measured b-value according to the following evaluation criteria. The evaluation results are shown in table 1.
B is lower than 1.6.
The value b is 1.6 or more.
In the following table, pg/M represents the molar ratio of the molar amount of the piperidinyl groups in the piperidinyl group-containing compound to the molar amount of the entire amount of the monomer used.
In the following table, H/Pc represents the mass ratio of the amount of hydrotalcite to the amount of the piperidinyl-containing compound.
In the following table, mm/Ms represents the ratio of the total molar amount Mm of all monomers to the molar amount Ms of the solvent in the reactor before the start of polymerization.
In the following table, the numerical values shown in the composition 1 represent the molar ratios (percentages) of the structural units derived from CTFE, the structural units derived from CHVE and the structural units derived from HBVE, respectively, with respect to all the structural units of the fluorocopolymer produced in each example, in order from the left side of the paper. The numerical values shown in the composition 2 represent the molar ratios (percentages) of the structural units derived from CTFE, the structural units derived from EVE, the structural units derived from CHVE and the structural units derived from HBVE, respectively, with respect to all the structural units of the fluorocopolymer produced in each example, in order from the left side of the paper.
TABLE 1
As shown in Table 1, it was confirmed that in the production method of a fluorocopolymer comprising polymerizing a monomer comprising CTFE and a vinyl ether using a radical polymerization initiator, a piperidyl-containing compound and hydrotalcite, the fluorocopolymer of the present invention, which has excellent thermal stability, excellent gloss for a coating film when used for forming a coating film and further suppressed coloring of a coating film when used for forming a coating film, can be produced by the production method of the present invention in which the molar ratio of the piperidyl group in the piperidyl-containing compound to the molar amount of the total amount of the monomer is 0.0032 to 0.010, the mass ratio of the hydrotalcite to the piperidyl-containing compound is 0.30 or more and less than 4.60, and chlorotrifluoroethylene and vinyl ether are continuously or intermittently supplied into the reaction system after the initiation of the polymerization.
The entire contents of the specification, claims and abstract of japanese patent application No. 2022-108313, filed on 7/5/2022, are incorporated herein by reference as if disclosed in the present specification.
Claims (10)
1. A process for producing a fluorocopolymer which comprises the steps of, which produces a fluorine-containing copolymer comprising a chlorotrifluoroethylene-based unit and a vinyl ether-based unit, in the production method,
Polymerizing a monomer comprising chlorotrifluoroethylene and a vinyl ether using a radical polymerization initiator, a piperidinyl-containing compound and hydrotalcite to produce the fluorocopolymer,
The ratio of the molar amount of the piperidyl groups in the piperidyl-containing compound to the molar amount of the whole amount of the monomers is 0.0032 to 0.010,
The mass ratio of the amount of hydrotalcite to the amount of the piperidyl-containing compound is 0.30 or more and less than 4.60,
After the polymerization is started, the chlorotrifluoroethylene and the vinyl ether are continuously or intermittently supplied into the reaction system.
2. The method for producing a fluorocopolymer according to claim 1, wherein the polymerization is carried out in a reactor,
The presence of solvent and the monomer in the reactor prior to the start of the polymerization,
In the reactor before the start of the polymerization, the ratio of the total molar amount of the monomers to the molar amount of the solvent is 0.30 or more.
3. The method for producing a fluorocopolymer according to claim 1 or 2, wherein the vinyl ether contains at least a vinyl ether having a crosslinkable group.
4. The method for producing a fluorocopolymer as claimed in claim 3, wherein the crosslinkable group is a hydroxyl group or a carboxyl group.
5. The method for producing a fluorocopolymer as claimed in claim 3, wherein the amount of said vinyl ether having a crosslinkable group is 1 to 20 mol% based on the total amount of said monomers.
6. The method for producing a fluorocopolymer as claimed in claim 1 or 2, wherein,
The vinyl ether includes a vinyl ether having a crosslinkable group and a vinyl ether having no crosslinkable group,
The amount of the vinyl ether having no crosslinkable group is 1 to 70 mol% based on the total amount of the monomers.
7. The method for producing a fluorocopolymer according to claim 1 or 2, wherein the molar ratio of the amount of chlorotrifluoroethylene to the total amount of the monomers is 30 to 70 mol%.
8. The method for producing a fluorocopolymer according to claim 1 or 2, wherein the fluorocopolymer has a weight average molecular weight of 10000 to 60000.
9. A process for producing a powder coating material, comprising producing a powder coating material using the fluorocopolymer produced by the process for producing a fluorocopolymer according to claim 1 or 2.
10. A method for producing a coated article, comprising applying the powder coating produced by the method for producing a powder coating according to claim 9 to a surface of a substrate to form a coating layer, and melt-curing the coating layer to form a coating film.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2022108313 | 2022-07-05 | ||
| JP2022-108313 | 2022-07-05 | ||
| PCT/JP2023/021769 WO2024009697A1 (en) | 2022-07-05 | 2023-06-12 | Method for producing fluorine-containing copolymer, method for producing powder coating material, method for producing coated article |
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| CN119487082A true CN119487082A (en) | 2025-02-18 |
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| JP3102514B2 (en) * | 1991-12-12 | 2000-10-23 | 大日本インキ化学工業株式会社 | Resin composition |
| WO2015056751A1 (en) * | 2013-10-17 | 2015-04-23 | 旭硝子株式会社 | Fluoroolefin-copolymer-containing solution composition, method for producing same, and coating material composition |
| CN107109097A (en) * | 2014-11-17 | 2017-08-29 | 旭硝子株式会社 | Manufacture method, powder coating composition, powder coating and the coated article of powder coating fluoroolefin copolymer powder |
| JP6753418B2 (en) * | 2016-01-14 | 2020-09-09 | Ａｇｃ株式会社 | Fluororesin-containing solution, method for producing fluororesin-containing solution, paint composition and painted article |
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