WO2017159817A1 - （メタ）アクリル酸エステル系塗料用ワニスの製造方法 - Google Patents

（メタ）アクリル酸エステル系塗料用ワニスの製造方法 Download PDF

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Publication number
WO2017159817A1
WO2017159817A1 PCT/JP2017/010772 JP2017010772W WO2017159817A1 WO 2017159817 A1 WO2017159817 A1 WO 2017159817A1 JP 2017010772 W JP2017010772 W JP 2017010772W WO 2017159817 A1 WO2017159817 A1 WO 2017159817A1
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WO
WIPO (PCT)
Prior art keywords
parts
meth
acrylic acid
acid ester
mass
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Application number
PCT/JP2017/010772
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English (en)
French (fr)
Japanese (ja)
Inventor
邦宏 伊藤
西川　徹
Original Assignee
日油株式会社
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Application filed by 日油株式会社 filed Critical 日油株式会社
Publication of WO2017159817A1 publication Critical patent/WO2017159817A1/ja

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    • 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
    • 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
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives

Definitions

  • the present invention relates to a method for producing a paint varnish. Specifically, (meth) acrylic polymerizes a monomer mixture containing a vinyl monomer containing (meth) acrylic acid ester and a hydroxyl group-containing (meth) acrylic acid ester in a specific ratio and containing an organic peroxide having a specific structure.
  • the present invention relates to a method for producing an acid ester paint varnish.
  • the varnish for paint is produced mainly using a vinyl monomer containing (meth) acrylic acid ester, a solvent, a polymerization initiator and the like. At this time, an organic peroxide, an azo compound or the like is mainly used as the polymerization initiator.
  • the polymerization initiator is appropriately selected in consideration of the cost, the temperature adjustment ability of the polymerization equipment, the quality of the target resin, etc., but when polymerization at a high temperature is required, a high half-life temperature suitable for the polymerization temperature is used.
  • the polymerization initiator is selected.
  • Many organic peroxides have a higher half-life temperature than azo compounds.
  • Patent Document 1 Japanese Patent Publication No. 48-26386
  • Patent Document 3 Japanese Patent Document 3
  • di-t-butyl peroxide is generally widely used in polymerization at high temperatures.
  • the present invention provides a method for producing a varnish for a (meth) acrylic acid ester-based paint having a low molecular weight and a low degree of dispersion and in which an increase in acid value is suppressed. Moreover, this invention provides the manufacturing method of the varnish for (meth) acrylic acid ester type coating materials which can suppress the raise of the acid value of a polymer.
  • the present invention (A) Vinyl monomer mixture containing (meth) acrylic acid ester; 70 to 80 parts by mass, (B) hydroxyl group-containing (meth) acrylic acid ester; 20 to 28 parts by mass, (C) Carboxylic acid group-containing monomer; 0.1 to 10 parts by mass, and (D) General formula (I)
  • R is a hydrogen atom or a methyl group
  • a varnish for a (meth) acrylate-based paint that has a low molecular weight, a low dispersity, and can realize an acid value as initially designed.
  • “according to the initial design” means that the difference between the raw acid value (measured value) and the theoretical acid value (acid value difference) is so small that the desired characteristics of the varnish can be maintained.
  • the method for producing a varnish for a (meth) acrylic acid ester paint of the present invention comprises (A) a vinyl monomer mixture containing (meth) acrylic acid ester, (B) a hydroxyl group-containing (meth) acrylic acid ester, and (C) carboxylic acid.
  • a polymerization monomer mixture for coating containing a group-containing monomer and (D) an organic peroxide is polymerized in an organic solvent.
  • (meth) acrylic acid ester is a general term for acrylic acid ester and methacrylic acid ester.
  • the (meth) acrylic acid ester of the vinyl monomer mixture containing the (A) (meth) acrylic acid ester of the present invention does not contain a hydroxyl group.
  • (meth) acrylic acid esters methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, It is preferable to use lauryl methacrylate or glycidyl methacrylate.
  • the (meth) acrylic acid ester can be used alone or in combination of two or more.
  • (A) can be used in combination with a (meth) acrylic acid ester and a vinyl monomer copolymerizable with the (meth) acrylic acid ester.
  • vinyl monomers include styrene, ⁇ -methylstyrene, vinyl acetate, vinyl chloride, butadiene, acrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, and anhydrous And maleic acid.
  • the amount of the vinyl monomer mixture containing (A) (meth) acrylic acid ester in the polymerization monomer mixture for coating containing the above (A) to (D) of the present invention is 70 to 80 parts by mass.
  • the vinyl monomer mixture containing (A) (meth) acrylic acid ester is preferably a mixture composed of (meth) acrylic acid ester.
  • Examples of the (B) hydroxyl group-containing (meth) acrylic acid ester of the present invention include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate, 2-Hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 3-hydroxy-1-adamantyl methacrylate, or the like can be used.
  • hydroxyl group-containing (meth) acrylic acid esters 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferably used. These may be used alone or in combination.
  • the amount of the (B) hydroxyl group-containing (meth) acrylic acid ester used in the polymerization monomer mixture for coatings containing the above (A) to (D) of the present invention is 20 to 28 parts by mass.
  • (C) carboxylic acid group-containing monomer of the present invention for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid or the like can be used.
  • carboxylic acid group-containing monomers it is preferable to use acrylic acid or methacrylic acid. These may be used alone or in combination.
  • the amount of the (C) carboxylic acid group-containing monomer used in the coating polymerization monomer mixture containing the above (A) to (D) of the present invention is 0.1 to 10 parts by mass.
  • a conventionally known organic solvent can be used.
  • the organic solvent include, for example, toluene, ethylbenzene, xylene, aromatic petroleum naphtha, tetralin, Solvesso 100 (registered trademark of ExxonMobil), Solvesso 150 (registered trademark of ExxonMobil), and Solvesso 200 (registered trademark of ExxonMobil).
  • Aromatic hydrocarbons methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl n-butyl ketone, ethyl amyl ketone, cyclohexanone, diacetone alcohol, diisobutyl ketone, diethyl ketone, dibutyl ketone, methyl isopropyl ketone And ketones such as diisobutyl ketone; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol Esters such as monoethyl ether, propylene glycol acetate monoethyl ether, methoxybutyl acetate, propyl propionate, butyl propionate, and ethoxyeth
  • aromatic compounds such as xylene, Solvesso 100 (registered trademark of ExxonMobil), and Solvesso 150 (registered trademark of ExxonMobil); ketones such as methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone; acetic acid It is preferable to use esters such as n-butyl, amyl acetate, and ethyl 3-ethoxypropionate; or alcohols such as 1-pentanol, 1-hexanol, isoamyl alcohol, cyclohexanol, and 2-ethylhexanol; .
  • Di-t-hexyl peroxide and di-t-amyl peroxide may be used alone or in combination. Further, it is possible to add further to reduce the residual monomer at the latter stage of the polymerization reaction.
  • the amount of the organic peroxide used in the coating monomer mixture for coating containing the above (A) to (D) of the present invention is 5 to 5 parts per 100 parts by mass of the total amount of the above (A) to (C). 15 parts by mass, preferably 7 to 13 parts by mass. Less than 5 parts by mass is not preferable because a large amount of unreacted vinyl monomer remains and the molecular weight of the polymer becomes high. On the other hand, when the amount exceeds 15 parts by mass, the polymer acid value increases, the unreacted organic peroxide remains, and many decomposition products derived from the organic peroxide are generated.
  • the polymerization temperature is usually preferably 100 to 200 ° C, more preferably 120 to 180 ° C.
  • the polymerization rate is slow, and a large amount of unreacted monomer may remain, or the molecular weight of the resulting polymer may increase.
  • it exceeds 200 degreeC superposition
  • rate is too quick and by-production of an oligomer may occur.
  • the polymerization time (dropping time and reaction time) is usually preferably 2 to 10 hours, more preferably 3 to 7 hours. If the polymerization time is less than 2 hours, a large amount of unreacted monomer or organic peroxide may remain. Moreover, since productivity may fall when it exceeds 10 hours, it is unpreferable.
  • MMA methyl methacrylate
  • BA n-butyl methacrylate
  • St styrene
  • HEMA 2-hydroxyethyl methacrylate
  • HEA 2-hydroxyethyl acrylate
  • MAA methacrylic acid
  • AA acrylic acid
  • HxD di- t-Hexyl peroxide (manufactured by NOF Corporation: Perhexyl (registered trademark)
  • AmD Di-t-amyl peroxide
  • BuD Di-t-butyl peroxide (manufactured by NOF Corporation: Perbutyl (registered trademark) D)
  • Example 1 In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, 35 parts of Solvesso 100 (registered trademark of ExxonMobil Co., Ltd.) was placed, and the temperature was raised to 150 ° C. while introducing nitrogen gas.
  • Solvesso 100 registered trademark of ExxonMobil Co., Ltd.
  • Example 2 Polymerization was performed in the same manner as in Example 1 except that the monomer was changed to MMA / BA / HEMA / MAA (40 parts / 33 parts / 25 parts / 2 parts) to obtain a paint varnish.
  • Example 3 Example 1 Polymerization was performed to obtain a paint varnish.
  • Example 4 Polymerization was carried out in the same manner as in Example 1 except that the monomer was changed to MMA / BMA / HEMA / MAA (40 parts / 30 parts / 28 parts / 2 parts) to obtain a paint varnish.
  • Example 5 Polymerization was performed in the same manner as in Example 1 except that the monomer was changed to MMA / BMA / HEA / MAA / AA (40 parts / 33 parts / 25 parts / 1 part / 1 part) to obtain a paint varnish. .
  • Comparative Example 2 The monomer is MMA / BMA / HEMA / MAA (40 parts / 8 parts / 50 parts / 2 parts), the organic peroxide is di-t-hexyl peroxide (manufactured by NOF Corporation: Perhexyl (registered trademark) D), Polymerization was conducted in the same manner as in Comparative Example 1 except that the organic solvent was changed to ethoxyethyl propionate to obtain a paint varnish.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
PCT/JP2017/010772 2016-03-18 2017-03-16 （メタ）アクリル酸エステル系塗料用ワニスの製造方法 WO2017159817A1 (ja)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016055415 2016-03-18
JP2016-055415 2016-03-18

Publications (1)

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WO2017159817A1 true WO2017159817A1 (ja) 2017-09-21

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JP (1) JP2017171908A (zh)
TW (1) TWI751145B (zh)
WO (1) WO2017159817A1 (zh)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07149836A (ja) * 1993-07-23 1995-06-13 Hoechst Ag Ｏｈ基含有コポリマーの製造方法、およびそのハイソリッド塗料としての用途
JPH11293179A (ja) * 1998-04-15 1999-10-26 Nof Corp 塗料用ワニス及びその製造方法並びに塗料組成物
JP2001354897A (ja) * 2000-06-12 2001-12-25 Kansai Paint Co Ltd 熱硬化型塗料組成物、その組成物を用いてなる被膜形成方法及びそれらのものから得られる塗装物品
BG109974A (bg) * 2007-10-15 2009-05-29 "Оргахим" Ад Акрилатен кополимер, метод за неговото получаване и приложението му
JP2009275170A (ja) * 2008-05-16 2009-11-26 Mitsubishi Rayon Co Ltd ビニル系重合体の製造方法、該ビニル系重合体を含有する塗料及び該塗料を用いた塗膜の形成方法。
JP2013511578A (ja) * 2009-11-20 2013-04-04 エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング 水性アルカリに可溶性である、（メタ）アクリレートコポリマーの塊状重合
WO2015161167A1 (en) * 2014-04-17 2015-10-22 Ppg Industries Ohio, Inc. Primer coating composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5525401A (en) * 1978-08-10 1980-02-23 Kansai Paint Co Ltd High solid coating composition
JPS57209963A (en) * 1981-06-22 1982-12-23 Toyo Ink Mfg Co Ltd Aqueous clear varnish composition and method for using same as topcoating agent
CA1325076C (en) * 1985-12-11 1993-12-07 Albert Ilya Yezrielev High solids acrylic-based coatings
JPH0741203B2 (ja) * 1986-12-29 1995-05-10 関西ペイント株式会社 メタリツク仕上げ方法
JPS63168415A (ja) * 1987-01-02 1988-07-12 ペンウオルト・コ−ポレ−シヨン ｔ−アルキルヒドロペルオキシドを用いたアクリル酸誘導体モノマ−の溶液重合方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07149836A (ja) * 1993-07-23 1995-06-13 Hoechst Ag Ｏｈ基含有コポリマーの製造方法、およびそのハイソリッド塗料としての用途
JPH11293179A (ja) * 1998-04-15 1999-10-26 Nof Corp 塗料用ワニス及びその製造方法並びに塗料組成物
JP2001354897A (ja) * 2000-06-12 2001-12-25 Kansai Paint Co Ltd 熱硬化型塗料組成物、その組成物を用いてなる被膜形成方法及びそれらのものから得られる塗装物品
BG109974A (bg) * 2007-10-15 2009-05-29 "Оргахим" Ад Акрилатен кополимер, метод за неговото получаване и приложението му
JP2009275170A (ja) * 2008-05-16 2009-11-26 Mitsubishi Rayon Co Ltd ビニル系重合体の製造方法、該ビニル系重合体を含有する塗料及び該塗料を用いた塗膜の形成方法。
JP2013511578A (ja) * 2009-11-20 2013-04-04 エボニック レーム ゲゼルシャフト ミット ベシュレンクテル ハフツング 水性アルカリに可溶性である、（メタ）アクリレートコポリマーの塊状重合
WO2015161167A1 (en) * 2014-04-17 2015-10-22 Ppg Industries Ohio, Inc. Primer coating composition

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JP2017171908A (ja) 2017-09-28
TW201802126A (zh) 2018-01-16
TWI751145B (zh) 2022-01-01

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