Source: https://patents.google.com/patent/US5959028A/en
Timestamp: 2019-06-18 00:21:38
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US5959028A - Curable resin composition for coating use - Google Patents
Curable resin composition for coating use Download PDF
US5959028A
US5959028A US08/859,912 US85991297A US5959028A US 5959028 A US5959028 A US 5959028A US 85991297 A US85991297 A US 85991297A US 5959028 A US5959028 A US 5959028A
US08/859,912
1996-05-22 Priority to JP8-151546 priority Critical
1996-05-22 Priority to JP15154696 priority
1997-05-21 Application filed by Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
1998-07-10 Assigned to NIPPON PAINT CO., LTD. reassignment NIPPON PAINT CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AOKI, KEI, IRIE, TAKASHI
1999-09-28 Publication of US5959028A publication Critical patent/US5959028A/en
A resin composition curable through a Michael reaction between (a) a component having a plurality of α,β-unsaturate carbonyl groups and (b) a component having a plurality of activated methylene group in the presence of a catalyst is disclosed. The activated methylene component is a polymer of an asymmetric malonate ester in which one of carboxyl groups is esterified with an alkanol while the other carboxyl group is esterified with hydroxyalkyl (meth) acrylate or polyoxyalkylene glycol mono(meth)acrylate.
This invention relates to a curable resin composition for coating use. More paticularly, it relates to a resinous composition which cures through a Michael reaction.
Michael reactions in which base-catalysed addition of activated methylene to polarized double bond are utilized in the crosslinking of resinous compositions for coating use. Theses compositions are advantageous in that the Michael reaction gives a chemically stable crosslinking bond without forming any reaction by-product.
According to the present invention, a curable resin composition having enhanced weatherability is provided by using as an activated methylene component a malonate group-containing acrylate polymer in place of an acetoacetate group-containing acrylate polymer.
When used as a coating composition, it may contain a variety of conventional additives such as extender pigments, coloring pigments, sag-preventing agents, UV absorbers and the like. After applying onto a substrate as a film, the composition may be cured, depending upon the type of catalyst, by leaving at ambient temperature or baking the film at a temperature between 100° C. and 200° C., preferably between 120° C. and 150° C.
To a 4-necked flask charged with 360 parts of xylene was added dropwise a monomer mixture containing a polymerization initiator shown in Table 1 at 110° C. over 3 hours. After the addition, the mixture was allowed to react at 110° C. for 30 minutes. Then 2 parts of KAYAESTER O (t-butylperoxyoctate sold by Nippon Kayaku Co., Ltd.) in 40 parts of xylene were added dropwise at 110° C. over 30 minutes and the mixture allowed to react at the same temperature for additional 90 minutes. An acrylic resin solution having 49.4 % nonvolatiles, a number average molecular weight Mn measured by the GPC method of 5,400, and an activated methylene equivalent weight of 200 was obtained.
PRODUCTION EXAMPLES 2-10
Production Example 1 was followed using a mixture shown in Table 1 and Table 2, respectively. Nonvolatile contents, Mn's and other data are also shown in Table 1 and Table 2.
TABLE 1______________________________________      Production ExampleMaterial, Parts        1       2       3     4     5______________________________________2-(ethoxymalonyloxy)-        244     244     244   244   244ethyl methacrylaten-butyl acrylate        48      129     117   125   129styrene      80      --      --    --    28glycidyl methacrylate        28      28      --    --    --M-100.sup.1) --      --      39    --    --M-GMA.sup.2) --      --      --    31    --KAYAESTER O  18      18      18    18    18Nonvolatiles, %        49.4    49.4    50.0  48.7  50.5Mn           5400    5300    4300  4600  5000Activated methyle        200     200     200   200   200E.W..sup.3)Epoxy E.W..sup.3)        2004    2004    2004  2004  --______________________________________ .sup.1) 3,4epoxycyclohexylmethyl methacrylate, Daicel Chemical Industries Ltd. .sup.2) methylglycidyl methacrylate, Daicel Chemical Industries, Ltd. .sup.3) Resin solids basis.
PRODUCTION EXAMPLES 11-15 (FOR COMPARISON)
Production Example 1 was followed using a mixture shown in Table 3, respectively. Nonvolatile contents, Mn's and other data are shown also in Table 3.
TABLE 3______________________________________      Production ExampleMaterial, parts        11      12      13    14    15______________________________________2-Acetoacetoxyethyl        214     214     214   214   214methacrylaten-Butyl methacrylate        78      129     129   129   129Styrene      80      30      30    30    30Glycidyl methacrylate        28      28      --    --    --M-100.sup.1) --      --      39    --    --M-GMA.sup.2) --      --      --    31    --KAYAESTER O  18      18      18    18    18Nonvolatiles, %        49.4    50.0    51.2  49.6  50.1Mn           4,900   4,900   4,400 4,600 4,900Activated methylene        200     200     200   200   200E.W..sup.3)Epoxy E.W..sup.3)        2,004   2,004   2,004 2,004 --______________________________________ .sup.1) 3,4epoxycyclohexylmethyl methacrylate, Daicel Chemical Industries Ltd. .sup.2) methylglycidyl methacrylate, Daicel Chemical Industries, Ltd. .sup.3) Resin solids basis.
405 parts of the resin solution of Production Example 1 (200 parts as solids), 50 parts of pentaerythritol triacrylate (PETA), 2 parts of tetrabutylammonium bromide (TBABr), 10 parts of UV absorber (TINUBIN 900 sold by Ciba-Geigy AG) and 5 parts of photostabilizer (SANOL LS-400 sold by Ciba-Geigy AG) were thoroughly mixed to make a solution. The solution was applied on a tinplate using #40 bar coater and heated in an oven at 140° C. for 20 minutes. The resulting cured film was tested for gel fraction and weatherability. The gel fraction was determined based on the difference of weight before and after soaking the film in a 1:1 mixture of acetone and methanol at room temperature for 48 hours. The weatherability of the cured film was evaluated in terms of degree of yellowing when subjecting to five cycles of standard weathering test in a sunshine weatherometer.
Example 1 was followed, respectively, except that the formulation was changed as shown in Table 4 through Table 9. The results are shown in Table 4 through Table 9.
TABLE 4______________________________________Example1            2        3        4      5______________________________________Component   PETA     PETA     PETA   PTEA   PETA(a),parts   50       50       50     50     50Component   Pro. Ex. 1            Pro. Ex. 1                     Pro. Ex. 1                            Pro. Ex. 1                                   Pro. Ex. 1(b),parts   405      405      405    405    405Component   TBABr    TBANO    TBACl  TBAPA  TBASA(c),parts   2        2        2      2      2Curing  140° C. ×            140° C. ×                     140° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   99.8     98.5     97.6   98.1   98.1Weather-   GG       GG       GG     GG     GGability______________________________________ PETA: pentaerythritol triacrylate TBABr: tetrabutylammonium bromide TBANO: tetrabutylammonium nitrate TBACl: tetrabutylammonium chloride TBAPA: tetrabutylammonium phthalate TBASA: tetrabutylammonium salicylate
TABLE 5______________________________________Example6            7        8        9      10______________________________________Component   PETA     PETA     PETA   PTEA   PETA(a),parts   50       50       50     50     50Component   Pro. Ex. 1            Pro. Ex. 1                     Pro. Ex. 1                            Pro. Ex. 1                                   Pro. Ex. 1(b),parts   405      405      405    405    405Component   TBABA    TBAP     TBAI   TBAAc  TMBACl(c),parts   2        2        2      2      2Curing  140° C. ×            140° C. ×                     140° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   98.4     95.2     93.5   98.8   98.1Weather-   GG       GG       GG     GG     GGability______________________________________ TBABA: tetrabutylammonium benzoate TBAP: tetrabutylammonium dit-butylphosphate TBAI: tetrabutylammonium iodide TBAAC: tetrabutylammonium acetate TMBACl: trimethylbenzylammonium chloride
TABLE 6______________________________________Example11           12       13       14     15______________________________________Component   TMPTA    PETA     PETA   DPCA-  UA306H(a),                             120parts   50       50       50     150    50Component   Pro. Ex. 1            Pro. Ex. 1                     Pro. Ex. 1                            Pro. Ex. 2                                   Pro. Ex. 5(b),parts   405      405      405    405    396Component   TBPBr    TMSI     CPBr   TBACl  TBABr(c),parts   2        4        4      2      2Epoxy   --       --       --     --     EPIKOTEcompound                                825parts                                   15Curing  140° C. ×            140° C. ×                     140° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   98.4     90.2     96.5   92.8   93.1Weather-   GG       G        G      GG     GGability______________________________________ TMPTA: trimethylolpropane triacrylate DPCA120: KAYARAD DPCA120, dipentaerythritol/caprolactone (1:12) adduct hexacrylate sold by Nippon Kayaku Co., Ltd. UA 306H: HMDI/pentaerythritol (1:2) adduct sold by Kyoeisha Yushi Kagaku Kogyo K.K. TBPBr: tetrabutylphosphonium bromide; TMSI: trimethylsulfonium iodide; CPBr: cetylpyridiniumbromide; EPIKOTE 825: bisphenol A diglycidyl ether
TABLE 7______________________________________Example16           17       18       19     20______________________________________Component   A-400    3002A    PETA   PTEA   TMPTGA(a),parts   200      200      50     50     50Component   Pro. Ex. 3            Pro. Ex. 4                     Pro. Ex. 5                            Pro. Ex. 5                                   Pro. Ex. 5(b),parts   400      411      396    396    396Component   TBACl    TBACl    TBAOH  TBAF   NaOMe(c),parts   2        2        2      2      2Curing  140° C. ×            140° C. ×                     140° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   93.7     94.8     96.0   94.0   90.4Weather-   G        G        GG     GG     Gability______________________________________ A-400: NK ESTER A400, polyethylene glycol diacrylate sold by ShinNakamura Kagaku Kogyo K.K. 3002A: EPOXY ESTER 3002A, reaction product of bisphenol A/propylene oxide (1:2) adduct diglycidyl ether and acrylic acid sold by Kyoeisha Yushi Kagaku Kogyo K.K. TBAOH: tetrabutylammonium hydroxide; TBAF: tetrabutylammonium fluoride; NaOMe: sodium methoxide
TABLE 8______________________________________21           22       23       24     25______________________________________Component   PETA     PETA     PETA   PTEA   PETA(a),parts   50       50       50     50     50Component   Pro. Ex. 1            Pro. Ex. 1                     Pro. Ex. 1                            Pro. Ex. 1                                   Pro. Ex. 1(b),parts   405      405      405    405    405Component   Pro. Ex. 6            TBABH4   QDMC   TMOBr  GTAC(c),parts   50       2        2      2      2Curing  140° C. ×            140° C. ×                     140° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   98.9     99.2     97.5   98     97.1Weather-   GG       GG       GG     GG     GGability______________________________________ TBABH4: tetrabutylammonium tetrahydroborate QDMC: 2(methacryloyloxy)ethyltrimethylammonium chloride TMOBr: trimethyloctylammonium bromide GTAC: glycidyltrimethylammonium chloride
TABLE 9______________________________________Example26           27       28       29     30______________________________________Component   PETA     PETA     PETA   PTEA   PETA(a),parts   50       50       50     50     50Component   Pro.     Pro.     Pro.   Pro.   Pro.(b),    Ex. 1    Ex. 8    Ex. 9  Ex. 10 Ex. 10parts   405      405      405    405    405Component   Pro.     TBABr    TBABr  TBAOH  TMBOH(c),    Ex. 7parts   50       2        2      2      2Curing  140° C. ×            140° C. ×                     140° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   98.2     99.2     97.2   98     97.1Wether- GG       GG       GG     GG     GGability______________________________________ TMBOH: trimethylbenzylammonium hydroxide
Example 1 was followed, respectively, except that the formulation was changed as shown in Table 10 through Table 13. These Comparative Examples correspond to Examples 1-20. The results are shown in Table 10 through Table 13.
TABLE 10______________________________________Comparative Example1            2        3        4      5______________________________________Component   PETA     PETA     PETA   PTEA   PETA(a),parts   50       50       50     50     50Component   Pro.     Pro.     Pro.   Pro.   Pro.(b),    Ex. 11   Ex. 11   Ex. 11 Ex. 11 Ex. 11parts   405      405      405    405    405Component   TBABr    TBANO    TBACl  TBAPA  TBASA(c),parts   2        2        2      2      2Curing  140° C. ×            140° C. ×                     140° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   98.8     97.8     98.6   98.0   96.9Weather-   B        B        B      B      Bability______________________________________
TABLE 11______________________________________Comparative Example6            7        8        9      10______________________________________Component   PETA     PETA     PETA   PTEA   PETA(a),parts   50       50       50     50     50Component   Pro.     Pro.     Pro.   Pro.   Pro.(b),    Ex. 11   Ex. 11   Ex. 11 Ex. 11 Ex. 11parts   405      405      405    405    405Component   TBABA    TBAP     TBAI   TBAAc  TMBACl(c),parts   2        2        2      2      2Curing  140° C. ×            160° C. ×                     160° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   98.8     97.8     98.6   98.0   96.9Weather-   B        B        B      B      Bability______________________________________
TABLE 12______________________________________Comparative Example11           12       13       14     15______________________________________Component   TMPTA    PETA     PETA   DPCA-  UA306H(a),                             120parts   50       50       50     150    50Component   Pro.     Pro.     Pro.   Pro.   Pro.(b),    Ex. 11   Ex. 11   Ex. 11 Ex. 12 Ex. 15parts   405      405      405    400    399Component   TBPBr    TMSI     CPBr   TBACl  TBABr(c),parts   2        4        4      2      2Epoxy   --       --       --     --     EPIKOTEcompound                                825parts                                   15Curing  140° C. ×            160° C. ×                     160° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   98.7     88.8     86.9   93.8   95.4Weather-   B        B        B      B      Bability______________________________________
TABLE 13______________________________________Comparative Example16           17       18       19     20______________________________________Component   A-400    3002A    PETA   PTEA   TMPTA(a),parts   200      200      50     50     50Component   Pro.     Pro.     Pro.   Pro.   Pro.(b),    Ex. 13   Ex. 14   Ex. 15 Ex. 15 Ex. 15parts   391      403      399    399    399Component   TBACl    TBACl    TBAOH  TBAF   NaOMe(c),parts   2        2        2      2      2Curing  140° C. ×            140° C. ×                     140° C. ×                            140° C. ×                                   140° C. ×condition   20 min.  20 min.  20 min.                            20 min.                                   20 min.Gel fraction,   94.5     93.3     96.6   95.8   92.5Weather-   B        B        B      B      Bability______________________________________
A zinc phosphate-treated steel plate of 0.8 mm thickness was coated with a cathodic electrodeposition paint (POWER TOP PU-50, Nippon Paint Co., Ltd.) electrically to a dry film thickness of about 25 μm, then with a midlayer paint (ORGA P-2 sealer, Nippon Paint Co., Ltd.) by air spraying to a dry film thickness of about 40 μm. Then, both paint films were baked at 140° C. for 30 minutes.
Then, the solution of Example 1 adjusted to Ford cup #4 viscosity of 30 seconds was applied electrostatically onto the base coat film wet-on-wet, and baked both films simultaneously at 140° C. for 25 minutes.
Example 31 was followed except that the solution of Example 1 was replaced with the solution of Comparative Example 1.
Wetherability Evaluation
Cured multilayer coats of Example 31 and Comparative Example 21 were subjected to the wetherability test as in Example 1. The degree of yellowing was not observed with the multilayer coat of Example 31 while the multilayer coat of Comparative Example 21 was remarkably yellowed.
(b) a copolymer of a malonate monomer of the formula ##STR2## wherein R1 is hydrogen or methyl, R2 is a C2 -C6 alkylene, R3 is a C1 -C6 alkyl and n is a integer from 1 to 10, and an ethylenically unsaturated monomer copolymerizable therewith; and
(c) a catalyst capable of promoting the Michael reaction between said components (a) and (b).
2. The composition of claim 1, wherein said component (a) is a polyol poly(meth)acrylate, an unsaturated polyester resin, a polyester acrylate resin, an epoxy acrylate resin, a urethane acrylate resin, an α,β-unsaturated carbonyl group-containing acrylic resin, a polyether acrylate resin, a silicone oligomer having (meth) acryloyl groups, or an α,β-unsaturated carbonyl group-containing fluororesin.
US08/859,912 1996-05-22 1997-05-21 Curable resin composition for coating use Expired - Fee Related US5959028A (en)
JP8-151546 1996-05-22
JP15154696 1996-05-22
US5959028A true US5959028A (en) 1999-09-28
ID=15520886
US08/859,912 Expired - Fee Related US5959028A (en) 1996-05-22 1997-05-21 Curable resin composition for coating use
US (1) US5959028A (en)
EP (1) EP0808860A3 (en)
KR (1) KR100232793B1 (en)
CA (1) CA2205765A1 (en)
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US20140221542A1 (en) * 2011-10-07 2014-08-07 Nuplex Resins B.V. Crosslinkable composition cross-linkable by real michael addition reaction and resins for use in said composition
PL2764038T3 (en) * 2011-10-07 2017-08-31 Nuplex Resins B.V. Crosslinkable composition
SI2984133T1 (en) 2013-04-08 2018-06-29 Allnex Netherlands B.V. Composition crosslinkable by real michael addition (rma) reaction
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1997-05-21 US US08/859,912 patent/US5959028A/en not_active Expired - Fee Related
1997-05-21 EP EP97108237A patent/EP0808860A3/en not_active Ceased
1997-05-21 CA CA 2205765 patent/CA2205765A1/en not_active Abandoned
1997-05-22 KR KR1019970019916A patent/KR100232793B1/en not_active IP Right Cessation
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WO2004029118A3 (en) * 2002-09-26 2004-06-24 Ashland Inc Liquid uncrosslinked michael addition oligomers prepared in the presence of a catalyst having both an epoxy moiety and a quaternary salt
US9181452B2 (en) * 2010-04-07 2015-11-10 Nuplex Resins B.V. Crosslinkable composition crosslinkable with a latent base catalyst
US20160168320A1 (en) * 2010-04-07 2016-06-16 Nuplex Resins B.V. Crosslinkable composition crosslinkable with a latent base catalyst
US9534081B2 (en) * 2010-04-07 2017-01-03 Nuplex Resins B.V. Crosslinkable composition crosslinkable with a latent base catalyst
KR970074866A (en) 1997-12-10
CA2205765A1 (en) 1997-11-22
EP0808860A2 (en) 1997-11-26
EP0808860A3 (en) 1999-02-10
KR100232793B1 (en) 1999-12-01
EP0636669B1 (en) 1999-04-14 Radiation curable binder composition for powder paint formulations
CA1336304C (en) 1995-07-11 Top coating composition
EP0391166B2 (en) 1996-07-03 Chip resistant coatings and methods for application
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