JPH0827402A - Epoxy resin powder coating composition - Google Patents
Epoxy resin powder coating compositionInfo
- Publication number
- JPH0827402A JPH0827402A JP18873494A JP18873494A JPH0827402A JP H0827402 A JPH0827402 A JP H0827402A JP 18873494 A JP18873494 A JP 18873494A JP 18873494 A JP18873494 A JP 18873494A JP H0827402 A JPH0827402 A JP H0827402A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- epoxy
- powder coating
- coating composition
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 41
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 41
- 239000000843 powder Substances 0.000 title claims abstract description 29
- 239000008199 coating composition Substances 0.000 title claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 35
- -1 phenol compound Chemical class 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000012756 surface treatment agent Substances 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 abstract description 13
- 238000003860 storage Methods 0.000 abstract description 13
- BKCCAYLNRIRKDJ-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1h-imidazole Chemical compound N1CCN=C1C1=CC=CC=C1 BKCCAYLNRIRKDJ-UHFFFAOYSA-N 0.000 abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002845 discoloration Methods 0.000 abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002989 phenols Chemical class 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 3
- 238000001723 curing Methods 0.000 description 26
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- DPZSNGJNFHWQDC-ARJAWSKDSA-N (z)-2,3-diaminobut-2-enedinitrile Chemical compound N#CC(/N)=C(/N)C#N DPZSNGJNFHWQDC-ARJAWSKDSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NCVGSSQICKMAIA-UHFFFAOYSA-N 2-heptadecyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NCCN1 NCVGSSQICKMAIA-UHFFFAOYSA-N 0.000 description 1
- WVNBMMKXLDHERT-UHFFFAOYSA-N 2-heptyl-4,5-dihydro-1h-imidazole Chemical compound CCCCCCCC1=NCCN1 WVNBMMKXLDHERT-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VWSLLSXLURJCDF-UHFFFAOYSA-N 2-methyl-4,5-dihydro-1h-imidazole Chemical compound CC1=NCCN1 VWSLLSXLURJCDF-UHFFFAOYSA-N 0.000 description 1
- ROHTVIURAJBDES-UHFFFAOYSA-N 2-n,2-n-bis(prop-2-enyl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N(CC=C)CC=C)=N1 ROHTVIURAJBDES-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- JIYNFFGKZCOPKN-UHFFFAOYSA-N sbb061129 Chemical compound O=C1OC(=O)C2C1C1C=C(C)C2C1 JIYNFFGKZCOPKN-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- MDCWDBMBZLORER-UHFFFAOYSA-N triphenyl borate Chemical compound C=1C=CC=CC=1OB(OC=1C=CC=CC=1)OC1=CC=CC=C1 MDCWDBMBZLORER-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、常温における長期保存
性と加熱硬化時における急速な硬化性を有するエポキシ
樹脂粉体塗料組成物に関するものであり、硬化特性に優
れ、保存安定性が高く、且つ硬化時の変色性を少なくし
たエポキシ樹脂粉体塗料組成物を提供するものである。FIELD OF THE INVENTION The present invention relates to an epoxy resin powder coating composition having long-term storability at room temperature and rapid curability at the time of heat curing, which has excellent curing characteristics and high storage stability. Further, the present invention provides an epoxy resin powder coating composition having reduced discoloration upon curing.
【０００２】[0002]
【従来の技術】本発明者等は、先にアルキルアミン類、
芳香族アミン類あるいは含窒素複素環化合物をエポキシ
樹脂に付加させて得られるエポキシ樹脂付加物（以下、
エポキシアダクトという）を用い、このエポキシアダク
トの表面をホウ酸エステル化合物等を用いて処理するこ
とにより得られる一液性エポキシ配合物に好適な硬化剤
あるいは硬化促進剤を提供している（特開平６−７３１
５６号公報参照）。2. Description of the Related Art The present inventors have previously reported that alkylamines,
An epoxy resin adduct obtained by adding an aromatic amine or a nitrogen-containing heterocyclic compound to an epoxy resin (hereinafter,
(Referred to as "epoxy adduct"), and a curing agent or curing accelerator suitable for a one-pack type epoxy compound obtained by treating the surface of the epoxy adduct with a boric acid ester compound or the like (Japanese Patent Laid-Open No. Hei 10-1999) 6-731
No. 56).
【０００３】また粉体塗料用途にイミダゾリン系化合物
を用いたものとしては、特公昭６１−２１０４号公報及
び特開昭５７−６１０６５号公報には脂肪族アミンとイ
ミダゾリンを硬化剤として用いるエポキシ樹脂粉体塗
料、また特公平１−４００６６号公報にはイミダゾリン
系化合物とカルボン酸との反応物を硬化促進剤成分とし
て用いる粉体塗料用樹脂組成物がそれぞれ開示されてい
る。Further, as the one using an imidazoline compound for powder coating application, an epoxy resin powder using an aliphatic amine and imidazoline as a curing agent is disclosed in JP-B-61-2104 and JP-A-57-61065. Body paints and Japanese Patent Publication No. 1-40066 each disclose a resin composition for powder paints which uses a reaction product of an imidazoline compound and a carboxylic acid as a curing accelerator component.
【０００４】[0004]
【発明が解決しようとする課題】粉体塗料は加熱硬化さ
せる過程において、その樹脂分が溶融され平滑化された
塗膜が形成されるが、その硬化温度が高ければ、得られ
た塗膜に焼けによる変色を生じ、得られた塗膜の着色性
能が低下するなどの問題があった。また、粉体塗料の取
扱いを簡便にするため、予め硬化剤が粉体塗料に配合さ
れている場合においても、長期にわたる保存安定性の要
望も強いものがあった。本発明の目的は、硬化特性及び
保存安定性のいずれもが高く、変色性の低い硬化塗膜が
得られるエポキシ樹脂粉体塗料組成物を提供するもので
ある。In the process of heating and curing the powder coating material, the resin component is melted to form a smoothed coating film. If the curing temperature is high, the obtained coating film will be There is a problem that discoloration due to burning occurs and the coloring performance of the obtained coating film is deteriorated. In addition, there is a strong demand for long-term storage stability even when a curing agent is mixed in advance with the powder coating material in order to facilitate handling of the powder coating material. An object of the present invention is to provide an epoxy resin powder coating composition which has both a high curing property and a high storage stability and which gives a cured coating film with low discoloration.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、このよう
な事情に鑑み鋭意検討を重ねた結果、エポキシ化合物に
イミダゾリン化合物を反応させて得られるエポキシアダ
クトを硬化剤あるいは硬化促進剤として用いる際に、ホ
ウ酸エステル及びフェノール化合物を共に用いることに
より、所期の目的が達成できることを見い出し、本発明
のエポキシ樹脂粉体塗料組成物を完成させるに至った。Means for Solving the Problems The inventors of the present invention have made extensive studies in view of such circumstances, and as a result, use an epoxy adduct obtained by reacting an imidazoline compound with an epoxy compound as a curing agent or a curing accelerator. At that time, it was found that the intended purpose can be achieved by using both the borate ester and the phenol compound, and the epoxy resin powder coating composition of the present invention was completed.
【０００６】本発明の実施において用いられるエポキシ
アダクトは、イミダゾリン化合物とエポキシ樹脂の付加
反応させたのち、得られたエポキシアダクトを粉砕する
ことによって調製することができ、調製に当たって用い
られるイミダゾリン化合物の代表的なものとしては、２
−メチルイミダゾリン、２−ヘプチルイミダゾリン、２
−ヘプタデシルイミダゾリン、２−フェニルイミダゾリ
ンなどである。また用いられるエポキシ樹脂の代表的な
ものとしては、ビスフェノールＡ型エポキシ樹脂、ビス
フェノールＦ型エポキシ樹脂、環式脂肪族系エポキシ樹
脂、グリシジルエステル系エポキシ樹脂、グリシジルア
ミン系エポキシ樹脂、ヒダントイン型エポキシ樹脂、ト
リグリシジルイソシアヌレート、フェニルグリシジルエ
ーテル及びブチルグリシジルエーテル等が挙げられ、こ
れらの樹脂は単独あるいは複数混合して用いられる。The epoxy adduct used in the practice of the present invention can be prepared by subjecting an imidazoline compound and an epoxy resin to an addition reaction and then pulverizing the resulting epoxy adduct, which is a typical imidazoline compound used in the preparation. The two are
-Methyl imidazoline, 2-heptyl imidazoline, 2
-Heptadecyl imidazoline, 2-phenyl imidazoline and the like. Typical examples of the epoxy resin used include bisphenol A type epoxy resin, bisphenol F type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, Examples thereof include triglycidyl isocyanurate, phenyl glycidyl ether and butyl glycidyl ether, and these resins may be used alone or in combination of two or more.
【０００７】本発明の実施に当たってホウ酸あるいはホ
ウ酸エステル化合物及びフェノール化合物の混合物が、
前記エポキシアダクトの表面処理を目的として使用され
るが、ホウ酸エステル化合物の代表的なものとしては、
ホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロ
ピル、ホウ酸トリブチル及びホウ酸トリフェニルなどで
あり、またフェノール化合物の代表的なものとしては、
カテコール、４−ｔ−ブチルカテコール、ピロガロー
ル、レゾルシン、ハイドロキノン、フロログルシノー
ル、ビスフェノールＡ、ビスフェノールＦ、ジヒドロキ
シビフェニル、ジヒドロキシナフタレン、１、１、１−
トリス（４−ヒドロキシフェニル）エタン及びビス（４
−ヒドロキシフェニル）スルフォン等の化合物、ノボラ
ック型あるいはレゾール型のフェノール樹脂並びにポリ
ビニルフェノール等のフェノール系重合体などである。In carrying out the present invention, a mixture of boric acid or boric acid ester compound and a phenol compound is used.
It is used for the purpose of surface treatment of the epoxy adduct, but as a typical boric acid ester compound,
Trimethyl borate, triethyl borate, tripropyl borate, tributyl borate, triphenyl borate, and the like, and typical phenol compounds include:
Catechol, 4-t-butylcatechol, pyrogallol, resorcin, hydroquinone, phloroglucinol, bisphenol A, bisphenol F, dihydroxybiphenyl, dihydroxynaphthalene, 1,1,1-
Tris (4-hydroxyphenyl) ethane and bis (4
Compounds such as -hydroxyphenyl) sulfone, novolac type or resol type phenolic resins, and phenolic polymers such as polyvinylphenol.
【０００８】本発明のエポキシ樹脂粉体塗料組成物の製
造に当たって、ホウ酸あるいはホウ酸エステル化合物の
配合割合は、エポキシアダクト１００重量部に対して
０．０１〜２００重量部の範囲であり、好ましくは０．
５〜４０重量部である。０．０１重量部未満の添加量で
は十分な保存安定性を確保し難く、また２００重量部を
超えると硬化不良を誘発するので好ましくない。In the production of the epoxy resin powder coating composition of the present invention, the compounding ratio of boric acid or borate ester compound is in the range of 0.01 to 200 parts by weight, preferably 100 parts by weight of the epoxy adduct. Is 0.
5 to 40 parts by weight. If the amount added is less than 0.01 parts by weight, it is difficult to ensure sufficient storage stability, and if it exceeds 200 parts by weight, curing failure is induced, which is not preferable.
【０００９】本発明のエポキシ樹脂粉体塗料組成物の製
造に当たって用いられるフェノール化合物の配合割合
は、エポキシ樹脂１００重量部に対して０．００１〜５
０部重量部の範囲であり、好ましくは０．０５〜１０重
量部である。またこの添加されるフェノール化合物の量
は、エポキシアダクトの表面処理剤として同時に使用さ
れるホウ酸あるいはホウ酸エステル化合物の量とも関連
するものであり、フェノール水酸基とホウ酸またはホウ
酸エステルの当量割合は、１：０．２〜１：５の範囲が
好適である。The compounding ratio of the phenol compound used in the production of the epoxy resin powder coating composition of the present invention is 0.001 to 5 with respect to 100 parts by weight of the epoxy resin.
The range is 0 part by weight, preferably 0.05 to 10 parts by weight. The amount of the phenol compound added is also related to the amount of the boric acid or borate ester compound used at the same time as the surface treating agent for the epoxy adduct, and the equivalent ratio of the phenolic hydroxyl group and boric acid or borate ester. Is preferably in the range of 1: 0.2 to 1: 5.
【００１０】本発明のエポキシ樹脂粉体塗料組成物の製
造において、硬化剤を配合する割合としては、エポキシ
樹脂１００重量部に対して硬化剤を０．５〜５０重量
部、好ましくは１〜２０重量部添加すればよい。また本
発明の実施において、無水マレイン酸、無水フタル酸、
無水トリメリット酸、無水ピロメリット酸、無水コハク
酸、無水メチルナジック酸及び無水クロレンデック酸等
の酸無水物並びにジシアンジアミド、有機酸ヒドラジッ
ド、ジアミノマレオニトリル、ジアリルメラミン及びア
ミンイミドなどを硬化剤とし、表面処理されたエポキシ
アダクトを硬化促進剤として使用した場合においても、
同様に保存安定性に優れたエポキシ樹脂粉体塗料組成物
が得られる。In the production of the epoxy resin powder coating composition of the present invention, the proportion of the curing agent is 0.5 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the epoxy resin. It may be added in parts by weight. In the practice of the present invention, maleic anhydride, phthalic anhydride,
Surface treatment with trimellitic anhydride, pyromellitic anhydride, succinic anhydride, acid anhydrides such as methyl nadic acid anhydride and chlorendeic anhydride, and dicyandiamide, organic acid hydrazide, diaminomaleonitrile, diallyl melamine and amine imide as a curing agent. Even when using the epoxy adduct prepared as a curing accelerator,
Similarly, an epoxy resin powder coating composition having excellent storage stability can be obtained.
【００１１】本発明のエポキシ樹脂粉体塗料組成物の調
製に当たっては、必要に応じて充填剤、酸化防止剤、難
燃剤、可塑化剤、反応性希釈剤、着色剤及び粘度調整剤
等の添加剤を使用してもよく、充填剤の代表的なものと
しては溶融シリカ、結晶性シリカ、炭酸カルシウム、酸
化チタン、酸化アンチモン、アスベスト及びガラス繊維
などであり、好ましくはシラン系あるいはチタネート系
等のカップリング剤を用いて表面を処理したものが用い
られる。以下、実施例及び比較例によって本発明の内容
を具体的に説明する。In preparing the epoxy resin powder coating composition of the present invention, if necessary, a filler, an antioxidant, a flame retardant, a plasticizer, a reactive diluent, a colorant, a viscosity modifier and the like are added. Agents may be used, and typical examples of the filler include fused silica, crystalline silica, calcium carbonate, titanium oxide, antimony oxide, asbestos and glass fiber, and preferably silane-based or titanate-based fillers. A product whose surface is treated with a coupling agent is used. Hereinafter, the content of the present invention will be specifically described with reference to Examples and Comparative Examples.
【００１２】[0012]
（実施例１）エポキシ化合物〔商品名：エピコート＃８
２８、油化シェルエポキシ（株）製〕と２−フェニルイ
ミダゾリン〔商品名：２ＰＺＬ、四国化成工業（株）
製〕を当量比１：１をメチルエチルケトンに溶解したの
ち、加熱反応して得られた反応付加物を粉砕し、粉末状
のエポキシアダクトを得た。(Example 1) Epoxy compound [trade name: Epicoat # 8
28, manufactured by Yuka Shell Epoxy Co., Ltd. and 2-phenylimidazoline [trade name: 2PZL, Shikoku Chemicals Co., Ltd.]
The product was dissolved in methyl ethyl ketone in an equivalent ratio of 1: 1 and the reaction product was heated and pulverized to obtain a powdery epoxy adduct.
【００１３】次いで、エポキシ樹脂〔商品名：エピコー
ト＃１００４、油化シェルエポキシ（株）製〕１００重
量部に硬化剤として前記エポキシアダクト２０重量部、
また表面処理剤としてホウ酸エステル１重量部及びフェ
ノール樹脂１重量部、充填剤としてシリカ３重量部を加
え、この配合物を８０℃の温度で溶融混合したのち、冷
却し粉砕してエポキシ樹脂粉体塗料組成物を得た。得ら
れたエポキシ樹脂粉体塗料を余熱したセラミック基板上
にスプレーし、約２３０℃の温度で焼付けを行った。Next, 100 parts by weight of an epoxy resin (trade name: Epicoat # 1004, manufactured by Yuka Shell Epoxy Co., Ltd.) and 20 parts by weight of the epoxy adduct as a curing agent,
Further, 1 part by weight of boric acid ester and 1 part by weight of phenol resin as a surface treating agent, and 3 parts by weight of silica as a filler were added, and the mixture was melt-mixed at a temperature of 80 ° C., then cooled and pulverized to obtain an epoxy resin powder. A body coating composition was obtained. The obtained epoxy resin powder coating material was sprayed onto a preheated ceramic substrate and baked at a temperature of about 230 ° C.
【００１４】なお、エポキシ樹脂粉体塗料組成物の保存
安定性は、ゲル化時間が調製直後より１割減少するのに
要する時間を日数で表し、ゲル化時間は１５０℃の温度
を保持した熱板上において、ストロークキュアー法によ
り求め、また着色性は目視にて行い、その結果は表１に
示すとおりであった。The storage stability of the epoxy resin powder coating composition is represented by the number of days required for the gelation time to decrease by 10% from the time immediately after the preparation, and the gelation time is the heat at a temperature of 150 ° C. It was determined on the plate by the stroke cure method, and the coloring property was visually observed. The results are shown in Table 1.
【００１５】（実施例２）実施例１において、エポキシ
アダクトを調製する際に用いたエポキシ化合物〔商品
名：エピコート＃８２８〕の代わりにエポキシ化合物
〔商品名：エピコート＃４３８、油化シェルエポキシ
（株）製〕を用いた以外は、全く実施例１と同じ方法に
より、エポキシアダクトを調製した。得られたエポキシ
アダクトを用いて、実施例１と同様の方法によりエポキ
シ樹脂粉体塗料組成物を調製し、ゲル化時間、保存安定
性及び着色性をみたところ、その結果は表１に示すとお
りであった。(Example 2) Instead of the epoxy compound (trade name: Epicoat # 828) used in the preparation of the epoxy adduct in Example 1, an epoxy compound [trade name: Epicoat # 438, oiled shell epoxy ( Manufactured by K.K.) was used to prepare an epoxy adduct by the same method as in Example 1. Using the obtained epoxy adduct, an epoxy resin powder coating composition was prepared in the same manner as in Example 1, and the gelling time, storage stability and colorability were examined. The results are shown in Table 1. Met.
【００１６】（実施例３）実施例１において、エポキシ
アダクトを調製する際に用いた２−フェニルイミダゾリ
ンの代わりに２−メチルイミダゾリン〔商品名：２ＭＺ
Ｌ、四国化成工業（株）製〕を用いた以外は、全く実施
例１と同じ方法により、エポキシアダクトを調製した。
得られたエポキシアダクトを用いて、実施例１と同様の
方法によりエポキシ樹脂粉体塗料組成物を調製し、ゲル
化時間、保存安定性及び着色性をみたところ、その結果
は表１に示すとおりであった。Example 3 Instead of 2-phenylimidazoline used in the preparation of the epoxy adduct in Example 1, 2-methylimidazoline [trade name: 2MZ
L, manufactured by Shikoku Chemicals Co., Ltd.] was used to prepare an epoxy adduct by the same method as in Example 1.
Using the obtained epoxy adduct, an epoxy resin powder coating composition was prepared in the same manner as in Example 1, and the gelling time, storage stability and colorability were examined. The results are shown in Table 1. Met.
【００１７】（実施例４）実施例１で用いたのと同じエ
ポキシ樹脂１００重量部に硬化剤としてジシアンジアミ
ド１５重量部、硬化促進剤として実施例１において得ら
れたエポキシアダクト５重量部、また表面処理剤として
ホウ酸エステル１重量部及びフェノール樹脂１重量部、
充填剤としてシリカ３重量部を加え、実施例１と同様の
方法によりエポキシ樹脂粉体塗料組成物を調製し、ゲル
化時間、保存安定性及び着色性をみたところ、その結果
は表１に示すとおりであった。(Example 4) 100 parts by weight of the same epoxy resin as used in Example 1, 15 parts by weight of dicyandiamide as a curing agent, 5 parts by weight of the epoxy adduct obtained in Example 1 as a curing accelerator, and surface 1 part by weight of boric acid ester and 1 part by weight of phenolic resin as a treating agent,
An epoxy resin powder coating composition was prepared in the same manner as in Example 1 except that 3 parts by weight of silica was added as a filler, and the gelling time, storage stability and colorability were examined. The results are shown in Table 1. It was as it was.
【００１８】（比較例１）実施例１ないし３における硬
化剤としてのエポキシアダクト、表面処理剤としてのホ
ウ酸エステルなどの代わりに、硬化剤として２−フェニ
ルイミダゾリンのみを用いた以外は、全く実施例１と同
じ方法によりエポキシ樹脂粉体塗料組成物を調製し、ゲ
ル化時間、保存安定性及び着色性をみたところ、その結
果は表１に示すとおりであった。COMPARATIVE EXAMPLE 1 Except that only 2-phenylimidazoline was used as the curing agent in place of epoxy adduct as the curing agent and boric acid ester as the surface treatment agent in Examples 1 to 3 except that only 2-phenylimidazoline was used. An epoxy resin powder coating composition was prepared by the same method as in Example 1, and the gelling time, storage stability and colorability were examined. The results are shown in Table 1.
【００１９】（比較例２）実施例４における硬化促進剤
としてのエポキシアダクト、表面処理剤としてのホウ酸
エステルなどの代わりに、硬化促進剤として２−フェニ
ルイミダゾリンを用いた以外は、全く実施例４と同じ方
法によりエポキシ樹脂粉体塗料組成物を調製し、ゲル化
時間、保存安定性及び着色性をみたところ、その結果は
表１に示すとおりであった。(Comparative Example 2) In place of the epoxy adduct as the curing accelerator and the boric acid ester as the surface treatment agent in Example 4, 2-phenylimidazoline was used as the curing accelerator, except that Example 2 was used. An epoxy resin powder coating composition was prepared by the same method as in Example 4, and the gelation time, storage stability and colorability were examined. The results are shown in Table 1.
【００２０】[0020]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】本発明のエポキシ樹脂粉体塗料組成物
は、硬化剤あるいは硬化促進剤としてエポキシアダクト
を使用し、エポキシアダクトの表面処理を目的としてホ
ウ酸あるいはホウ酸エステル化合物及びフェノール系化
合物を共存させているので、良好な貯蔵安定性と優れた
硬化特性を発現でき、焼付け塗装後の塗料の変色も少な
いため、塗料材料として有用である。The epoxy resin powder coating composition of the present invention uses an epoxy adduct as a curing agent or a curing accelerator, and contains boric acid or a borate ester compound and a phenolic compound for the purpose of surface treatment of the epoxy adduct. Since they are made to coexist, good storage stability and excellent curing characteristics can be exhibited, and there is little discoloration of the paint after baking coating, so it is useful as a paint material.
Claims (2)
ゾリン化合物を反応させて得られるエポキシ付加物から
なる硬化剤、ホウ酸エステル及びフェノール化合物を必
須成分として含有することを特徴とするエポキシ樹脂粉
体塗料組成物。1. An epoxy resin powder coating composition comprising an epoxy resin, a curing agent composed of an epoxy adduct obtained by reacting an epoxy compound with an imidazoline compound, a borate ester, and a phenol compound as essential components. Stuff.
にイミダゾリン化合物を反応させて得られるエポキシ付
加物からなる硬化促進剤、ホウ酸エステル及びフェノー
ル化合物を含む表面処理剤を必須成分として含有するこ
とを特徴とするエポキシ樹脂粉体塗料組成物。2. An epoxy resin, a curing agent, a curing accelerator composed of an epoxy adduct obtained by reacting an epoxy compound with an imidazoline compound, a surface treatment agent containing a borate ester and a phenol compound as essential components. A characteristic epoxy resin powder coating composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18873494A JPH0827402A (en) | 1994-07-18 | 1994-07-18 | Epoxy resin powder coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18873494A JPH0827402A (en) | 1994-07-18 | 1994-07-18 | Epoxy resin powder coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0827402A true JPH0827402A (en) | 1996-01-30 |
Family
ID=16228846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18873494A Pending JPH0827402A (en) | 1994-07-18 | 1994-07-18 | Epoxy resin powder coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0827402A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7784952B2 (en) | 2004-03-10 | 2010-08-31 | Kiwa Chemical Industry Co., Ltd. | Enclosed lens type retroreflective sheet with wide-angle reflective performance and external illumination system |
| JP2011518936A (en) * | 2008-04-30 | 2011-06-30 | シーカ・テクノロジー・アーゲー | Activator for epoxy resin composition |
-
1994
- 1994-07-18 JP JP18873494A patent/JPH0827402A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7784952B2 (en) | 2004-03-10 | 2010-08-31 | Kiwa Chemical Industry Co., Ltd. | Enclosed lens type retroreflective sheet with wide-angle reflective performance and external illumination system |
| JP2011518936A (en) * | 2008-04-30 | 2011-06-30 | シーカ・テクノロジー・アーゲー | Activator for epoxy resin composition |
| US20130253094A1 (en) * | 2008-04-30 | 2013-09-26 | Sika Technology Ag | Activator for epoxy resin compositions |
| US8859695B2 (en) | 2008-04-30 | 2014-10-14 | Sika Technology Ag | Activator for epoxy resin compositions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4546155A (en) | Latent curing agents for epoxy resins | |
| EP0569044B1 (en) | Latent curing agents for epoxy resins | |
| EP0659793A1 (en) | One component epoxy resin compositions containing modified epoxy-amine adducts as curing agents | |
| US4440914A (en) | Solid epoxy resin systems | |
| US5500461A (en) | Stable waterborne epoxy resin dispersion containing micronized DICY | |
| US4894431A (en) | Accelerated curing systems for epoxy resins | |
| EP0459951A2 (en) | Char forming nonhalogenated flame retardant epoxy composition | |
| JP2756630B2 (en) | Epoxy resin composition | |
| JPH0619064B2 (en) | Pioneer solid epoxy resin | |
| JP3476994B2 (en) | Epoxy resin composition | |
| JPH10298405A (en) | Epoxy resin composition and cured product composite | |
| JPH0699542B2 (en) | Hardener mixture for epoxy resin and method of use thereof | |
| JPH0827402A (en) | Epoxy resin powder coating composition | |
| EP0761709B1 (en) | 1-Imidazolylmethyl-2-naphthols as catalysts for curing epoxy resins | |
| JPH0336847B2 (en) | ||
| JP3835725B2 (en) | Flame retardant epoxy resin powder coating | |
| JP2000191953A (en) | Flame-retardant epoxy resin powder coating | |
| JPH04300974A (en) | Epoxy resin powder coating material | |
| JP2001002960A (en) | Flame retardant epoxy resin powder coating material | |
| JPS61190521A (en) | Epoxy resin composition | |
| JP2001172555A (en) | Flame-retardant epoxy resin powder coating material | |
| JPS6053524A (en) | Flame-retardant epoxy resin composition | |
| JPH04142360A (en) | Flame-retardant resin composition | |
| US5210115A (en) | Allyl magnesium halide modified epoxy resin composition | |
| JPH01110526A (en) | Epoxy resin composition for prepreg |