JP5784484B2 - Water-based coating agent composition - Google Patents
Water-based coating agent composition Download PDFInfo
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- JP5784484B2 JP5784484B2 JP2011289134A JP2011289134A JP5784484B2 JP 5784484 B2 JP5784484 B2 JP 5784484B2 JP 2011289134 A JP2011289134 A JP 2011289134A JP 2011289134 A JP2011289134 A JP 2011289134A JP 5784484 B2 JP5784484 B2 JP 5784484B2
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- 239000011248 coating agent Substances 0.000 title description 56
- 239000000203 mixture Substances 0.000 title description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title description 12
- 239000008199 coating composition Substances 0.000 claims description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 239000011230 binding agent Substances 0.000 claims description 25
- 229920001296 polysiloxane Polymers 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 16
- 239000002518 antifoaming agent Substances 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 229910052845 zircon Inorganic materials 0.000 claims description 12
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000454 talc Substances 0.000 claims description 11
- 229910052623 talc Inorganic materials 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229920003986 novolac Polymers 0.000 claims description 9
- 230000009970 fire resistant effect Effects 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000576 coating method Methods 0.000 description 43
- 206010010904 Convulsion Diseases 0.000 description 35
- 239000004576 sand Substances 0.000 description 31
- 238000005266 casting Methods 0.000 description 30
- 239000002245 particle Substances 0.000 description 10
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- 229910052751 metal Inorganic materials 0.000 description 7
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- 230000003254 anti-foaming effect Effects 0.000 description 5
- 230000000573 anti-seizure effect Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- 239000007849 furan resin Substances 0.000 description 4
- -1 polyoxymethylene Polymers 0.000 description 4
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- 229910001018 Cast iron Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 3
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- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004637 bakelite Substances 0.000 description 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- OWEYKIWAZBBXJK-UHFFFAOYSA-N 1,1-Dichloro-2,2-bis(4-hydroxyphenyl)ethylene Chemical compound C1=CC(O)=CC=C1C(=C(Cl)Cl)C1=CC=C(O)C=C1 OWEYKIWAZBBXJK-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-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
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 229930003836 cresol Natural products 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
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- 239000010445 mica Substances 0.000 description 1
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- 239000002480 mineral oil Substances 0.000 description 1
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- 238000002156 mixing Methods 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
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- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
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- 235000019353 potassium silicate Nutrition 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
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Description
本発明は、耐焼着性に優れた水性塗型剤組成物に関する。 The present invention relates to an aqueous coating composition having excellent anti-seizure properties.
鋳造用塗型剤は、溶湯が接する砂型（鋳型）の表面に塗布して塗型膜を塗装することにより、砂型の表面を保護するものであることが知られている。このような鋳造用塗型剤は、溶湯と砂型表面との化学反応や、鋳物の焼着欠陥の発生を防止するために用いられる。特にこの焼着欠陥は、鋳込み重量が大きいほど、また、肉厚箇所が多いほど発生しやすくなる。すなわち、注湯から凝固までの時間が長いほど焼着が発生しやすくなる。 It is known that the casting mold agent protects the surface of the sand mold by coating the surface of the sand mold (mold) with which the molten metal comes into contact and coating the coating film. Such a casting coating agent is used to prevent the chemical reaction between the molten metal and the sand mold surface and the occurrence of casting defects in the casting. In particular, this seizure defect is more likely to occur as the casting weight increases and as the thickness increases. That is, as the time from pouring to solidification is longer, seizure is more likely to occur.
これらの焼着欠陥を低減するために、最も重要な塗型物性のひとつとして、注湯時の熱によって加熱された時の塗膜強度、いわゆる「熱間塗膜強度」が挙げられる。また、その熱間塗膜強度以外にも、鋳型に塗型を塗装したときに生じる「はじき」や水性塗型剤特有の泡による乾燥後の塗膜に生じる「ピンホール状の塗膜欠陥」を作らないことも特に重要である。 In order to reduce these seizure defects, one of the most important coating physical properties is the coating strength when heated by the heat during pouring, so-called “hot coating strength”. In addition to the strength of the hot coating film, the “repellency” that occurs when the mold is applied to the mold and the “pinhole-shaped coating film defect” that occurs in the coating film after drying due to the foam specific to aqueous coating agents. It is especially important not to make.
すなわち、焼着が少ない健全な鋳物を作製するためには、高い熱間塗膜強度と、「はじき」や「ピンホール状の塗膜欠陥」が生じない健全な塗膜を作製することが特に重要である。 In other words, in order to produce a sound casting with less seizure, it is particularly necessary to produce a strong coating film with high hot coating film strength and no “repelling” or “pinhole-like coating film defects”. is important.
特許文献１では、脱泡剤として、シリコーンまたは鉱物油を含む塗型剤組成物の提案が、また、先行文献２では、メタノール、エタノールを含む塗型剤が、先行文献３では、フェノール樹脂等の有機バインダーと消泡剤を含む塗型剤が提案されている。
しかし、特許文献１，２，及び３記載の塗型剤では、重量が大きい、もしくは、肉厚の鋳物を製造するには耐焼着性が不充分であることが本発明者らの検討により判明した。また、ノボラック型フェノール樹脂は熱間塗膜強度に優れるが、水に溶けず、水性塗型剤組成物中では分散しており、はじきのない塗膜を形成することが困難であることを見出した。 However, the inventors have found that the coating agents described in Patent Documents 1, 2, and 3 are insufficient in seizure resistance to produce heavy or thick castings. did. In addition, the novolac type phenolic resin is excellent in hot coating film strength, but does not dissolve in water and is dispersed in the aqueous coating composition, and it is difficult to form a coating without repelling. It was.
本発明は、耐焼着性及び塗膜剥離防止性に優れ、塗布作業時の泡を低減できる引火危険性のない水性塗型剤組成物を提供する。 The present invention provides an aqueous coating composition that is excellent in anti-seizure property and coating film peeling prevention, and can reduce the foam during the coating operation and has no ignition risk.
本発明の水性塗型剤組成物は、耐火性骨材、バインダー、消泡剤及び溶媒を含む水性塗型剤組成物であって、前記バインダーとしてノボラック型フェノール樹脂を含有し、前記耐火性骨材１００重量部に対し、前記消泡剤として固形分中のＳｉ濃度が３．０〜６．０重量％であるポリエーテル変性シリコーンエマルジョンを固形分として０．０２〜０．３０重量部、及び前記溶媒として炭素数１〜３の１価アルコール０．２〜２．４重量部を含有する水性塗型剤組成物である。 The aqueous coating composition of the present invention is an aqueous coating composition comprising a fire-resistant aggregate, a binder, an antifoaming agent and a solvent, containing a novolac-type phenol resin as the binder, and the fire-resistant bone composition 0.02 to 0.30 parts by weight of a polyether-modified silicone emulsion having a solid content of 3.0 to 6.0% by weight as the antifoaming agent, based on 100 parts by weight of the material, and It is an aqueous coating agent composition containing 0.2 to 2.4 parts by weight of a monohydric alcohol having 1 to 3 carbon atoms as the solvent.
本発明の水性塗型剤組成物は、耐焼着性及び塗膜剥離防止性に優れ、塗布作業時の泡を低減できる引火危険性のない水性塗型剤組成物を提供できる。即ち、本発明の水性塗型剤組成物によれば、熱間塗膜強度が高く、「はじき」や「ピンホール状の塗膜欠陥」が生じない健全な塗膜を作製することができる。その結果、焼着が大幅に低減できるため、生産性の向上やコストの低減を容易に達成することができる。 The aqueous coating composition of the present invention can provide an aqueous coating composition that is excellent in seizure resistance and coating film peeling prevention and can reduce foam during the coating operation and has no ignition risk. That is, according to the aqueous coating composition of the present invention, it is possible to produce a healthy coating film having high hot coating film strength and free from “repelling” and “pinhole-shaped coating film defects”. As a result, the seizure can be greatly reduced, so that an improvement in productivity and a reduction in cost can be easily achieved.
本発明の水性塗型剤組成物は、耐火性骨材、バインダー、消泡剤及び溶媒を含むものであり、前記バインダーとしてノボラック型フェノール樹脂を含有し、前記耐火性骨材１００重量部に対し、前記消泡剤として固形分中のＳｉ濃度が３．０〜６．０重量％であるポリエーテル変性シリコーンエマルジョンを固形分として０．０２〜０．３０重量部、及び前記溶媒として炭素数１〜３の１価アルコール０．２〜２．４重量部を含有する水性塗型剤組成物である。本発明の水性塗型剤組成物は、耐焼着性及び塗膜剥離防止性に優れる。このような効果を奏する理由は定かではないが、以下のように考えられる。
特定量の特定構造を有するポリエーテル変性シリコーンエマルジョンと特定量の炭素数１〜３の１価アルコールを併用することにより、水に不溶であるノボラック型フェノール樹脂の分散力を高め、砂型への水性塗型剤組成物の濡れ性が向上し、その結果、砂型への密着性が向上した緻密な膜が形成でき、ノボラック型フェノール樹脂の熱間塗膜強度が発揮され、耐焼着性が飛躍的に改善できるものと推察される。
以下、本発明の水性塗型剤組成物に含有される成分について説明する。
The aqueous coating composition of the present invention contains a fireproof aggregate, a binder, an antifoaming agent and a solvent, contains a novolac type phenol resin as the binder, and is based on 100 parts by weight of the fireproof aggregate. , 0.02 to 0.30 parts by weight of a polyether-modified silicone emulsion having a Si concentration of 3.0 to 6.0% by weight as a solid content as the antifoaming agent, and 1 carbon atom as the solvent A water-based coating agent composition containing 0.2 to 2.4 parts by weight of a monohydric alcohol of .about.3. The aqueous coating composition of the present invention is excellent in seizure resistance and coating film peeling prevention. The reason for such an effect is not clear, but is considered as follows.
By using together a polyether-modified silicone emulsion having a specific amount of a specific structure and a specific amount of monohydric alcohol having 1 to 3 carbon atoms, the dispersibility of water-insoluble novolak-type phenol resin is increased, and water-based sand type The wettability of the coating composition is improved, and as a result, a dense film with improved adhesion to the sand mold can be formed, the hot coating strength of the novolac type phenolic resin is exhibited, and the seizure resistance is dramatically improved. It is speculated that it can be improved.
Hereinafter, the components contained in the aqueous coating composition of the present invention will be described.
＜耐火性骨材＞
耐火性骨材としては、特に限定されないが、塗型の耐火性、経済性、及び溶融金属との耐反応性の観点から、ムライト、シリカ、アルミナ、マグネシア、ジルコン、アルミナシリケート、黒曜石、オリビン、タルク、黒鉛及び雲母から選ばれる１種以上を使用することが好ましい。また、耐焼着性の観点から、ジルコン、タルク及び黒鉛（中でも鱗状黒鉛）から選ばれる１種以上を使用することが好ましく、ジルコン、タルク及び黒鉛（中でも鱗状黒鉛）を併用することがより好ましい。
<Fireproof aggregate>
The refractory aggregate is not particularly limited, but from the viewpoint of coating fire resistance, economy, and reaction resistance with molten metal, mullite, silica, alumina, magnesia, zircon, alumina silicate, obsidian, olivine, It is preferable to use one or more selected from talc, graphite and mica. Moreover, it is preferable to use 1 or more types chosen from a zircon, talc, and graphite (especially scaly graphite) from a viewpoint of seizure resistance, and it is more preferable to use zircon, talc, and graphite (especially scaly graphite) together.
ジルコン、タルク及び黒鉛を併用する場合、鋳物の耐焼着性の観点から、ジルコンとタルクと黒鉛の重量比率は、ジルコン：タルク：黒鉛＝１５〜３５：３５〜５５：２０〜４０が好ましく、２０〜３０：４０〜５０：２５〜３５がより好ましく、２２〜２８：４２〜４８：２７〜３３が更に好ましい。 When zircon, talc and graphite are used in combination, the weight ratio of zircon, talc and graphite is preferably zircon: talc: graphite = 15 to 35:35 to 55:20 to 40, from the viewpoint of seizure resistance of the casting. -30: 40-50: 25-35 are more preferable, and 22-28: 42-48: 27-33 are still more preferable.
本発明で使用される耐火性骨材は、塗布作業性を向上させる観点から、平均粒径が０．５〜１００μｍであることが好ましく、１〜７０μｍであることがより好ましく、５〜５０μｍであることが更に好ましい。ここで、耐火性骨材の平均粒径は、レーザー回折式粒度分布測定装置（堀場製作所社製ＬＡ−９２０）を用いて測定された体積中位粒径（Ｄ５０）である。分析条件は下記の通りである。
測定方法：フロー法
分散媒：イオン交換水にヘキサメタリン酸ナトリウム（０．１重量％）を加えた溶媒
分散方法：攪拌、内蔵超音波照射（３分間）
試料濃度：２ｍｇ／１００ｍｌ
From the viewpoint of improving the coating workability, the fire resistant aggregate used in the present invention preferably has an average particle size of 0.5 to 100 μm, more preferably 1 to 70 μm, and 5 to 50 μm. More preferably it is. Here, the average particle diameter of the refractory aggregate is a volume-median particle diameter (D50) measured using a laser diffraction particle size distribution analyzer (LA-920 manufactured by Horiba, Ltd.). The analysis conditions are as follows.
Measurement method: Flow method Dispersion medium: Solvent dispersion method in which sodium hexametaphosphate (0.1% by weight) is added to ion-exchanged water: Stirring, built-in ultrasonic irradiation (3 minutes)
Sample concentration: 2 mg / 100 ml
＜バインダー＞
バインダーは、鋳込み時において、耐火性骨材同士又は耐火性骨材と砂型とを結合させる働きを持つもので、加熱時の強度を維持することができるものである。本発明では、耐焼着性を向上させる観点から、ノボラック型フェノール樹脂により形成されたバインダーを使用する。ノボラック型フェノール樹脂は、フェノール類とアルデヒド類を酸触媒下で縮合重合させて得られる。本発明において、耐焼着の向上する推定メカニズムは次の通りである。すなわち、大型の鋳物、厚肉の鋳物については、鋳込み時間が長くなり、溶湯の熱による輻射熱の影響で溶湯と接していない側面や天面が高熱に曝されるが、ノボラック型フェノール樹脂であれば、堅固な架橋構造となっているので、塗膜が劣化するのを防止する働きがあると推察される。
<Binder>
The binder has a function of bonding the refractory aggregates or the refractory aggregate and the sand mold at the time of casting, and can maintain the strength during heating. In the present invention, from the viewpoint of improving the seizure resistance, a binder formed of a novolac type phenol resin is used. The novolac type phenol resin is obtained by subjecting phenols and aldehydes to condensation polymerization under an acid catalyst. In the present invention, the presumed mechanism for improving seizure resistance is as follows. That is, for large castings and thick castings, the casting time becomes longer, and the side and top surface not in contact with the molten metal are exposed to high heat due to the influence of the radiant heat caused by the molten metal. For example, it is presumed that it has a function of preventing the coating film from deteriorating because it has a firm cross-linked structure.
前記ノボラック型フェノール樹脂の合成に使用できるフェノール類は、特に限定されないが、フェノール、クレゾール、３，５−キシレノール、ノニルフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、イソプロペニルフェノール、フェニルフェノール等のアルキルフェノール、レゾルシノール、キシレノール、カテコール、ハイドロキノン、フロログルシノール等の多価フェノール、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＣ、ビスフェノールＥ等のビスフェノール等が例示できる。耐焼着性の観点から、フェノールを使用することが好ましい。 Phenols that can be used for the synthesis of the novolak type phenol resin are not particularly limited, but phenol, cresol, 3,5-xylenol, nonylphenol, p-tert-butylphenol, isopropenylphenol, phenylphenol and other alkylphenols, resorcinol, xylenol And polyphenols such as catechol, hydroquinone and phloroglucinol, and bisphenols such as bisphenol A, bisphenol F, bisphenol C and bisphenol E. From the viewpoint of anti-seizure property, it is preferable to use phenol.
前記ノボラック型フェノール樹脂の合成に使用できるアルデヒド類は、特に限定されないが、ホルムアルデヒド、ホルマリン、パラホルムアルデヒド、ポリオキシメチレン、グリオキサール、フルフラール及びこれらの混合物等が例示できる。なかでも、耐焼着性の観点から、ホルムアルデヒド、ホルマリン及びパラホルムアルデヒドを使用することが好ましい。 Aldehydes that can be used for the synthesis of the novolak type phenol resin are not particularly limited, and examples thereof include formaldehyde, formalin, paraformaldehyde, polyoxymethylene, glyoxal, furfural, and mixtures thereof. Of these, formaldehyde, formalin and paraformaldehyde are preferably used from the viewpoint of seizure resistance.
前記ノボラック型フェノール樹脂の合成に使用できる酸触媒は、特に限定されないが、シュウ酸、ｐ−トルエンスルホン酸、塩酸、硫酸等が例示できる。なかでも、生産性の観点から、硫酸を使用することが好ましい。 Although the acid catalyst which can be used for the synthesis | combination of the said novolak-type phenol resin is not specifically limited, An oxalic acid, p-toluenesulfonic acid, hydrochloric acid, a sulfuric acid etc. can be illustrated. Of these, sulfuric acid is preferably used from the viewpoint of productivity.
また、本発明では、耐焼着性を向上させる観点から、前記ノボラック型フェノール樹脂として、ＪＩＳ Ｋ ６９１０：２００７に記載された流れＡ法により１２５℃の条件で測定された流れ長さ（以下、単に「流れ長さ」ともいう）が２０〜７０ｍｍのものを使用する。同様の観点から、流れ長さが２２ｍｍ以上であることが好ましく、２４ｍｍ以上であることがより好ましく、２６ｍｍ以上であることが更に好ましい。同様の観点から、流れ長さが６０ｍｍ以下であることが好ましく、５０ｍｍ以下であることがより好ましく、４０ｍｍ以下であることが更に好ましく、３０ｍｍ以下であることが更により好ましく、２８ｍｍ以下であることが更により好ましい。前記観点を総合すると、本発明で使用されるノボラック型フェノール樹脂の流れ長さは、２０〜７０ｍｍであり、２２〜６０ｍｍであることが好ましく、２４〜５０ｍｍであることがより好ましく、２６〜４０ｍｍであることが更に好ましく、２６〜３０ｍｍであることが更により好ましく、２６〜２８ｍｍであることが更により好ましい。 Further, in the present invention, from the viewpoint of improving the seizure resistance, the novolac type phenol resin is measured as a flow length (hereinafter, simply referred to as 125 ° C.) according to the flow A method described in JIS K 6910: 2007. The one having a “flow length” of 20 to 70 mm is used. From the same viewpoint, the flow length is preferably 22 mm or more, more preferably 24 mm or more, and further preferably 26 mm or more. From the same viewpoint, the flow length is preferably 60 mm or less, more preferably 50 mm or less, further preferably 40 mm or less, still more preferably 30 mm or less, and 28 mm or less. Is even more preferred. When the said viewpoint is put together, the flow length of the novolak-type phenol resin used by this invention is 20-70 mm, It is preferable that it is 22-60 mm, It is more preferable that it is 24-50 mm, 26-40 mm It is still more preferable, it is still more preferable that it is 26-30 mm, and it is still more preferable that it is 26-28 mm.
流れ長さ２０〜７０ｍｍのノボラック型フェノール樹脂の例としては、ＡＶライトレジンＢＰ５５０Ｃ（旭有機材工業社製、流れ長さ２７ｍｍ）、ＡＶライトレジンＳＰ６６１（旭有機材工業社製、流れ長さ３０ｍｍ）、ＡＶライトレジンＳＰ５０Ｙ（旭有機材工業社製、流れ長さ４５ｍｍ）、ＡＶライトレジンＳＰ１００６ＮＰ（旭有機材工業社製、流れ長さ５０ｍｍ）、ＡＶライトレジンＢＰ２００Ｈ（旭有機材工業社製、流れ長さ５５ｍｍ）、ＡＶライトレジンＳＰ６１０（旭有機材工業社製、流れ長さ７０ｍｍ）、ＰＲ−３１１（住友ベークライト社製、流れ長さ５６ｍｍ）、ＰＲ−５０８６９（住友ベークライト社製、流れ長さ４０ｍｍ）、ＰＲ−５１５１０（住友ベークライト社製、流れ長さ３５ｍｍ）等が挙げられる。 Examples of novolak type phenolic resins having a flow length of 20 to 70 mm include AV Light Resin BP550C (Asahi Organic Materials Industries Co., Ltd., Flow Length 27 mm), AV Light Resin SP661 (Asahi Organic Materials Industries Co., Ltd., Flow Length 30 mm) ), AV Light Resin SP50Y (Asahi Organic Materials Industries, flow length 45 mm), AV Light Resin SP1006NP (Asahi Organic Materials Industries, flow length 50 mm), AV Light Resin BP200H (Asahi Organic Materials Industries, Flow length 55 mm), AV light resin SP610 (Asahi Organic Materials Co., Ltd., flow length 70 mm), PR-311 (Sumitomo Bakelite, flow length 56 mm), PR-50869 (Sumitomo Bakelite, flow length) 40 mm), PR-51510 (Sumitomo Bakelite Co., Ltd., flow length 35 mm), and the like.
本発明で使用されるバインダーの平均粒径は、水性塗型剤組成物の塗布作業性、バインダーの塗型への分散性及び鋳物の耐焼着性の観点から２〜５０μｍであり、５〜５０μｍであることが好ましく、１０〜４０μｍであることがより好ましく、２０〜３０μｍであることが更に好ましい。ここで、バインダーの平均粒径は、レーザー回折式粒度分布測定装置（堀場製作所社製ＬＡ−９２０）を用いて測定された体積中位粒径（Ｄ５０）である。分析条件は下記の通りである。
測定方法：湿式法
分散媒：水
分散方法：攪拌、内蔵超音波照射（３分間）
試料濃度：２００ｍｇ／１００ｍｌ
The average particle size of the binder used in the present invention is 2 to 50 μm, and 5 to 50 μm from the viewpoints of coating workability of the aqueous coating composition, dispersibility of the binder in the coating mold, and seizure resistance of the casting. It is preferably 10 to 40 μm, more preferably 20 to 30 μm. Here, the average particle size of the binder is a volume median particle size (D50) measured using a laser diffraction particle size distribution measuring device (LA-920 manufactured by Horiba, Ltd.). The analysis conditions are as follows.
Measurement method: Wet method Dispersion medium: Water dispersion method: Stirring, built-in ultrasonic irradiation (3 minutes)
Sample concentration: 200 mg / 100 ml
水性塗型剤組成物中のバインダーの含有量は、耐焼着性の観点から、耐火性骨材１００重量部に対し１重量部以上であることが好ましく、２重量部以上であることがより好ましく、３重量部以上であることが更に好ましく、４重量部以上であることが更により好ましい。熱分解ガス量を低減して耐焼着性を向上させる観点からは、耐火性骨材１００重量部に対し、１０重量部以下であることが好ましく、８重量部以下であることがより好ましく、７重量部以下であることが更に好ましく、６重量部以下であることが更により好ましい。前記観点を総合すると、水性塗型剤組成物中のバインダーの含有量は、耐火性骨材１００重量部に対し１〜１０重量部であることが好ましく、２〜８重量部であることがより好ましく、３〜７重量部であることが更に好ましく、４〜６重量部であることが更により好ましい。 From the viewpoint of seizure resistance, the content of the binder in the aqueous coating agent composition is preferably 1 part by weight or more and more preferably 2 parts by weight or more with respect to 100 parts by weight of the refractory aggregate. The amount is more preferably 3 parts by weight or more, and still more preferably 4 parts by weight or more. From the viewpoint of improving the seizure resistance by reducing the amount of pyrolysis gas, it is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, based on 100 parts by weight of the fireproof aggregate. The amount is more preferably no more than parts by weight and even more preferably no more than 6 parts by weight. When the said viewpoint is put together, it is preferable that it is 1-10 weight part with respect to 100 weight part of fireproof aggregates, and, as for content of the binder in an aqueous coating agent composition, it is more preferable that it is 2-8 weight part. It is preferably 3 to 7 parts by weight, more preferably 4 to 6 parts by weight.
＜消泡剤＞
本発明の水性塗型剤組成物は、消泡剤として、耐焼着性と塗膜剥離防止性の観点から、ポリエーテル変性シリコーンエマルジョンを含有し、好ましくは更にシリカを含有する。本発明の前記ポリエーテル変性シリコーンエマルジョンは、耐焼着性と塗膜剥離防止性の観点から、固形分中のＳｉ濃度が３．０〜６．０重量％以下であり、好ましくは３．０〜５．０重量％であり、より好ましくは３．０〜４．０重量％である。ポリエーテル変性シリコーンエマルジョンは、ポリエーテル変性シリコーンが直鎖状であっても、分岐状であってもよい。直鎖状の場合は、ポリエーテルとシリコーンが交互に結合した直鎖状のブロック共重合体である。分岐状の場合は、シリコーン鎖の側鎖にポリエーテル鎖を有する側鎖ポリエーテル変性シリコーンである。また、本発明の水性塗型剤組成物において、耐焼着性と消泡性の観点から、前記ポリエーテル変性シリコーンエマルジョンの含有量は固形分として、耐火性骨材１００重量部に対して、０．０２重量部以上であり、好ましくは０．０４５重量部以上であり、より好ましくは０．１０重量部以上である。また、耐焼着性と塗膜剥離防止性の観点から、耐火性骨材１００重量部に対して、０．３０重量部以下であり、好ましくは０．２５重量部以下であり、より好ましくは０．２０重量部以下である。これらの観点を総合すると前記ポリエーテル変性シリコーンエマルジョンの含有量は固形分として、耐火性骨材１００重量部に対して、０．０２〜０．３０重量部であり、０．０４５〜０．２５重量部が好ましい。さらに、耐焼着性と消泡性の観点から、耐火性骨材１００重量部に対して、０．１０〜０．２５重量部が好ましい。また、塗膜剥離防止性の観点から、耐火性骨材１００重量部に対して、０．０４５〜０．２０重量部がさらに好ましい。
また、本発明の水性塗型剤組成物において、本発明の前記ポリエーテル変性エマルジョンは、耐焼着性と消泡性の観点から、耐火性骨材１００重量部に対して、Ｓｉの含有量が０．０００７重量部以上が好ましく、０．００１重量部以上がより好ましく、０．００３重量部以上が更に好ましい。また、耐焼着性と塗膜剥離防止性の観点から、耐火性骨材１００重量部に対して、０．０１重量以下が好ましく、０．００９重量部以下がより好ましく、０．００７重量部以下が更に好ましい。これらの観点を総合すると前記ポリエーテル変性シリコーンエマルジョンのＳｉ含有量は、耐火性骨材１００重量部に対して、０．０００７〜０．０１重量部が好ましく、０．００１〜０．００９重量部がより好ましい。さらに、耐焼着性と消泡性の観点から、耐火性骨材１００重量部に対して、０．００３〜０．００９重量部が好ましい。また、塗膜剥離防止性の観点から、耐火性骨材１００重量部に対して、０．００１〜０．００７重量部がさらに好ましい。
<Antifoaming agent>
The aqueous coating composition of the present invention contains a polyether-modified silicone emulsion as an antifoaming agent, and preferably further contains silica, from the viewpoints of seizure resistance and coating film peeling prevention. The polyether-modified silicone emulsion of the present invention has a Si concentration in the solid content of 3.0 to 6.0% by weight, preferably 3.0 to 6.0% from the viewpoint of seizure resistance and coating film peeling prevention. The amount is 5.0% by weight, and more preferably 3.0 to 4.0% by weight. In the polyether-modified silicone emulsion, the polyether-modified silicone may be linear or branched. In the case of the linear form, it is a linear block copolymer in which polyether and silicone are alternately bonded. When branched, it is a side chain polyether-modified silicone having a polyether chain in the side chain of the silicone chain. Further, in the aqueous coating composition of the present invention, from the viewpoint of seizure resistance and antifoaming property, the content of the polyether-modified silicone emulsion is 0 as a solid content with respect to 100 parts by weight of the refractory aggregate. 0.02 parts by weight or more, preferably 0.045 parts by weight or more, more preferably 0.10 parts by weight or more. Further, from the viewpoints of seizure resistance and coating film peeling prevention, it is 0.30 part by weight or less, preferably 0.25 part by weight or less, more preferably 0 with respect to 100 parts by weight of the fireproof aggregate. 20 parts by weight or less. Taking these viewpoints together, the content of the polyether-modified silicone emulsion is 0.02 to 0.30 parts by weight with respect to 100 parts by weight of the refractory aggregate as a solid content, and 0.045 to 0.25. Part by weight is preferred. Furthermore, from the viewpoint of seizure resistance and antifoaming properties, 0.10 to 0.25 parts by weight is preferable with respect to 100 parts by weight of the fireproof aggregate. Moreover, from a viewpoint of coating film peeling prevention property, 0.045-0.20 weight part is further more preferable with respect to 100 weight part of refractory aggregates.
In the aqueous coating composition of the present invention, the polyether-modified emulsion of the present invention has a Si content of 100 parts by weight of the refractory aggregate from the viewpoints of seizure resistance and antifoaming properties. 0.0007 weight part or more is preferable, 0.001 weight part or more is more preferable, and 0.003 weight part or more is still more preferable. In addition, from the viewpoints of seizure resistance and coating film peeling prevention, it is preferably 0.01 parts by weight or less, more preferably 0.009 parts by weight or less, and 0.007 parts by weight or less with respect to 100 parts by weight of the fireproof aggregate. Is more preferable. From these viewpoints, the Si content of the polyether-modified silicone emulsion is preferably 0.0007 to 0.01 parts by weight, and 0.001 to 0.009 parts by weight with respect to 100 parts by weight of the refractory aggregate. Is more preferable. Furthermore, from the viewpoint of seizure resistance and antifoaming properties, 0.003 to 0.009 parts by weight is preferable with respect to 100 parts by weight of the fireproof aggregate. Moreover, from a viewpoint of coating-film peeling prevention property, 0.001-0.007 weight part is further more preferable with respect to 100 weight part of refractory aggregates.
＜溶剤＞
本発明の水性塗型剤組成物は、主溶剤の水の量は特に限定されないが、耐火性骨材１００重量部に対して、１０重量部以上が好ましく、１０〜５０重量部がより好ましく２０〜４０重量部が更に好ましい。
また、本発明の水性塗型剤組成物は、炭素数１〜３の１価アルコールを含有する。炭素数１〜３の１価アルコールとしては、メタノール、エタノール、プロパノール、イソプロパノールが挙げられるが、消泡の観点からメタノール、エタノールが好ましく、メタノールが更に好ましい。水性塗型剤組成物中の炭素数１〜３の１価アルコールの含有量は、耐焼着性と消泡性の観点から、耐火性骨材１００重量部に対して、０．２重量部以上であり、０．５重量部以上が好ましく、０．８重量部以上がより好ましく、１．５重量部以上が更に好ましい。安全性の観点（消防法の非該当、即ち引火性でない）から、耐火性骨材１００重量部に対して、２．４重量部以下であり、２．３重量部以下が好ましく、２．２重量部以下がより好ましく、２．１重量部以下が更に好ましい。これらの観点を総合すると水性塗型剤組成物中の炭素数１〜３の１価アルコールの含有量は、０．２〜２．４重量部であり、０．５〜２．３重量部が好ましく、０．８〜２．２重量部がより好ましく、１．５〜２．１重量部が更に好ましい。これは、消泡剤の拡散を著しく助ける働きがあり、消泡に対して素早く効果を発揮する。
<Solvent>
In the aqueous coating composition of the present invention, the amount of water of the main solvent is not particularly limited, but is preferably 10 parts by weight or more, more preferably 10 to 50 parts by weight with respect to 100 parts by weight of the refractory aggregate. More preferred is ˜40 parts by weight.
Moreover, the aqueous | water-based coating agent composition of this invention contains a C1-C3 monohydric alcohol. Examples of the monohydric alcohol having 1 to 3 carbon atoms include methanol, ethanol, propanol, and isopropanol. From the viewpoint of defoaming, methanol and ethanol are preferable, and methanol is more preferable. The content of the monohydric alcohol having 1 to 3 carbon atoms in the aqueous coating composition is 0.2 parts by weight or more with respect to 100 parts by weight of the refractory aggregate from the viewpoint of seizure resistance and antifoaming property. 0.5 parts by weight or more is preferable, 0.8 parts by weight or more is more preferable, and 1.5 parts by weight or more is still more preferable. From the viewpoint of safety (not applicable to the Fire Service Act, ie, not flammable), it is 2.4 parts by weight or less, preferably 2.3 parts by weight or less, based on 100 parts by weight of fireproof aggregate, 2.2 More preferred is less than or equal to parts by weight, and still more preferred is less than or equal to 2.1 parts by weight. Taking these viewpoints together, the content of the monohydric alcohol having 1 to 3 carbon atoms in the aqueous coating composition is 0.2 to 2.4 parts by weight, and 0.5 to 2.3 parts by weight. Preferably, 0.8 to 2.2 parts by weight are more preferable, and 1.5 to 2.1 parts by weight are still more preferable. This has the function of remarkably assisting the diffusion of the antifoaming agent, and exhibits a quick effect against the defoaming.
＜その他の成分＞
本発明の塗型剤組成物に配合できるその他の成分として、アラビアガム等の粘結剤、アタパルジャイト、ベントナイト等の焼結剤、顔料や染料などの着色剤、塗布作業性を向上させるレオロジー調整剤、沈降防止剤、界面活性剤などの添加剤を使用できる。また、ヒドロキシアルキル化セルロース等のセルロース誘導体、ポリビニルアルコール、アルギン酸ソーダなどの増粘剤や防腐剤などの添加剤も使用できる。水性塗型剤組成物中における前記その他の成分の含有量は、耐火性骨材１００重量部に対し、通常０．１〜１０重量部程度である。
<Other ingredients>
Other components that can be blended in the coating composition of the present invention include binders such as gum arabic, sintering agents such as attapulgite and bentonite, colorants such as pigments and dyes, and rheology modifiers that improve coating workability. Additives such as anti-settling agents and surfactants can be used. In addition, additives such as thickeners and preservatives such as cellulose derivatives such as hydroxyalkylated cellulose, polyvinyl alcohol and sodium alginate can also be used. Content of the said other component in an aqueous coating agent composition is about 0.1-10 weight part normally with respect to 100 weight part of refractory aggregates.
本発明の水性塗型剤組成物は、砂型（鋳型）の表面に水性塗型剤組成物を塗布してなる鋳造用砂型を使用する鋳物の製造方法に好適である。 The aqueous coating composition of the present invention is suitable for a casting production method using a casting sand mold formed by applying an aqueous coating composition to the surface of a sand mold (mold).
本発明の水性塗型剤組成物を砂型の表面及び冷し金の表面に塗布する方法は、特に限定されず、例えば、流し塗り（ブッカケ法）、浸漬（ドブ漬け法）、刷毛塗り、スプレー塗布等の従来知られている方法が使用できる。 The method of applying the aqueous coating composition of the present invention to the surface of the sand mold and the surface of the cooling metal is not particularly limited. For example, the coating method (bukkake method), dipping (dipping method), brush coating, spraying Conventionally known methods such as coating can be used.
また、砂型に用いる鋳物砂としては、石英質を主成分とする珪砂の他、ジルコン砂、クロマイト砂、合成ムライト砂等の新砂又はこれらの再生砂が使用される。鋳物砂は、粘結剤を添加せずに用いることもでき、その場合には充填性が良好であるが、高い砂型強度が要求される場合には、粘結剤を添加し、硬化剤により硬化させるのが好ましい。
なお、前記砂型は、一般的に、フラン樹脂、アルカリフェノール樹脂等の有機粘結剤や水ガラス等の無機粘結剤を鋳物砂に混合し、製品（鋳物）と同一形状の木型のまわりに充填した後、硬化、抜型して得られるものである。
Further, as the foundry sand used for the sand mold, silica sand mainly composed of quartz, new sand such as zircon sand, chromite sand, synthetic mullite sand, or regenerated sand thereof is used. Foundry sand can also be used without the addition of a binder, in which case the filling property is good, but when high sand mold strength is required, a binder is added and a hardener is used. It is preferable to cure.
In addition, the sand mold is generally mixed with foundry sand with an organic binder such as furan resin or alkali phenol resin or an inorganic binder such as water glass, and around the same shape as the product (cast). After being filled in, it is obtained by curing and die cutting.
水性塗型剤組成物は、保存時においては溶媒濃度が低い（固形分濃度が高い）状態の組成物（保存用組成物）としておき、使用時に適正な粘度が得られるように、溶媒で希釈して使用される。前記高固形分濃度の組成物（保存用組成物）は、溶媒量等を調整して、通常、針入度２００程度とすればよい。前記使用時の適正な粘度（濃度）は、３０〜８０ボーメである。また、インスタントタイプとして、使用する濃度３０〜８０ボーメをドラムに入れておくと作業者が調整する作業が省け即座に使用できる。 The aqueous coating agent composition is stored as a composition (preservation composition) in a state where the solvent concentration is low (solid content concentration is high) during storage, and diluted with a solvent so that an appropriate viscosity can be obtained during use. Used. The composition having a high solid content (preservation composition) may be adjusted to the amount of solvent and the like, and usually has a penetration of about 200. The proper viscosity (concentration) at the time of use is 30 to 80 baume. Moreover, as an instant type, if the density | concentration 30-80 Baume to be used is put into a drum, the operation | work which an operator will adjust will be skipped and it can use immediately.
本発明の水性塗型剤組成物は、アルミニウム鋳物のような非鉄合金系鋳物や、鋳鋼系鋳物あるいは鋳鉄系鋳物等の鋳造に使用できる。なかでも、鋳鉄の鋳込み重量が大きい、又は、例えば３０ｃｍ以上肉厚部が多い製品では、焼着が多く発生し、それを取り除くことに、多大な量力と時間を要していたが、本発明の水性塗型剤組成物を鋳鉄の鋳造に使用することにより、焼着の発生を防止もしくは著しく低減させることが可能になる。 The aqueous coating composition of the present invention can be used for casting non-ferrous alloy castings such as aluminum castings, cast steel castings or cast iron castings. Among them, cast iron has a large casting weight, or, for example, a product having a large thickness part of 30 cm or more generates many seizures, and it takes a great amount of power and time to remove it. By using this aqueous coating composition for casting of cast iron, it becomes possible to prevent or significantly reduce the occurrence of seizure.
本発明の水性塗型剤組成物を用いて鋳物を製造すると、焼着欠陥が少ない美麗な鋳物が得られるため、複雑な構造や、鋳肌表面の美しさが要求されるもの等に好適である。具体的な鋳物の例としては、建設機械の油圧バルブ、モーター、金型、エンジンフレーム、工作機械、建築部材等に用いられる、部材、部品等が挙げられる。 When a casting is produced using the aqueous coating composition of the present invention, a beautiful casting with few seizure defects can be obtained. Therefore, it is suitable for a complex structure or a product that requires a beautiful casting surface. is there. Specific examples of castings include members, parts, and the like used for hydraulic valves, motors, molds, engine frames, machine tools, building members, and the like of construction machines.
本発明の組成物は、
＜１＞ 耐火性骨材、バインダー、消泡剤及び溶媒を含む水性塗型剤組成物であって、前記バインダーとしてノボラック型フェノール樹脂を含有し、前記耐火性骨材１００重量部に対し、前記消泡剤として固形分中のＳｉ濃度が３．０〜６．０重量％であるポリエーテル変性シリコーンエマルジョンを固形分として０．０２〜０．３０重量部、及び前記溶媒として炭素数１〜３の１価アルコール０．２〜２．４重量部を含有する水性塗型剤組成物である。
The composition of the present invention comprises:
<1> An aqueous coating composition containing a fire-resistant aggregate, a binder, an antifoaming agent and a solvent, containing a novolac-type phenol resin as the binder, and with respect to 100 parts by weight of the fire-resistant aggregate, A polyether-modified silicone emulsion having a Si concentration in the solid content of 3.0 to 6.0% by weight as an antifoaming agent is 0.02 to 0.30 parts by weight as the solid content, and the solvent has 1 to 3 carbon atoms. It is an aqueous coating composition containing 0.2 to 2.4 parts by weight of a monohydric alcohol.
本発明は、さらに以下の組成物が好ましい。
＜２＞ 前記ポリエーテル変性シリコーンエマルジョンがシリカを含有する、前記＜１＞の水性塗型剤組成物。
＜３＞ 前記消泡剤の固形分中のＳｉ濃度が３．０〜５．０重量％であり、好ましくは３．０〜４．０重量％である、前記＜１＞又は＜２＞の水性塗型剤組成物。
＜４＞ 前記耐火性骨材１００重量部に対して、ポリエーテル変性シリコーンエマルジョンの含有量が固形分として０．０４５〜０．２５重量部である前記＜１＞〜＜３＞の何れかの水性塗型剤組成物。
＜５＞ 前記炭素数１〜３の１価アルコールがメタノールである前記＜１＞〜＜４＞の何れかの水性塗型剤組成物。
＜６＞ 前記耐火性骨材として、ジルコン、タルク及び黒鉛からなる群から選ばれる一種以上の化合物を含有する前記＜１＞〜＜５＞の何れかの水性塗型剤組成物。
＜７＞ 前記ジルコンと前記タルクと前記黒鉛の重量比率が、ジルコン：タルク：黒鉛＝１５〜３５：３５〜５５：２０〜４０であり、好ましくは２０〜３０：４０〜５０：２５〜３５であり、より好ましくは２２〜２８：４２〜４８：２７〜３３である前記＜６＞の水性塗型剤組成物。
＜８＞ 前記ノボラック型フェノール樹脂の含有量が、前記耐火性骨材１００重量部に対し、１〜１０重量部であり、好ましくは２〜８重量部であり、より好ましくは３〜７重量部であり、更に好ましくは４〜６重量部である前記＜１＞〜＜７＞の何れかの水性塗型剤組成物。
＜９＞ 前記炭素数１〜３の１価アルコールの含有量が、前記耐火性骨材１００重量部に対し、０．２〜２．４重量部であり、０．５〜２．３重量部が好ましく、より好ましくは０．８〜２．２重量部であり、更に好ましくは１．５〜２．１重量部である前記＜１＞〜＜８＞の何れかの水性塗型剤組成物。
In the present invention, the following compositions are more preferable.
<2> The aqueous coating composition according to <1>, wherein the polyether-modified silicone emulsion contains silica.
<3> The concentration of Si in the solid content of the antifoaming agent is 3.0 to 5.0% by weight, preferably 3.0 to 4.0% by weight, according to <1> or <2> An aqueous coating composition.
<4> The content of the polyether-modified silicone emulsion is 0.045 to 0.25 part by weight as a solid content with respect to 100 parts by weight of the fireproof aggregate, and any one of the above <1> to <3> An aqueous coating composition.
<5> The aqueous coating composition according to any one of <1> to <4>, wherein the monohydric alcohol having 1 to 3 carbon atoms is methanol.
<6> The aqueous coating composition according to any one of <1> to <5>, wherein the fireproof aggregate contains one or more compounds selected from the group consisting of zircon, talc, and graphite.
<7> The weight ratio of the zircon, the talc, and the graphite is zircon: talc: graphite = 15-35: 35-55: 20-40, preferably 20-30: 40-50: 25-35. Yes, More preferably, it is 22-28: 42-48: 27-33.
<8> The content of the novolac type phenolic resin is 1 to 10 parts by weight, preferably 2 to 8 parts by weight, more preferably 3 to 7 parts by weight with respect to 100 parts by weight of the refractory aggregate. The aqueous coating composition according to any one of <1> to <7>, more preferably 4 to 6 parts by weight.
<9> The content of the monohydric alcohol having 1 to 3 carbon atoms is 0.2 to 2.4 parts by weight, and 0.5 to 2.3 parts by weight with respect to 100 parts by weight of the refractory aggregate. The aqueous coating composition according to any one of <1> to <8>, preferably 0.8 to 2.2 parts by weight, and more preferably 1.5 to 2.1 parts by weight. .
以下、本発明を具体的に示す実施例等について説明する。 Examples and the like specifically showing the present invention will be described below.
実施例１〜８及び比較例１〜１９
＜水性塗型剤組成物の調製＞
表２に示すバインダー、消泡剤、アルコールを用い、表１に示す配合量で各成分を混合し、２５℃において、混練機にて３０分間混練し、ペースト状の水性塗型剤組成物を得た。なお、表１に示す耐火性骨材の平均粒径は、ジルコンが７μｍ、タルクが２２μｍ、鱗状黒鉛が３９μｍであった。また、用いたバインダー、消泡剤を表３〜５に示す。得られた水性塗型剤組成物を離合社製針入度測定装置８００Ｓ−０１により測定したところ、針入度は何れも２００であった。
尚、本発明の、バインダーである、ノボラック型フェノール樹脂は旭有機材工業（株）製（商品名：ＡＶライトレジンＳＰ６６１）であり、平均粒径が２７μｍ、流れ長さが
３０ｍｍであった。
Examples 1-8 and Comparative Examples 1-19
<Preparation of aqueous coating composition>
Using the binder, antifoaming agent, and alcohol shown in Table 2, the components were mixed in the blending amounts shown in Table 1, and kneaded for 30 minutes at 25 ° C. with a kneader to obtain a paste-like aqueous coating composition. Obtained. The average particle size of the refractory aggregate shown in Table 1 was 7 μm for zircon, 22 μm for talc, and 39 μm for scaly graphite. Moreover, the used binder and an antifoamer are shown to Tables 3-5. When the obtained aqueous coating composition was measured by a needle penetration measuring device 800S-01 manufactured by Kotosha Co., Ltd., the penetration was 200 in all cases.
The novolak type phenolic resin, which is a binder of the present invention, was manufactured by Asahi Organic Materials Co., Ltd. (trade name: AV Light Resin SP661), and had an average particle size of 27 μm and a flow length of 30 mm.
＜評価方法＞
（１）強制攪拌後の消泡時間
配合した水性塗型剤組成物を固形分５０％になるように水を添加し、５００ｍｌデスカップの２５０ｍｌまで塗型を入れる。東京理化機械(株)製の卓上攪拌機（ＴＹＰＥ ＤＣ−２Ｓ、軸Φ８、攪拌羽根径Φ６０）を用い、攪拌羽根が前記水性塗型剤組成物（２５℃調整）を入れたデスカップの底部から１０ｍｍの高さになるように固定した。５００ｒｐｍの回転数で３０秒間攪拌し停止させた後、泡が消えるまでの時間を測定した。
<Evaluation method>
(1) Defoaming time after forced stirring Water is added to the blended aqueous coating composition so as to have a solid content of 50%, and the mold is put up to 250 ml in a 500 ml descup. Using a desktop stirrer (TYPE DC-2S, shaft Φ8, stirring blade diameter Φ60) manufactured by Tokyo Rika Kikai Co., Ltd., the stirring blade is 10 mm from the bottom of the descup containing the aqueous coating composition (adjusted at 25 ° C.). It was fixed to become the height of. After stirring and stopping for 30 seconds at a rotation speed of 500 rpm, the time until the bubbles disappeared was measured.
（２）塗膜のはじき性
フラン再生砂（ＡＦＳ指数４５）を鋳物砂として使用し、花王クエーカー(株)社製フラン樹脂ＥＦ−５３０２（対砂０．８％重量％）、硬化剤Ｃ−１４（対樹脂４０重量％）を混合させ硬化させた２５０×２５０×３５Ｈ（ｍｍ）の板状試験片に固形分５０％に調整したデスカップ入り水性塗型剤組成物の流し塗りを行い、３０秒後に塗膜の状態を観察し以下の塗膜のはじきの評価を行った。なお、はじきとは塗膜が砂型表面に付着せず砂型表面が見える状態のことである。
１：塗膜のはじきの面積０％
２：塗膜のはじきの面積１〜２０％の範囲
３：塗膜のはじきの面積２０％以上
(2) Repellency of coating film Furan regenerated sand (AFS index 45) is used as foundry sand, furan resin EF-5302 (0.8% by weight with respect to sand) manufactured by Kao Quaker Co., Ltd., curing agent C- A plate-shaped test piece of 250 × 250 × 35H (mm) mixed with 14 (40% by weight of resin) and cured was subjected to a flow coating of an aqueous coating composition containing a descup adjusted to a solid content of 50%. The state of the coating film was observed after 2 seconds, and the following film repelling was evaluated. In addition, the repellency is a state where the sand mold surface can be seen without the coating film adhering to the sand mold surface.
1: 0% area of film repellency
2: Range of 1 to 20% of film repellency 3: 20% or more of film repellency area
（３）耐焼着試験
フラン再生砂（ＡＦＳ指数４５）を鋳物砂として使用し、花王クエーカー(株)社製フラン樹脂（ＥＦ−５３０２）を鋳物砂１００重量部に対して０．８重量％添加し、硬化剤（Ｃ−１４）をフラン樹脂１００重量部に対して４０重量部添加して得られた混練砂を型込めし、図１に示す五角柱形状の中子１を８個作製した。そして、上記水性塗型剤組成物を固形分５０％になるように水を添加し調整した。この水性塗型剤組成物に８個の中子１をそれぞれ浸漬し、１０５℃の熱風で１時間乾燥した。次いで、直径３５０ｍｍ×高さ４００ｍｍの鋳物を形成するための主型の底面に、上記乾燥後の８個の中子を図１に示すように同一円周上（直径２５０ｍｍ）に均等に配置した。この鋳型に、溶湯（材質ＦＣ−２５０）を１４２０℃で注湯し、２４時間放置した。その後、鋳型をばらして鋳物を取り出し、得られた鋳物における中子が配置されていた空隙部に水を入れて、中子が配置されていた空隙部の焼着していない体積を求め、以下の式により焼着率を算出した。
焼着率（％）＝〔（中子が配置されていた空隙部の全体積−中子が配置されていた空隙部の焼着していない体積）／中子が配置されていた空隙部の全体積〕×１００
１：焼着率０〜１５％
２：焼着率１６〜３０％
３：焼着率３１〜４５％
４：焼着率４５％以上
(3) Anti-seizure test Furan regenerated sand (AFS index 45) is used as foundry sand, and 0.8% by weight of furan resin (EF-5302) manufactured by Kao Quaker Co., Ltd. is added to 100 parts by weight of foundry sand. Then, the kneaded sand obtained by adding 40 parts by weight of the curing agent (C-14) to 100 parts by weight of the furan resin was molded, and eight pentagonal cores 1 shown in FIG. 1 were produced. . And the water-based coating agent composition was adjusted by adding water so that the solid content was 50%. Eight cores 1 were each immersed in this aqueous coating composition and dried with hot air at 105 ° C. for 1 hour. Next, on the bottom surface of the main mold for forming a casting having a diameter of 350 mm and a height of 400 mm, the eight cores after the drying are equally arranged on the same circumference (diameter 250 mm) as shown in FIG. . Molten metal (material FC-250) was poured into this mold at 1420 ° C. and left for 24 hours. Thereafter, the casting mold is taken out, the casting is taken out, water is put into the void portion where the core is arranged in the obtained casting, and the non-baked volume of the void portion where the core is arranged is determined as follows. The bake rate was calculated according to the formula:
Rate of seizure (%) = [(total volume of voids in which the core was disposed−volume of the voids in which the core was disposed) / volume of the voids in which the core was disposed Total volume] × 100
1: Erosion rate 0-15%
2: Seizure rate 16-30%
3: Seizure rate 31-45%
4: More than 45% seizure rate
（４）引火危険性
配合した水性塗型剤組成物を消防庁の第４類危険物（引火性液体）の試験方法に準じて行なった。なお、試験方法は迅速平衡密閉式試験方法で７９℃以下で引火するものを「引火性あり」８０℃まで引火しないものを「引火性なし」とした。
(4) Flammability Hazard The blended aqueous coating composition was carried out in accordance with the test method for Class 4 hazardous materials (flammable liquid) of the Fire Department. The test method was a rapid equilibrium sealed test method that ignited at 79 ° C. or less was “flammable”, and the one that did not ignite to 80 ° C. was “not flammable”.
表２に示すように、実施例１〜８は、比較例１〜１９に比べ、いずれも耐焼着性、塗膜剥離性（塗膜のはじき性）、消泡性（強制攪拌後の消泡時間が短い）及び引火危険性のないことを同時に満足し良好な結果となった。この結果から、本発明によれば、耐焼着性及び塗膜剥離防止性に優れ、塗布作業時の泡を低減できる引火危険性のない水性塗型剤組成物を提供できることが確認された。 As shown in Table 2, each of Examples 1 to 8 is more resistant to seizure, coating peelability (repellency of the coating), and defoaming (defoaming after forced stirring) compared to Comparative Examples 1 to 19. The time was short) and there was no risk of ignition. From these results, it was confirmed that according to the present invention, it is possible to provide an aqueous coating composition that is excellent in anti-seizure property and anti-peeling property and can reduce bubbles during application work and has no ignition risk.
Claims (5)
〜２．４重量部を含有する水性塗型剤組成物。 An aqueous coating composition comprising a fire resistant aggregate, a binder, an antifoaming agent and a solvent, comprising a novolac type phenol resin as the binder, and the antifoaming agent with respect to 100 parts by weight of the fire resistant aggregate As a solid content, 0.02 to 0.30 parts by weight of a polyether-modified silicone emulsion having a Si concentration of 3.0 to 6.0% by weight as a solid content, and a monovalent valence having 1 to 3 carbon atoms as the solvent. Alcohol 0.2
An aqueous coating composition containing ~ 2.4 parts by weight.
The aqueous coating composition according to any one of claims 1 to 4, comprising one or more compounds selected from the group consisting of zircon, talc, and graphite as the refractory aggregate.
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