JP2007182524A - Composition for molding and coating of melamine-based resin and molded article coated with the composition - Google Patents
Composition for molding and coating of melamine-based resin and molded article coated with the composition Download PDFInfo
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- JP2007182524A JP2007182524A JP2006003712A JP2006003712A JP2007182524A JP 2007182524 A JP2007182524 A JP 2007182524A JP 2006003712 A JP2006003712 A JP 2006003712A JP 2006003712 A JP2006003712 A JP 2006003712A JP 2007182524 A JP2007182524 A JP 2007182524A
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 77
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 238000000576 coating method Methods 0.000 title claims abstract description 58
- 238000000465 moulding Methods 0.000 title claims abstract description 55
- 229920005989 resin Polymers 0.000 title claims abstract description 29
- 239000011347 resin Substances 0.000 title claims abstract description 29
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000004640 Melamine resin Substances 0.000 claims abstract description 52
- 239000000049 pigment Substances 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 35
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 27
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010445 mica Substances 0.000 claims abstract description 7
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 239000008199 coating composition Substances 0.000 claims description 24
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical group NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012778 molding material Substances 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 11
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 11
- 239000002932 luster Substances 0.000 description 11
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 7
- 239000003086 colorant Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000014347 soups Nutrition 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
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 1
- DUZLHGMYNVZMCO-UHFFFAOYSA-N 6-[2-[3-[2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]ethyl]-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(CCC2OCC3(CO2)COC(CCC=2N=C(N)N=C(N)N=2)OC3)=N1 DUZLHGMYNVZMCO-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241000238558 Eucarida Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 210000000038 chest Anatomy 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- -1 guanamines Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Table Devices Or Equipment (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、皿、茶碗、盆等のアミノ樹脂成形品の表面装飾に適した成形被覆用組成物に関し、特に、該成形被覆用組成物を使用して被覆成形された耐クラック性と意匠性に優れた被覆成型物に関する。 The present invention relates to a molding and coating composition suitable for surface decoration of amino resin molded products such as dishes, teacups and trays, and in particular, crack resistance and design properties formed by coating using the molding and coating composition. It is related with the coating molding excellent in.
メラミン系樹脂成形材料は、耐熱性、耐溶剤性、耐摩耗性および電気絶縁性等に優れ、皿、茶碗、盆、お椀等の食器類、机、たんす、げた箱等における化粧板類および接続器、転換器、配電盤、絶縁がい子等の電気機器部品類等の各種の分野で成型されて使用されている。
中でも、皿、茶碗、盆、お椀等の食器類は、色や柄模様等の意匠性を要求される分野であり、従来より、着色顔料を配合した成形材料を用いて着色成型物を成型する方法で用いられている。また、成型物を更に成形被覆して表面特性を改善する方法、いわゆるグレーズ法が適用されている。
Melamine-based resin molding materials are excellent in heat resistance, solvent resistance, wear resistance, electrical insulation, etc., decorative plates and connectors in dishes such as dishes, teacups, trays, bowls, desks, chests, and boxes It is molded and used in various fields such as electrical equipment parts such as converters, switchboards and insulators.
Among them, dishes such as dishes, teacups, trays, bowls, etc. are fields that require design properties such as colors and patterns, and conventionally, colored moldings are molded using molding materials containing colored pigments. Used in the method. Further, a so-called glaze method is applied which further improves the surface characteristics by molding and covering the molded product.
グレーズ法の例としては、特許文献１には、着色成型物をメラミン及び／又はグアナミン類とホルムアルデヒドとの反応物からなるアミノ系樹脂と硬化触媒等を配合した透明性の被覆成形材料で被覆して、表面保護と意匠性（透明性）を兼備した食器を得る方法が開示されている。
しかしながら、メラミン樹脂は、工業的製法で容易に製造することが可能ではあるが、メラミン樹脂だけでは、耐水性、可撓性（耐クラック性）や汚染性にやや乏しく、また、グアナミン樹脂及びメラミン−グアナミン共縮合樹脂は、耐水性、可撓性（耐クラック性）や汚染性は改善されるものの、製造工程に於いて板状物又は固形状物を粉砕する作業等が必要であり、該作業に多大の労力を要するため、工業的に製造することが難しいという問題点があった。
また、従来のいわゆるグレーズ法では、被覆樹脂が透明色又は単色であり、多様な色彩を揃えることも困難であった。
As an example of the glaze method, Patent Document 1 discloses that a colored molding is coated with a transparent coating molding material containing an amino resin composed of a reaction product of melamine and / or guanamines and formaldehyde, a curing catalyst, and the like. A method for obtaining tableware having both surface protection and design (transparency) is disclosed.
However, although melamine resin can be easily produced by an industrial manufacturing method, melamine resin alone is somewhat poor in water resistance, flexibility (crack resistance) and contamination, and guanamine resin and melamine -Although guanamine co-condensation resin has improved water resistance, flexibility (crack resistance) and contamination, it is necessary to perform operations such as crushing a plate or solid in the production process. Since a lot of labor is required for the work, there is a problem that it is difficult to manufacture industrially.
Further, in the conventional so-called glaze method, the coating resin is transparent or single color, and it is difficult to arrange various colors.
本発明は、前記グレーズ法での工業的製法として容易に得ることが可能なメラミン樹脂を単独で用いた場合は、耐水性、可撓性（耐クラック性）や汚染性に乏しくなるという問題点と、これらの性能を満足することが出来るグアナミン樹脂及びメラミン−グアナミン共縮合樹脂が工業的に製造することが難しいと言う問題点を解消すること目的とする。
更には、得られた被覆成型品が透明色又は単色で意匠性に乏しいという欠点を解消することを目的とする。
The present invention has a problem that water resistance, flexibility (crack resistance) and contamination are poor when a melamine resin that can be easily obtained as an industrial process in the glaze method is used alone. And it aims at solving the problem that it is difficult to manufacture industrially the guanamine resin and melamine-guanamine cocondensation resin which can satisfy these performances.
Furthermore, it aims at eliminating the fault that the obtained coated molded product is transparent or monochromatic and poor in design.
本発明は、メラミン樹脂に、グアナミン類を配合することにより、工業的製法で極めて容易に成形被覆用組成物を得ることが出来、メラミン樹脂単独では劣る物性をカバーし、更には本発明の被覆組成物に被覆顔料を必須成分として配合することにより、意匠性に乏しい不利益性を解消するだけでなく、耐クラック性が更に向上することを見出したことにより達成されたものである。
即ち本発明は、メラミン樹脂１００重量部に対して、グアナミン類を５〜１００重量部含有させたメラミン系樹脂１００重量部に対して、マイカ粒子及び／又はアルミナ粒子表面を酸化チタン及び／又は酸化鉄で被覆した被覆顔料を１〜３０重量部配合することにより、高光沢、耐クラック性及び意匠性に優れたメラミン系樹脂成形被覆用組成物を得ることが出来、該被覆組成物を被覆した耐クラック性及び意匠性に優れた成型物を得ることができる。
According to the present invention, a composition for molding and coating can be obtained very easily by an industrial production method by blending guanamines with melamine resin, and the physical properties which are inferior with melamine resin alone are covered. This is achieved by not only eliminating the disadvantage of poor design but also improving crack resistance by blending the coating pigment as an essential component in the composition.
That is, according to the present invention, the surface of mica particles and / or alumina particles is titanium oxide and / or oxidized with respect to 100 parts by weight of melamine resin containing 5 to 100 parts by weight of guanamines with respect to 100 parts by weight of melamine resin. By blending 1 to 30 parts by weight of the coating pigment coated with iron, a melamine-based resin molding coating composition excellent in high gloss, crack resistance and design can be obtained, and the coating composition is coated. A molded product having excellent crack resistance and design properties can be obtained.
本発明におけるメラミン系樹脂成形被覆用組成物は、工業的製法で容易に製造することが可能であり、光沢、耐水性、耐クラック性等の物性にも優れた被覆用組成物であり、更に多彩な色調が得られると共に、この組成物を被覆した成型品もまた、多彩な紋様、色調を有する優れた成型品となり得るというものである。 The melamine-based resin molding coating composition according to the present invention is a coating composition that can be easily produced by an industrial production method and has excellent physical properties such as gloss, water resistance, and crack resistance. A variety of colors can be obtained, and a molded product coated with the composition can also be an excellent molded product having a variety of patterns and colors.
以下、本発明のメラミン系樹脂成形被覆用組成物、及び該被覆用組成物を被覆した成型物について詳しく説明する。
本発明でいうメラミン樹脂とは、メラミンとホルムアルデヒドとを反応せしめて得られるメラミン／ホルムアルデヒド樹脂（以下「メラミン樹脂」と略称することがある。）である。
該メラミン樹脂は、メラミンとホルムアルデヒドとをモル比１：１．５〜１：４．５、好ましくは１：２〜１：３の範囲で、水溶液中で反応させて初期縮合物水溶液を製造する。その際、メラミン濃度２０〜６０％、反応温度４０〜１００℃、弱酸性〜弱アルカリ性で反応させことにより、１０〜１００分間程度で反応は完了する。得られた初期縮合物水溶液をスプレードライ等の工業的な製法で固形粉末状メラミン樹脂とする。
その際、メラミンに対するホルムアルデヒドのモル比が１．５モル未満では、加工性が低下すると共に、反応速度が遅くて好ましくなく、また４．５モル超では、メラミン樹脂がややもろくなるので好ましくない。
Hereinafter, the melamine-based resin molding coating composition of the present invention and the molded article coated with the coating composition will be described in detail.
The melamine resin referred to in the present invention is a melamine / formaldehyde resin obtained by reacting melamine and formaldehyde (hereinafter sometimes abbreviated as “melamine resin”).
The melamine resin is prepared by reacting melamine and formaldehyde in an aqueous solution in a molar ratio of 1: 1.5 to 1: 4.5, preferably in a range of 1: 2 to 1: 3 to produce an initial condensate aqueous solution. . At that time, the reaction is completed in about 10 to 100 minutes by reacting at a melamine concentration of 20 to 60%, a reaction temperature of 40 to 100 ° C., and weakly acidic to weakly alkaline. The obtained initial condensate aqueous solution is made into a solid powdery melamine resin by an industrial production method such as spray drying.
At that time, if the molar ratio of formaldehyde to melamine is less than 1.5 mol, the processability is lowered and the reaction rate is slow, which is not preferable. If it exceeds 4.5 mol, the melamine resin becomes slightly brittle, which is not preferable.
メラミン樹脂に配合するグアナミン類としては、例えば、ベンゾグアナミン、アセトグアナミン、ホルムグアナミン、フェニルアセトグアナミン、ＣＴＵグアナミン等を挙げることができ、中でも耐水性や光沢等の特性からベンゾグアナミンが好ましい。
メラミン樹脂へのグアナミン類の配合量は、メラミン樹脂１００重量部に対してグアナミン類５〜１００重量部である。グアナミン類が５重量部未満では、耐汚染性や可撓性が悪くなるので好ましくなく、１００重量部超では、表面硬度や流動性が低下し、成形性が悪くなるので好ましくない。
Examples of guanamines to be blended with the melamine resin include benzoguanamine, acetoguanamine, formguanamine, phenylacetoguanamine, CTU guanamine, and the like. Among them, benzoguanamine is preferable in view of characteristics such as water resistance and gloss.
The compounding quantity of the guanamine to a melamine resin is 5-100 weight part of guanamines with respect to 100 weight part of melamine resins. Less than 5 parts by weight of guanamine is not preferable because the stain resistance and flexibility are deteriorated, and more than 100 parts by weight is not preferable because the surface hardness and fluidity are lowered and the moldability is deteriorated.
本発明のメラミン系樹脂成形被覆用組成物は、前記のメラミン系樹脂１００重量部に対して、更にマイカ粒子及び／又はアルミナ粒子の表面を酸化チタン及び／又は酸化鉄で被覆した被覆顔料を１〜３０重量部配合する。該配合量が１重量部未満では、耐クラック性等の効果に乏しく、３０重量部超では、被覆成形材料の流動性が悪くなり、その結果、耐汚染性や耐水性等に悪影響を及ぼす。
マイカ粒子及び／又はアルミナ粒子の表面を酸化チタン及び／又は酸化鉄で被覆した被覆顔料は、酸化チタンの被覆率で１４〜６８％、酸化鉄の被覆率で４〜５８％である。被覆率や該被覆顔料の粒度の違いにより、様々な色調の顔料が得られる。
前記被覆顔料の粒度は１〜１８０μｍ、好ましくは１０〜１５０μｍが用いられ、大きな粒子はキラキラした光沢をもたらし、小さな粒子は柔らかい光沢をもたらす。更には被覆層を透過した光線と反射光線の違いにより見る角度によって、多彩な色調をもたらすのでこれらの粒子を目的、用途により適宜選択、併用して使用する。
The composition for melamine resin molding coating of the present invention is a coating pigment obtained by further coating the surface of mica particles and / or alumina particles with titanium oxide and / or iron oxide with respect to 100 parts by weight of the melamine resin. -30 parts by weight are blended. When the blending amount is less than 1 part by weight, the effect such as crack resistance is poor, and when it exceeds 30 parts by weight, the fluidity of the coating molding material is deteriorated, and as a result, the stain resistance and water resistance are adversely affected.
The coated pigment obtained by coating the surfaces of mica particles and / or alumina particles with titanium oxide and / or iron oxide has a titanium oxide coverage of 14 to 68% and an iron oxide coverage of 4 to 58%. Depending on the coverage and the particle size of the coated pigment, pigments of various colors can be obtained.
The coated pigment has a particle size of 1 to 180 μm, preferably 10 to 150 μm. Large particles give a shiny gloss and small particles give a soft gloss. Furthermore, since various color tones are brought depending on the viewing angle due to the difference between the light beam transmitted through the coating layer and the reflected light beam, these particles are appropriately selected and used in combination according to the purpose and application.
例えば、酸化チタンの被覆率が２９％で主たる粒度が１０〜６０μの顔料（Iriodin 100 ）では標準パール光沢であり、酸化チタンの被覆率が４３％で主たる粒度が＜１５μの顔料（Iriodin 111 ）ではより穏やかなパール光沢であり、酸化チタンの被覆率が１４％で主たる粒度が２０〜１８０μの顔料（Iriodin 163 ）ではよりキラキラしたメタリック調である。
また、酸化チタンの被覆率が５７％で主たる粒度が５〜２５μの顔料（Iriodin 201 ）では金色で穏やかなパール光沢を有し、酸化チタンの被覆率が６２％で主たる粒度が５〜２５μの顔料（Iriodin 221 ）では青色で穏やかなパール光沢を有し、酸化チタンの被覆率が６８％で主たる粒度が５〜２５μの顔料（Iriodin 231 ）では緑色で穏やかなパール光沢を有する。
更に、酸化チタンの被覆率が４８％、酸化鉄被覆率が１０％で主たる粒度が５〜２５μの顔料（Iriodin 302 ）では穏やかな赤味のある金色を呈し、酸化チタンの被覆率が３８％、酸化鉄被覆率が４％で主たる粒度が１０〜６０μの顔料（Iriodin 320 ）ではやや濃い金色を呈し、酸化鉄被覆率が５８％で主たる粒度が５〜２５μの顔料（Iriodin 524 ）では穏やかな赤の金属光沢を有する。
For example, a pigment with a titanium oxide coverage of 29% and a primary particle size of 10-60μ (Iriodin 100) has a standard pearl luster, and a pigment with a titanium oxide coverage of 43% and a primary particle size of <15μ (Iriodin 111) In the case of a pigment (Iriodin 163) having a more gentle pearly luster and a titanium oxide coverage of 14% and a main particle size of 20 to 180 μm, it has a more brilliant metallic tone.
Further, a pigment (Iriodin 201) having a titanium oxide coverage of 57% and a main particle size of 5 to 25 μm has a golden and gentle pearly luster, a titanium oxide coverage of 62% and a main particle size of 5 to 25 μm. The pigment (Iriodin 221) has a blue and gentle pearly luster, and the pigment having a titanium oxide coverage of 68% and a main particle size of 5 to 25 μm (Iriodin 231) has a green and mild pearly luster.
Furthermore, a pigment with a titanium oxide coverage of 48%, an iron oxide coverage of 10% and a primary particle size of 5 to 25μ (Iriodin 302) exhibits a mild reddish gold color and a titanium oxide coverage of 38%. A pigment with an iron oxide coverage of 4% and a primary particle size of 10-60μ (Iriodin 320) exhibits a slightly darker gold color, while a pigment with an iron oxide coverage of 58% and a primary particle size of 5-25μ (Iriodin 524) has a mild color. It has a bright red metallic luster.
これら被覆顔料の例としてはマイカ粒子を基材とした被覆顔料として、例えば、酸化チタンの被覆率１４〜４３％、主な粒度（μ）１〜１８０で銀白色光沢のIriodin 100 シリーズ（100,103,103WNT,111,111WNT,120,121WNT,123,151,153,163,173）、例えば、酸化チタンの被覆率２９〜６８％、主な粒度（μ）５〜１２５で色彩効果を有するIriodin 200 シリーズ（201,201WNT,211,211WNT,221,221WNT,223,223WNT,231,205,205WNT,215,215WNT,217,219WNT,225,225WNT,235,235WNT,249,259,289,299）、例えば、酸化チタンの被覆率１５〜４８％、酸化鉄の被覆率４〜２６％、主な粒度（μ）５〜１００でパール光沢とカラーが一体となったIriodin 300 シリーズ（300,302,303,303WNT,306,309,320,323,323WNT,351,355）、例えば、酸化鉄の被覆率２６〜５８％、主な粒度（μ）５〜１２５で着色力、光沢共に強い効果を有するIriodin 500 シリーズ（500,502,502WNT,504,504WNT,505,505WNT,507,507WNT,508WNT,520,522,522WNT,524,524WNT,525WNT,527WNT,530,532,534）等（いずれもＭＥＲＣＫ社の登録商標）が挙げられる。
また、アルミナ粒子を基材とした被覆顔料の例としては、シラリック(xirallic)T60-10WNT、T60-20WNT、T60-21WNT、T60-23WNT、T60-24WNT、F60-50WNT、F60-51WNT（いずれもＭＥＲＣＫ社の登録商標で粒径５〜３０μ）が挙げられる。これらの被覆顔料は単独でも複数でも用いることができる。
また、これら被覆顔料は、エポキシシラン系、アミノシラン系、メタクリロキシシラン系等やエポキシ樹脂、メラミン樹脂等の各種樹脂で表面処理して、ぬれ性やメラミン系樹脂との接着強度を改善したものや、超微粒子をカットしたもの等も使用可能である。
Examples of these coated pigments include mica particle-based coated pigments, such as Iriodin 100 series (100,103,103WNT), which has a coating ratio of titanium oxide of 14 to 43%, main particle size (μ) of 1 to 180, and silver white gloss. , 111,111WNT, 120,121WNT, 123,151,153,163,173), for example, Iriodin 200 series (201,201WNT, 211,211WNT, 221,221WNT, 223,223) having a color effect at a main particle size (μ) of 5-125 with a titanium oxide coverage of 29-68% WNT, 231,205,205WNT, 215,215WNT, 217,219WNT, 225,225WNT, 235,235WNT, 249,259,289,299), for example, titanium oxide coverage 15 to 48%, iron oxide coverage 4 to 26%, main particle size (μ) 5 Iriodin 300 series (300, 302, 303, 303 WNT, 306, 309, 320, 323, 323 WNT, 351, 355) with pearl luster and color integrated at 100, for example, iron oxide coverage 26-58%, main particle size (μ) 5-125 coloring power, gloss Iriodin 500 Siri which has a strong effect together 'S (500,502,502WNT, 504,504WNT, 505,505WNT, 507,507WNT, 508WNT, 520,522,522WNT, 524,524WNT, 525WNT, 527WNT, 530,532,534) and the like (all MERCK Co. registered trademark).
Examples of coated pigments based on alumina particles include xirallic T60-10WNT, T60-20WNT, T60-21WNT, T60-23WNT, T60-24WNT, F60-50WNT, F60-51WNT (all MERCK is a registered trademark of MERCK Co., Ltd. These coating pigments can be used alone or in combination.
In addition, these coated pigments are surface treated with various resins such as epoxy silane, amino silane, methacryloxy silane, epoxy resin, melamine resin, etc. to improve wettability and adhesive strength with melamine resin. In addition, those obtained by cutting ultrafine particles can be used.
本発明のメラミン系樹脂成形被覆用組成物は、前記のメラミン系樹脂、被覆顔料の他に、例えば、無水フタル酸、ｐ−トルエンスルホン酸等の硬化触媒、ステアリン酸亜鉛、ミリスチン酸亜鉛等の滑剤、その他の添加剤等を含有させることができる。
本発明のメラミン系樹脂成形被覆用組成物を製造するには、メラミン樹脂、グアナミン類、被覆顔料及びその他の添加剤を均一に混合し得る任意の混合手段が採用できる。例えば、ニーダー、リボンブレンダー、ヘンシェルミキサー、ボールミル、ロール練り、らいかい機、タンブラー等の混合機を用いて製造する。
In addition to the melamine resin and the coating pigment, the melamine resin molding coating composition of the present invention includes, for example, a curing catalyst such as phthalic anhydride and p-toluenesulfonic acid, zinc stearate, and zinc myristate. A lubricant, other additives, and the like can be contained.
In order to produce the melamine resin molded coating composition of the present invention, any mixing means capable of uniformly mixing melamine resin, guanamines, coating pigments and other additives can be employed. For example, it manufactures using mixers, such as a kneader, a ribbon blender, a Henschel mixer, a ball mill, a roll kneading, a raking machine, and a tumbler.
以下に実施例などを挙げて本発明を更に詳しく説明するが、本発明はこれら実施例などによりなんら限定されるものではない。
（製造例１）
メラミン（三菱化学株式会社製：油化メラミン）１２６０ｇ（１０モル）とホルマリン（３７％濃度水溶液）１３７９ｇ（１７モル；１．７Ｆ／Ｍ）、及び水９００ｇを還流冷却器付きフラスコに入れ、攪拌しつつ９０℃で加熱反応させて、白濁点が６０℃になった時、０．３ｇのＮａＯＨを導入して冷却しメラミン樹脂初期縮合物を得た。
得られたメラミン樹脂水溶液をスプレードライヤー装置を用いて、約２００℃で乾燥して、粉末状メラミン樹脂が簡単に得られた。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
(Production Example 1)
Melamine (Mitsubishi Chemical Corporation: oil melamine) 1260 g (10 mol), formalin (37% strength aqueous solution) 1379 g (17 mol; 1.7 F / M), and water 900 g were placed in a flask with a reflux condenser and stirred. However, when the white cloud point reached 60 ° C. by heating at 90 ° C., 0.3 g of NaOH was introduced and cooled to obtain a melamine resin initial condensate.
The obtained melamine resin aqueous solution was dried at about 200 ° C. using a spray dryer apparatus to easily obtain a powdery melamine resin.
〔実施例１〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末３０重量部、及び無水フタル酸０．４重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合した。その後、被覆顔料としてＭＥＲＣＫ社製Iriodin （登録商標）１１１ＷＮＴ（酸化チタン被覆率＝４３％、主な粒度＜１５μ）を１０．４重量部（メラミン系樹脂１００重量部に対して８重量部）添加し、更に３０分間ボールミルを運転することにより、メラミン系樹脂成形被覆用組成物Ａを得た。
得られた組成物Ａを用いて、下記の試験片の作製条件で作製した成型物を下記の被覆成形条件で被覆成形した成型物は、下地の色目を損なうことなくパール調の光沢を持った意匠性に優れたものであった。
また、耐クラック性試験の結果、表−１に示すように非常に良好な耐クラック性を示すことが判った。
[Example 1]
100 parts by weight of powdered melamine resin obtained in Production Example 1, 30 parts by weight of benzoguanamine powder, 0.4 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Was mixed sufficiently uniformly. Then, 10.4 parts by weight (8 parts by weight based on 100 parts by weight of melamine resin) of Iriodin (registered trademark) 111 WNT (titanium oxide coverage = 43%, main particle size <15 μ) manufactured by MERCK was added as a coating pigment. And the composition A for melamine-type resin molding coating was obtained by operating a ball mill for 30 minutes.
Using the obtained composition A, the molded product produced under the following test molding conditions was coated and molded under the following coating molding conditions. The molded product had a pearly luster without damaging the underlying color. It was excellent in design.
Further, as a result of the crack resistance test, it was found that very good crack resistance was exhibited as shown in Table-1.
〔実施例２〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末５０重量部、及び無水フタル酸０．５重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合した。均一に分散された前記内容物に被覆顔料としてＭＥＲＣＫ社製Iriodin （登録商標）２２１ＷＮＴ（酸化チタン被覆率＝６２％、主たる粒度５〜２５μ）を２２．５重量部（メラミン系樹脂１００重量部に対して１５重量部）添加し、ヘンシェルミキサーを用いて５分間混合することにより、メラミン系樹脂成形被覆用組成物Ｂを得た。
得られた被覆用組成物Ｂを用いて、下記の試験片の作製条件で作製した成型物を下記の被覆成形条件で被覆成形した成型物は、下地の色目を損なうことなくパール調の光沢を持ち、また、見る角度により青味を帯びて見える意匠性に優れたものであった。
また、耐クラック性試験の結果、表−１に示すように非常に良好な耐クラック性を示すことが判った。
[Example 2]
100 parts by weight of powdered melamine resin obtained in Production Example 1, 50 parts by weight of benzoguanamine powder, 0.5 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Was mixed sufficiently uniformly. 22.5 parts by weight (100 parts by weight of melamine-based resin) of Iriodin (registered trademark) 221 WNT (titanium oxide coverage = 62%, main particle size 5 to 25 μm) manufactured by MERCK as a coating pigment is applied to the above uniformly dispersed contents. 15 parts by weight with respect to the mixture) and mixing for 5 minutes using a Henschel mixer, to obtain a composition B for melamine resin molding coating.
Using the obtained coating composition B, a molded product obtained by coating and molding a molded product produced under the following test piece production conditions under the following coated molding conditions exhibits a pearly luster without damaging the underlying color. In addition, it was excellent in design that looks bluish depending on the viewing angle.
Further, as a result of the crack resistance test, it was found that very good crack resistance was exhibited as shown in Table-1.
〔比較例１〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末３０重量部、及び無水フタル酸０．４重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合させる。その後被覆顔料としてＭＥＲＣＫ社製Iriodin（登録商標）１１１ＷＮＴ（酸化チタン被覆率＝４３％、主な粒度＜１５μ）を０．５重量部（メラミン系樹脂１００重量部に対して０．４重量部）添加し、更に３０分間運転することにより、メラミン系樹脂成形被覆用組成物Ｃを得た。
得られた被覆用組成物Ｃを用いて、下記の試験片の作製条件で作製した成型物を下記の被覆成形条件で被覆成形した成型物は、パール調の光沢が充分には得られないものであった。
また、耐クラック性試験の結果、表−１に示すように良好な耐クラック性は得られなかった。
[Comparative Example 1]
100 parts by weight of powdered melamine resin obtained in Production Example 1, 30 parts by weight of benzoguanamine powder, 0.4 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Are mixed uniformly enough. Thereafter, Iriodin (registered trademark) 111WNT manufactured by MERCK as a coating pigment (0.5% by weight of titanium oxide coating ratio = 43%, main particle size <15 μ) (0.4 parts by weight with respect to 100 parts by weight of melamine resin) By adding and operating for 30 minutes, the composition C for melamine-type resin molding coating was obtained.
Using the obtained coating composition C, a molded product obtained by coating and molding a molded product produced under the following test piece production conditions under the following coating molding conditions does not provide sufficient pearly luster. Met.
As a result of the crack resistance test, good crack resistance was not obtained as shown in Table-1.
〔比較例２〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末３０重量部、及び無水フタル酸０．４重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合させることにより、メラミン系樹脂成形被覆用組成物Ｄを得た。
得られた被覆用組成物Ｄを用いて、下記の試験片の作製条件で作製した成型物を下記の被覆成形条件で被覆成形した成型物を用いて耐クラック性試験を実施した結果、表−１に示すように良好な耐クラック性は得られなかった。
[Comparative Example 2]
100 parts by weight of powdered melamine resin obtained in Production Example 1, 30 parts by weight of benzoguanamine powder, 0.4 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Was sufficiently uniformly mixed to obtain a melamine-based resin-molding coating composition D.
As a result of performing a crack resistance test using a molded product obtained by coating and molding a molded product produced under the following test molding conditions using the obtained coating composition D, Table- As shown in FIG. 1, good crack resistance was not obtained.
〔比較例３〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末３０重量部、及び無水フタル酸０．４重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合させた。その後、酸化チタンを１０重量部添加し、更に３０分間運転することにより、メラミン系樹脂成形被覆用組成物Ｅを得た。
得られた被覆用組成物Ｅを用いて、下記の試験片の作製条件で作製した成型物を下記の被覆成形条件で被覆成形した成型物を用いて耐クラック性試験を実施した結果、表−１に示すように良好な耐クラック性は得られなかった。
[Comparative Example 3]
100 parts by weight of powdered melamine resin obtained in Production Example 1, 30 parts by weight of benzoguanamine powder, 0.4 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Were mixed uniformly enough. Thereafter, 10 parts by weight of titanium oxide was added, and the mixture was further operated for 30 minutes to obtain a composition E for melamine resin molding coating.
As a result of conducting a crack resistance test using a molded product obtained by coating and molding a molded product produced under the following test molding conditions using the obtained coating composition E under the following coating molding conditions, Table- As shown in FIG. 1, good crack resistance was not obtained.
（試験片の作製）
以下の条件により、成形被覆に供する試験片を作製した。
成形機：４５Ｔｏｎプレス機
金型：汁椀
下地の成形材料：ニカレットＭＣ ＣＥ３１８０Ｆ〔日本カーバイド工業株式会社製〕
金型温度（上型／下型）：１６５℃／１６５℃
型締め速度：５秒
初圧および時間：８．８ＭＰａ×２秒
ガス抜き：０．７秒
成形圧および時間：１１．８ＭＰａ×１２０秒
(Preparation of test piece)
A test piece to be used for forming coating was prepared under the following conditions.
Molding machine: 45Ton press Mold: Soup bowl Molding material of base: Nicaret MC CE3180F [manufactured by Nippon Carbide Industries Co., Ltd.]
Mold temperature (upper mold / lower mold): 165 ° C / 165 ° C
Clamping speed: 5 seconds Initial pressure and time: 8.8 MPa × 2 seconds Degassing: 0.7 seconds Molding pressure and time: 11.8 MPa × 120 seconds
（被覆成形条件）
上記条件にて下地の成形材料を成形後、以下の条件により、試験片上に成形被覆して試験片を作製した。
成形機：４５Ｔｏｎプレス機
金型：汁椀
金型温度（上型／下型）：１６５℃／１６５℃
型締め速度：５秒
初圧および時間：８．８ＭＰａ×２秒
ガス抜き：０．７秒
成形圧および時間：１５．７ＭＰａ×３０秒
(Coating molding conditions)
After molding the underlying molding material under the above conditions, the test piece was formed and coated on the test piece under the following conditions.
Molding machine: 45Ton press Mold: Soup bowl Mold temperature (upper mold / lower mold): 165 ° C / 165 ° C
Clamping speed: 5 seconds Initial pressure and time: 8.8 MPa × 2 seconds Degassing: 0.7 seconds Molding pressure and time: 15.7 MPa × 30 seconds
（試験方法）
耐クラック試験
沸騰水中で１時間煮沸した後、８０℃で１時間乾燥する工程を１サイクルとし、９サイクルまでの試験を実施した。煮沸後の試験片について、グレーズ層のクラックを確認することにより耐クラック性の優劣を判定した。
(Test method)
Crack resistance test After boiling in boiling water for 1 hour, the process of drying at 80 ° C for 1 hour was defined as 1 cycle, and tests up to 9 cycles were performed. About the test piece after boiling, the superiority or inferiority of crack resistance was determined by confirming the crack of the glaze layer.
〔実施例３〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末３０重量部、及び無水フタル酸０．４重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合した。その後、被覆顔料としてＭＥＲＣＫ社製Iriodin（登録商標）１６３（酸化チタン被覆率＝１４％、主たる粒度２０〜１８０μ）を１０．４重量部（メラミン系樹脂１００重量部に対して８重量部）添加し、更に３０分間ボールミルを運転することにより、メラミン系樹脂成形被覆用組成物Ｆを得た。
得られた被覆用組成物Ｆを用いて、上記の試験片の作製条件で作製した成型物を上記の被覆成形条件で被覆成形した成型物は、下地の色目を損なうことなくキラキラしたメタリック調の光沢を持った意匠性に優れたものであった。
また、耐クラック性試験の結果、表−２に示すように非常に良好な耐クラック性を示すことが判った。
Example 3
100 parts by weight of powdered melamine resin obtained in Production Example 1, 30 parts by weight of benzoguanamine powder, 0.4 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Was mixed sufficiently uniformly. Then, 10.4 parts by weight (8 parts by weight with respect to 100 parts by weight of melamine resin) of Iriodin (registered trademark) 163 manufactured by MERCK (titanium oxide coverage = 14%, main particle size 20 to 180 μ) was added as a coating pigment. And the composition F for melamine-type resin molding coating was obtained by operating a ball mill for 30 minutes.
Using the obtained coating composition F, the molded product produced under the above-mentioned test molding conditions was coated and molded under the above-mentioned coating molding conditions. The molded product had a glittering metallic tone without damaging the underlying color. The glossy design was excellent.
Moreover, as a result of the crack resistance test, it was found that very good crack resistance was exhibited as shown in Table-2.
〔実施例４〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末３０重量部、及び無水フタル酸０．４重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合した。その後、被覆顔料としてＭＥＲＣＫ社製Iriodin（登録商標）２３１（酸化チタン被覆率＝６８％、主たる粒度５〜２５μ）を１０．４重量部（メラミン系樹脂１００重量部に対して８重量部）添加し、更に３０分間ボールミルを運転することにより、メラミン系樹脂成形被覆用組成物Ｇを得た。
得られた被覆用組成物Ｇを用いて、上記の試験片の作製条件で作製した成型物を上記の被覆成形条件で被覆成形した成型物は、下地の色目を損なうことなく穏やかなパール調の光沢を持った意匠性に優れたものであった。
また、耐クラック性試験の結果、表−２に示すように非常に良好な耐クラック性を示すことが判った。
Example 4
100 parts by weight of powdered melamine resin obtained in Production Example 1, 30 parts by weight of benzoguanamine powder, 0.4 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Was mixed sufficiently uniformly. Thereafter, 10.4 parts by weight (8 parts by weight with respect to 100 parts by weight of the melamine resin) of Iriodin (registered trademark) 231 (titanium oxide coverage = 68%, main particle size 5 to 25 μ) manufactured by MERCK as a coating pigment was added. And the composition G for melamine-type resin molding coating was obtained by operating a ball mill for 30 minutes.
Using the obtained coating composition G, the molded product produced under the above-mentioned test piece production conditions was coated and molded under the above-mentioned coating molding conditions. The glossy design was excellent.
Moreover, as a result of the crack resistance test, it was found that very good crack resistance was exhibited as shown in Table-2.
〔実施例５〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末３０重量部、及び無水フタル酸０．５重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合した。その後、被覆顔料としてＭＥＲＣＫ社製Iriodin（登録商標）３０２（酸化チタン被覆率＝４８％、酸化鉄被覆率＝１０％、主たる粒度５〜２５μ）を１０．４重量部（メラミン系樹脂１００重量部に対して８重量部）添加し、更に３０分間ボールミルを運転することにより、メラミン系樹脂成形被覆用組成物Ｈを得た。
得られた被覆用組成物Ｈを用いて、上記の試験片の作製条件で作製した成型物を上記の被覆成形条件で被覆成形した成型物は、穏やかな赤味のある金色を示す意匠性に優れたものであった。
また、耐クラック性試験の結果、表−２に示すように非常に良好な耐クラック性を示すことが判った。
Example 5
100 parts by weight of powdered melamine resin obtained in Production Example 1, 30 parts by weight of benzoguanamine powder, 0.5 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Was mixed sufficiently uniformly. Thereafter, 10.4 parts by weight (100 parts by weight of melamine resin) of Iriodin (registered trademark) 302 manufactured by MERCK as a coating pigment (titanium oxide coverage = 48%, iron oxide coverage = 10%, main particle size 5 to 25 μ) 8 parts by weight) was added, and the ball mill was further operated for 30 minutes to obtain a melamine-based resin molding coating composition H.
Using the obtained coating composition H, a molded product obtained by coating and molding a molded product produced under the above-mentioned test piece production conditions under the above-mentioned coated molding conditions has a design property showing a mild reddish gold color. It was excellent.
Moreover, as a result of the crack resistance test, it was found that very good crack resistance was exhibited as shown in Table-2.
〔実施例６〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末３０重量部、及び無水フタル酸０．４重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合した。その後、被覆顔料としてＭＥＲＣＫ社製Iriodin（登録商標）５２４（酸化鉄被覆率＝５８％、主たる粒度５〜２５μ）を１０．４重量部（メラミン系樹脂１００重量部に対して８重量部）添加し、更に３０分間ボールミルを運転することにより、メラミン系樹脂成形被覆用組成物Ｉを得た。
得られた被覆用組成物Ｉを用いて、上記の試験片の作製条件で作製した成型物を上記の被覆成形条件で被覆成形した成型物は、穏やかな赤の金属光沢を持った意匠性に優れたものであった。
また、耐クラック性試験の結果、表−２に示すように非常に良好な耐クラック性を示すことが判った。
Example 6
100 parts by weight of powdered melamine resin obtained in Production Example 1, 30 parts by weight of benzoguanamine powder, 0.4 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Was mixed sufficiently uniformly. Then, 10.4 parts by weight (8 parts by weight with respect to 100 parts by weight of melamine resin) of Iriodin (registered trademark) 524 (iron oxide coverage = 58%, main particle size 5 to 25 μ) manufactured by MERCK as a coating pigment was added. And the composition I for melamine-type resin molding coating was obtained by operating a ball mill for 30 minutes.
Using the obtained coating composition I, a molded product produced under the above-mentioned coating molding conditions using a molded product produced under the above-described test specimen production conditions is designed to have a gentle red metallic luster. It was excellent.
Moreover, as a result of the crack resistance test, it was found that very good crack resistance was exhibited as shown in Table-2.
〔実施例７〕
製造例１で得られた粉末状メラミン樹脂１００重量部、ベンゾグアナミン粉末５０重量部、及び無水フタル酸０．５重量部、ステアリン酸亜鉛０．６重量部をボールミルにて８時間粉砕して内容物を充分に均一に混合した。その後、被覆顔料としてＭＥＲＣＫ社製Iriodin（登録商標）１６３（酸化チタン被覆率＝１４％、主たる粒度２０〜１８０μ）を２２．５重量部（メラミン系樹脂１００重量部に対して１５重量部）添加し、ヘンシェルミキサーを用いて５分間運転することにより、メラミン系樹脂成形被覆用組成物Ｊを得た。
得られた被覆用組成物Ｊを用いて、上記の試験片の作製条件で作製した成型物を上記の被覆成形条件で被覆成形した成型物は、下地の色目を損なうことなくキラキラしたメタリック調の光沢を持った意匠性に優れたものであった。
また、耐クラック性試験の結果、表−２に示すように非常に良好な耐クラック性を示すことが判った。
Example 7
100 parts by weight of powdered melamine resin obtained in Production Example 1, 50 parts by weight of benzoguanamine powder, 0.5 parts by weight of phthalic anhydride, and 0.6 parts by weight of zinc stearate are pulverized in a ball mill for 8 hours. Was mixed sufficiently uniformly. Thereafter, 22.5 parts by weight (15 parts by weight with respect to 100 parts by weight of melamine resin) of Iriodin (registered trademark) 163 (titanium oxide coverage = 14%, main particle size 20 to 180 μ) manufactured by MERCK as a coating pigment was added. And the composition J for melamine-type resin molding coating was obtained by driving | running for 5 minutes using a Henschel mixer.
Using the obtained coating composition J, the molded product produced under the above-mentioned test molding conditions was coated and molded under the above-mentioned coating molding conditions. The glossy design was excellent.
Moreover, as a result of the crack resistance test, it was found that very good crack resistance was exhibited as shown in Table-2.
本発明によるメラミン系樹脂成形被覆用組成物は、皿、茶碗、盆、お椀等の食器類の成型品の被覆用として用いられ、耐クラック性に優れ、多彩な色彩の意匠性にも優れた食器類等の成型品を提供する。 The composition for melamine resin molding coating according to the present invention is used for coating molded products of dishes such as dishes, teacups, trays, bowls, etc., and has excellent crack resistance and excellent design of various colors. Provide molded products such as tableware.
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| JPH11236520A (en) * | 1998-02-23 | 1999-08-31 | Nippon Paint Co Ltd | Bright coating composition, method for forming bright coating film, and coated article |
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| JPS6485173A (en) * | 1986-07-29 | 1989-03-30 | Nippon Paint Co Ltd | Method for formation of coating film |
| JPS6384936A (en) * | 1986-09-30 | 1988-04-15 | イビデン株式会社 | Decorative board with metallic gloss surface and manufacture thereof |
| JPH08199087A (en) * | 1995-01-27 | 1996-08-06 | Topy Ind Ltd | Novel pearlescent pigment, and coating composition, cosmetic, ink and plastic containing same |
| JPH10226990A (en) * | 1997-02-06 | 1998-08-25 | Tokyo Seishi Kk | Pearl pigment-coated paper |
| JPH11236520A (en) * | 1998-02-23 | 1999-08-31 | Nippon Paint Co Ltd | Bright coating composition, method for forming bright coating film, and coated article |
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| JP2013147623A (en) * | 2012-01-23 | 2013-08-01 | Nippon Carbide Ind Co Inc | Resin composition for coating |
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