TW201833249A - Plastic molded article decorated in metallic style - Google Patents
Plastic molded article decorated in metallic style Download PDFInfo
- Publication number
- TW201833249A TW201833249A TW107103422A TW107103422A TW201833249A TW 201833249 A TW201833249 A TW 201833249A TW 107103422 A TW107103422 A TW 107103422A TW 107103422 A TW107103422 A TW 107103422A TW 201833249 A TW201833249 A TW 201833249A
- Authority
- TW
- Taiwan
- Prior art keywords
- undercoat layer
- plastic molded
- solid content
- molded article
- fine particles
- Prior art date
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- 239000007787 solid Substances 0.000 claims abstract description 46
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- 239000002184 metal Substances 0.000 claims description 39
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- IZXGZAJMDLJLMF-UHFFFAOYSA-N methylaminomethanol Chemical compound CNCO IZXGZAJMDLJLMF-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- PYUYQYBDJFMFTH-WMMMYUQOSA-N naphthol red Chemical compound CCOC1=CC=CC=C1NC(=O)C(C1=O)=CC2=CC=CC=C2\C1=N\NC1=CC=C(C(N)=O)C=C1 PYUYQYBDJFMFTH-WMMMYUQOSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002755 pyrazolinyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- WUWHFEHKUQVYLF-UHFFFAOYSA-M sodium;2-aminoacetate Chemical compound [Na+].NCC([O-])=O WUWHFEHKUQVYLF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/067—Metallic effect
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2503/00—Polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
- B05D2601/22—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2601/00—Inorganic fillers
- B05D2601/20—Inorganic fillers used for non-pigmentation effect
- B05D2601/24—Titanium dioxide, e.g. rutile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemically Coating (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本發明係關於在塑膠基材上至少依序具有底塗層、無電解銀鍍覆層及上塗層之被加飾成金屬調性之塑膠成形品。詳而言之，係關於一種兼具高光澤性及優異耐久性的被加飾成金屬調性之塑膠成形品。 The present invention relates to a plastic shaped article that is decorated with metal tones and has at least an undercoat layer, an electroless silver plating layer and an overcoat layer on a plastic substrate in order. Specifically, it relates to a plastic molded product that is decorated with metal tones and has both high gloss and excellent durability.
塑膠基材之表面為被加飾成金屬調性之塑膠成形品，廣泛被利用作為新式樣性材料、光反射材料。將塑膠基材之表面加飾成金屬調性之方法之一，有在其表面進行無電解銀鍍覆之方法。銀在金屬中具有最高的光反射率，即使為薄膜亦顯示高的反射光澤，故在塑膠表面進行無電解銀鍍覆之方法，適宜作為獲得被加飾成金屬調性之塑膠成形品的方法。 The surface of the plastic substrate is a plastic molded product decorated with metal tones, which is widely used as a new style material and light reflecting material. One of the methods of decorating the surface of a plastic substrate into a metal tone is a method of performing electroless silver plating on the surface. Silver has the highest light reflectivity in metals and shows high reflective gloss even in thin films. Therefore, the method of electroless silver plating on the plastic surface is suitable as a method for obtaining plastic shaped articles decorated with metallic tones. .
但，無電解銀鍍覆層係薄且柔軟，力學的強度弱，故具有容易刮傷之缺點。又，銀在空氣中常常因腐蝕而變色，無法持續加飾之效果。為彌補如此之缺點，已知有藉由各種透明塗層劑在無電解銀鍍覆層之上設置上塗層之方法。特別是塑膠成形品之情形，使用可以比較低 溫形成強固的膜之胺基甲酸酯樹脂的上塗層較多被研究。例如，在專利文獻1、專利文獻2、專利文獻3中，記載可在無電解銀鍍覆層上之上塗層使用胺基甲酸酯樹脂。又，在專利文獻4揭示使用含有防鏽劑之胺基甲酸酯樹脂的上塗層。 However, the electroless silver plating layer is thin, soft, and weak in mechanical strength, and therefore has the disadvantage of being easily scratched. In addition, silver often discolors due to corrosion in the air, and the effect of decoration cannot be continued. In order to make up for such shortcomings, it is known to provide a coating layer on the electroless silver plating layer by various transparent coating agents. In particular, in the case of a plastic molded product, an overcoat layer using a urethane resin that can form a strong film at a relatively low temperature has been studied in many cases. For example, Patent Document 1, Patent Document 2, and Patent Document 3 describe that a urethane resin can be used as a coating on the electroless silver plating layer. Further, Patent Document 4 discloses an overcoat layer using a urethane resin containing a rust inhibitor.
如此，可以比較低溫形成強固的膜、而且耐久性及塗裝之作業性亦優異的胺基甲酸酯樹脂，被認為適宜作為藉由無電解銀鍍覆被加飾成金屬調性之塑膠成形品的上塗層之材料。但是，實際上，已知上塗層含有胺基甲酸酯樹脂作為主成分時，容易發生所謂未完成精美鏡面之外觀上不佳的情形。特別是在表面映照光源時，難以避免在光源之反射像周圍觀察到白色環或虹色環之被稱為月暈之現象。因此，金屬調性加飾之價值降低，成為在上塗層使用胺基甲酸酯樹脂之大障礙。 In this way, a urethane resin that can form a strong film at a relatively low temperature and has excellent durability and coating workability is considered to be suitable as a plastic molding that is decorated with metal tones by electroless silver plating. Material for the top coating of the product. However, in fact, when it is known that an overcoat layer contains a urethane resin as a main component, the appearance of a so-called unfinished fine mirror surface tends to be poor. Especially when the light source is reflected on the surface, it is difficult to avoid the phenomenon called the moon halo which is observed around the reflection image of the light source. As a result, the value of metallic tonal decoration is reduced, which is a major obstacle to the use of urethane resins in the top coat.
另一方面，當以無電解銀鍍覆製作金屬調性加飾成形品時，為了改善塑膠基材表面之粗度以獲得更有效果的金屬光澤之目的、以及確保無電解銀鍍覆層與基材之密著性之目的，已知有設置底塗層之方法。底塗層被要求與塑膠基材之密著性優異，且與設在底塗層上之無電解銀鍍覆層的密著性亦優異。 On the other hand, when electroless silver plating is used to produce metal toned decorative shaped articles, in order to improve the roughness of the surface of the plastic substrate to obtain a more effective metallic gloss, and to ensure that the electroless silver plating layer and the For the purpose of adhesion of a substrate, a method of providing an undercoat layer is known. The undercoat layer is required to have excellent adhesion to a plastic substrate, and also has excellent adhesion to an electroless silver plating layer provided on the undercoat layer.
如此之底塗層，例如前述專利文獻2中揭示一種含有金屬烷氧化物或金屬膠體及樹脂之底塗層。又，在專利文獻5中係記載分別以特定之比率含有丙烯酸樹脂、胺基樹脂、環氧樹脂及烷氧基鈦酯之底塗劑。此外， 在專利文獻6及專利文獻7中記載由含有特定成分的胺基甲酸酯樹脂所構成的底塗層，在專利文獻8記載含有胺基甲酸酯樹脂及環氧樹脂之底塗層。 Such an undercoat layer, for example, discloses an undercoat layer containing a metal alkoxide or a metal colloid and a resin in the aforementioned Patent Document 2. Further, Patent Document 5 describes a primer containing acrylic resin, amine-based resin, epoxy resin, and titanium alkoxylate at specific ratios. In addition, Patent Documents 6 and 7 describe an undercoat layer composed of a urethane resin containing a specific component, and Patent Document 8 describes an undercoat layer containing a urethane resin and an epoxy resin. .
但此等底塗層雖係主要與無電解銀鍍覆層之密著性優異者，但與含有如前述之胺基甲酸酯樹脂作為主成分之上塗層一齊使用時，仍無法解決在光源之反射像周圍觀察到白色環或虹色環之月暈問題，外觀上之問題仍然未解決。 However, although these undercoatings are mainly excellent in adhesion with the electroless silver plating layer, they cannot be resolved when used together with an overcoat layer containing the aforementioned urethane resin as a main component. The moon halo of white or iris rings is observed around the reflection image of the light source, and the appearance problem remains unresolved.
另一方面，有關底塗層之技術，在專利文獻9揭示一種在含有金屬氧化物水合物與黏結劑樹脂之底塗層上進行無電解鍍覆之電磁波屏蔽體，記載藉由如此之底塗層使形成於其上之金屬層難以被剝離。又，在專利文獻10揭示一種無電解鍍覆的遮光膜，該遮光膜具備含有無機填充劑及黏結劑樹脂之底塗層，記載可藉由如此之底塗層改善密著性及針孔的發生。 On the other hand, regarding the technology of the undercoat layer, Patent Document 9 discloses an electromagnetic wave shield body which is subjected to electroless plating on the undercoat layer containing a metal oxide hydrate and a binder resin. The layer makes it difficult to peel off the metal layer formed thereon. Further, Patent Document 10 discloses an electrolessly-plated light-shielding film having an undercoat layer containing an inorganic filler and a binder resin. It is described that such an undercoat layer can improve adhesion and pinholes. occur.
[專利文獻1]日本特開2000-129448號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2000-129448
[專利文獻2]日本特開2000-129452號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2000-129452
[專利文獻3]日本特開2001-164380號公報 [Patent Document 3] Japanese Patent Laid-Open No. 2001-164380
[專利文獻4]日本特開2006-111857號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2006-111857
[專利文獻5]日本特開2001-040486號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2001-040486
[專利文獻6]日本特開2004-359824號公報 [Patent Document 6] Japanese Patent Laid-Open No. 2004-359824
[專利文獻7]日本特開2007-23087號公報 [Patent Document 7] Japanese Patent Laid-Open No. 2007-23087
[專利文獻8]日本特開2014-108531號公報 [Patent Document 8] Japanese Patent Laid-Open No. 2014-108531
[專利文獻9]日本特開平9-135097號公報 [Patent Document 9] Japanese Patent Laid-Open No. 9-135097
[專利文獻10]日本特開2011-194824號公報 [Patent Document 10] Japanese Patent Laid-Open No. 2011-194824
本發明之目的係提供一種兼具高光澤性及優異耐久性之被加飾成金屬調性的塑膠成形品。更詳而言之，本發明之目的係解決具有底塗層、無電解銀鍍覆層、及上塗層之被加飾成金屬調性之塑膠成形品中在上塗層使用胺基甲酸酯樹脂時會發生之外觀上的不佳情形(月暈)，藉此提供一種兼具高光澤性及優異耐久性之被加飾成金屬調性之塑膠成形品。 An object of the present invention is to provide a plastic molded article decorated with metal tones that has both high gloss and excellent durability. In more detail, the object of the present invention is to solve the use of amino formic acid in the upper coating of plastic molded articles decorated with metal tones having an undercoat layer, an electroless silver plating layer, and an overcoat layer. Deterioration in appearance (moon halo) that occurs when an ester resin is used, thereby providing a plastic molded article decorated with metal tones that has both high gloss and excellent durability.
本發明之上述目的，基本上係藉由一種被加飾成金屬調性之塑膠成形品來達成，該被加飾成金屬調性之塑膠成形品係在塑膠基材上至少依序具有底塗層、無電解銀鍍覆層、以及含有胺基甲酸酯樹脂作為主成分之上塗層者，其特徵為：底塗層含有黏結劑樹脂及平均粒徑大於100nm且小於800nm之無機微粒子，無機微粒子在底塗層中的固體成分量相對於底塗層之全固體成分量為10至60質量%。 The above-mentioned object of the present invention is basically achieved by a plastic shaped article decorated with a metal tone. The plastic shaped article decorated with a metal tone has at least a primer coating on a plastic substrate in order. Layer, electroless silver plating layer, and an overcoat layer containing a urethane resin as a main component, which is characterized in that the undercoat layer contains a binder resin and inorganic fine particles having an average particle size of more than 100 nm and less than 800 nm, The solid content of the inorganic fine particles in the undercoat layer is 10 to 60% by mass based on the total solid content of the undercoat layer.
其中，無機微粒子以選自二氧化鈦、硫酸鋇及二氧化矽的無機微粒子為較佳，更佳係二氧化鈦為金 紅石型二氧化鈦、硫酸鋇為沈降性硫酸鋇、二氧化矽為球狀二氧化矽。又，較佳係無機微粒子之平均粒徑為155nm以上，較佳係無機微粒子之底塗層中的固體成分量相對於底塗層之全固體成分量為30質量%以上。再者，較佳係底塗層之黏結劑樹脂為胺基甲酸酯樹脂。 Among them, the inorganic fine particles are preferably inorganic fine particles selected from the group consisting of titanium dioxide, barium sulfate, and silicon dioxide. More preferred titanium dioxide is rutile-type titanium dioxide, barium sulfate is degradable barium sulfate, and silicon dioxide is spherical silicon dioxide. The average particle diameter of the inorganic fine particles is preferably 155 nm or more, and the solid content of the inorganic fine particles in the undercoat layer is preferably 30% by mass or more relative to the total solid content of the undercoat layer. Moreover, it is preferable that the binder resin of the undercoat layer is a urethane resin.
藉由本發明，可提供一種兼具高光澤性及優異耐久性之被加飾成金屬調性之塑膠成形品。 According to the present invention, it is possible to provide a plastic molded product decorated with metal tones that has both high gloss and excellent durability.
以下詳細說明本發明。 The present invention is explained in detail below.
本發明之塑膠成形品係塑膠部材之表面被加飾成金屬調性者，在塑膠基材上至少依序具有底塗層、無電解銀鍍覆層、以及含有胺基甲酸酯樹脂作為主成分之上塗層，該底塗層含有黏結劑樹脂及無機微粒子。 The surface of the plastic molded product of the present invention is a plastic material whose surface is decorated with metal tones. The plastic substrate has at least an undercoat layer, an electroless silver plating layer, and a urethane resin as the main component. The component is an overcoat layer, and the undercoat layer contains a binder resin and inorganic fine particles.
本發明之底塗層含有的黏結劑樹脂並無特別限制，但較佳係以在基材上塗設底塗之作業容易的熱硬化性樹脂作為主成分。熱硬化性樹脂可舉例如胺基甲酸酯樹脂、環氧樹脂、三聚氰胺樹脂、尿素樹脂、胺基醇酸樹脂、不飽和聚酯樹脂、酚樹脂、丙烯酸樹脂、聚矽氧樹脂等，此等樹脂可單獨使用，亦可混合2種類以上使用。進而，此等熱硬化性樹脂之中，又以使用因可在低溫硬化故塗裝作業性優異、而且對於塑膠基材及銀鍍覆層之密著性 亦優異的胺基甲酸酯樹脂為佳，較佳係使用相對於底塗層含有之全黏結劑樹脂的固體成分量70質量%以上之胺基甲酸酯樹脂。 The binder resin contained in the undercoat layer of the present invention is not particularly limited, but it is preferably based on a thermosetting resin that is easy to apply an undercoat on a substrate as a main component. Examples of the thermosetting resin include urethane resin, epoxy resin, melamine resin, urea resin, amino alkyd resin, unsaturated polyester resin, phenol resin, acrylic resin, silicone resin, and the like. The resin can be used alone or as a mixture of two or more types. Furthermore, among these thermosetting resins, urethane resins which are excellent in coating workability because they can be hardened at low temperatures and have excellent adhesion to plastic substrates and silver plating layers are used. Preferably, the urethane resin is used in an amount of 70% by mass or more based on the solid content of the total binder resin contained in the undercoat layer.
上述之胺基甲酸酯樹脂可舉例如將醇酸多元醇、聚酯多元醇、丙烯酸多元醇、聚醚多元醇、聚碳酸酯多元醇、聚丁內酯多元醇等由具有末端羥基之聚合物或寡聚物所構成之樹脂與作為硬化劑之異氰酸酯化合物混合而得之胺基甲酸酯樹脂。其中，較佳係混合丙烯酸多元醇樹脂與異氰酸酯化合物所得之胺基甲酸酯樹脂。藉此，可獲得耐久性特別優異的底塗層。 The above-mentioned urethane resin may be, for example, polymerized alkyd polyols, polyester polyols, acrylic polyols, polyether polyols, polycarbonate polyols, polybutyrolactone polyols, and the like by polymerization having terminal hydroxyl groups. A urethane resin obtained by mixing a resin composed of a polymer or an oligomer with an isocyanate compound as a hardener. Among them, a urethane resin obtained by mixing an acrylic polyol resin and an isocyanate compound is preferred. Thereby, an undercoat layer having particularly excellent durability can be obtained.
上述用來作為胺基甲酸酯樹脂之硬化劑的異氰酸酯化合物，可使用縮脲型、三聚異氰酸酯型、加成物型、二官能型之異氰酸酯，但從耐久性之觀點，較佳者為縮脲型之異氰酸酯化合物。 As the isocyanate compound used as the hardener of the urethane resin, a ureton type, a trimer isocyanate type, an adduct type, and a difunctional type isocyanate can be used, but from the viewpoint of durability, the preferred is Urea-type isocyanate compound.
又，上述之胺基甲酸酯樹脂亦可購入市售品後利用。可使用所謂2液型胺基甲酸酯塗料之市售塗料，在本發明中較佳使用之丙烯酸多元醇樹脂，例如Mirror shine undercoat Clear D-1及Under black No.128由大橋化學工業股份有限公司販售，又異氰酸酯化合物如底塗透明漆用硬化劑-N及防鏽底塗硬化劑亦由同公司販售，可購入彼等後利用。 In addition, the aforementioned urethane resin may be used after being purchased. Commercially available coatings of so-called two-component urethane coatings can be used. Acrylic polyol resins preferred in the present invention, such as Mirror shine undercoat Clear D-1 and Under black No. 128 are limited by Ohashi Chemical Industry Co., Ltd. The company sells isocyanate compounds such as hardener-N for priming clear lacquers and rust-proof undercoating hardeners. They are also sold by the same company and can be used after purchasing them.
本發明之底塗層係含有平均粒徑大於100nm且小於800nm之無機微粒子。藉由底塗層含有該無機微粒子，即使設置由胺基甲酸酯樹脂所構成之上塗層時，亦可 維持高光澤性。無機微粒子之平均粒徑太小時，有時產生凝集而難以提高無機微粒子之固體成分濃度，並且維持光澤之效果變小。無機微粒子之平均粒徑太大時，有時因銀鍍覆層表面變粗而光澤性降低。因此，底塗層含有之無機微粒子係平均粒徑大於100nm且小於800nm之無機微粒子，平均粒徑為155nm以上之無機微粒子更適當。 The undercoat layer of the present invention contains inorganic fine particles having an average particle diameter of more than 100 nm and less than 800 nm. By containing the inorganic fine particles in the undercoat layer, even when an overcoat layer composed of a urethane resin is provided, high gloss can be maintained. When the average particle diameter of the inorganic fine particles is too small, agglomeration may occur, which may make it difficult to increase the solid content concentration of the inorganic fine particles, and the effect of maintaining gloss may be reduced. When the average particle diameter of the inorganic fine particles is too large, the surface of the silver plated layer may become coarse and the gloss may decrease. Therefore, the inorganic fine particles contained in the undercoat layer are more suitable for inorganic fine particles having an average particle diameter of more than 100 nm and less than 800 nm, and inorganic particles having an average particle diameter of 155 nm or more.
本發明中之平均粒徑為體積基準之中值徑。如此之平均粒徑可以一般為人所知之公知方法測定，可舉例如篩法、Coulter法、動態光散射法、藉由顯微鏡觀察計測粒徑之方法、雷射繞射散射法等。在本發明中，較佳係使用藉由顯微鏡觀察計測粒徑之方法或雷射繞射散射法。 The average particle diameter in the present invention is a volume-based median diameter. Such an average particle diameter can be measured by a generally known method, and examples thereof include a sieve method, a Coulter method, a dynamic light scattering method, a method for measuring a particle diameter by a microscope observation, and a laser diffraction scattering method. In the present invention, it is preferable to use a method of measuring the particle diameter by a microscope observation or a laser diffraction scattering method.
本發明之底塗層含有的無機微粒子可舉例如碳酸鈣、碳酸鎂、氧化鋅、二氧化鈦、硫酸鋇、氫氧化鋁、氫氧化鋅、二氧化矽等。其中，從耐久性之觀點而言，以化學性安定之二氧化鈦、硫酸鋇、二氧化矽為較佳。 Examples of the inorganic fine particles contained in the undercoat layer of the present invention include calcium carbonate, magnesium carbonate, zinc oxide, titanium dioxide, barium sulfate, aluminum hydroxide, zinc hydroxide, and silicon dioxide. Among these, chemically stable titanium dioxide, barium sulfate, and silicon dioxide are preferred from the viewpoint of durability.
二氧化鈦較佳係不易受到紫外線影響之金紅石型二氧化鈦。有關其製法並無限定。再者，從分散安定性及紫外線惰性之觀點而言，亦可使用經施予各種表面處理者。市售之二氧化鈦的微粒子例如由堺化學工業股份有限公司販售者，可舉例如R-25、R-21、R-5N、R-62N、GTR-100等，由石原產業股份有限公司販售者可舉例如CR-90、CR-93、CR-97等，由鈦工業股份有限公司販售者可舉例如KR-380等，由Tayca股份有限公司販售者可舉 例如JR-403等。 Titanium dioxide is preferably rutile titanium dioxide which is not easily affected by ultraviolet rays. There are no restrictions on its manufacturing method. Furthermore, from the viewpoints of dispersion stability and ultraviolet inertness, those subjected to various surface treatments can also be used. Commercially available fine particles of titanium dioxide are sold by, for example, Sakai Chemical Industry Co., Ltd., and for example, R-25, R-21, R-5N, R-62N, GTR-100 and the like are sold by Ishihara Industry Co., Ltd. Examples include CR-90, CR-93, and CR-97, and those sold by Titanium Industry Co., Ltd. include KR-380, and those sold by Tayca Co., Ltd. include JR-403.
硫酸鋇較佳係使用沈降性硫酸鋇。沈降性硫酸鋇之微粒子，例如由堺化學工業股份有限公司販售稱為「Bariace」之各種粒徑者或經施予表面處理者等，但在本發明可從其中選擇平均粒徑適合者使用。 Barium sulfate is preferably precipitated barium sulfate. Fine particles of sedimentary barium sulfate, such as those with various particle sizes called "Bariace" sold by Hori Chemical Industry Co., Ltd., or those having been subjected to a surface treatment, etc., but in the present invention, a suitable average particle diameter can be selected for use .
二氧化矽之微粒子只要平均粒徑適合，可使用任一者，但較佳者為球狀二氧化矽。因球狀而不發生凝集，在塗膜中容易有效率地填充二氧化矽微粒子。球狀二氧化矽例如Admatechs股份有限公司販售「Admafine」系列，堺化學工業股份有限公司販售「sciqas」或「M SD」系列，日本觸媒股份有限公司販售「Seahoastar」系列，信越化學工業股份有限公司販售「QSG」系列，可從此等之中使用平均粒徑適合者。 As long as the average particle size of the silica particles is suitable, any of them can be used, but spherical silica is preferred. The spherical shape does not cause aggregation, and the coating film is easily and efficiently filled with silicon dioxide fine particles. Spherical silica such as Admatechs Co., Ltd. sells the "Admafine" series, Sakai Chemical Industry Co., Ltd. sells the "sciqas" or "M SD" series, and Japan Catalysts Co., Ltd. sells the "Seahoastar" series. Shin-Etsu Chemical Co., Ltd. Industrial Co., Ltd. sells the "QSG" series, from which the average particle size can be used.
上述之無機微粒子可單獨使用，亦可混合2種類以上使用。無機微粒子在底塗層中的固體成分量相對於底塗之全固體成分量為10至60質量%，更適宜為30質量%以上。藉此，可獲得光澤性特別優異的金屬調性之塑膠形成品。 The above-mentioned inorganic fine particles may be used alone or as a mixture of two or more kinds. The solid content of the inorganic fine particles in the undercoat layer is 10 to 60% by mass, and more preferably 30% by mass or more, relative to the total solid content of the undercoat layer. Thereby, a metal-formed plastic-formed product having particularly excellent gloss can be obtained.
本發明之底塗層可使用硬化促進劑。硬化促進劑可使用Nagashima股份有限公司之胺基甲酸酯硬化促進劑；三精塗料工業股份有限公司之乾燥促進劑A；日東物產股份有限公司、San-Apro股份有限公司、日本化學產業股份有限公司、三菱化學股份有限公司等販售作為硬化促進劑之1,8-二偶氮雙環[5.4.0]十一碳烯-7及1,5-二偶 氮雙環[4.3.0]壬烯-5之酚鹽、油酸鹽、辛酸鹽等。硬化促進劑之含量相對於底塗層含有之黏結劑樹脂的固體成分量以1質量%以下為較佳。 The undercoat layer of the present invention may use a hardening accelerator. The hardening accelerator can use the urethane hardening accelerator of Nagashima Co., Ltd .; the drying accelerator A of Mitsumi Coating Industry Co., Ltd .; Nitto Sanko Co., Ltd., San-Apro Co., Ltd., and Japan Chemical Industry Co., Ltd. Company, Mitsubishi Chemical Corporation, etc. sell 1,8-diazobicyclo [5.4.0] undecene-7 and 1,5-diazobicyclo [4.3.0] nonene as hardening accelerators -5 phenate, oleate, caprylate, etc. The content of the hardening accelerator is preferably 1% by mass or less based on the solid content of the binder resin contained in the undercoat layer.
本發明之底塗層為改善表面之面質，可含有調平劑。調平劑係可從東振化學股份有限公司、DIC股份有限公司、BYK股份有限公司等取得聚矽氧系調平劑、氟系調平劑等加以利用。調平劑之使用量相對於底塗層含有之黏結劑樹脂固體成分量以0.001至1質量%為較佳，更佳為0.005至0.5質量%。此等調平劑若添加量過多，有與銀鍍覆層之接著變弱之傾向，太少時，有時無法充分獲得調平之效果。 The undercoat layer of the present invention may contain a leveling agent in order to improve the surface quality. Leveling agents can be obtained from Toshin Chemical Co., Ltd., DIC Co., Ltd., BYK Co., Ltd., etc. The use amount of the leveling agent is preferably 0.001 to 1% by mass, and more preferably 0.005 to 0.5% by mass, relative to the solid content of the binder resin contained in the undercoat layer. If the amount of these leveling agents is too large, the adhesion with the silver plating layer tends to be weak, and when it is too small, the leveling effect may not be sufficiently obtained in some cases.
在本發明中，於塑膠基材上設置底塗層之方法，一般係將上述之樹脂組成物等溶解於有機溶劑後塗布在塑膠基材上之方法。塗布方法係只要使用以往公知之塗布方法即可，例如凹版輥塗布、逆式輥塗布、浸漬輥塗布、桿塗佈器塗布、模缝塗佈器塗布、簾幕式塗佈器塗布、刮刀塗佈器塗布、噴氣式噴塗塗布、無氣噴塗塗布、浸漬塗布等。其中，以亦可塗佈於複雜表面形狀之無氣噴塗塗布為較佳。乾燥後之底塗層的膜厚以5至30μm為較佳，但無特別限定。 In the present invention, a method for providing an undercoat layer on a plastic substrate is generally a method of dissolving the above-mentioned resin composition and the like in an organic solvent and then coating the plastic substrate on the plastic substrate. The coating method may be any conventionally known coating method, such as gravure roll coating, reverse roll coating, dip roll coating, rod coater coating, die gap coater coating, curtain coater coating, and doctor blade coating. Cloth coating, air-jet spray coating, airless spray coating, dip coating, etc. Among them, airless spray coating which can also be applied to complex surface shapes is preferred. The film thickness of the undercoat layer after drying is preferably 5 to 30 μm, but it is not particularly limited.
形成底塗層時使用之有機溶劑可舉例如甲苯、二甲苯、環己烷、Solvesso 100(商品名、Exxon mobile Chemical公司製)等烴類；甲醇、乙醇、異丙醇、丁基醇等醇類；丁基溶纖劑、四氫呋喃、甲基溶纖劑乙酸酯等醚類； 乙酸乙酯、乙酸-正丁酯、乙酸異丁酯、異酪酸異丁酯等酯類；甲乙酮、甲基異丁基酮、環己酮等酮類，但不限定於此等。此等有機溶劑係依據用以設置底塗層所使用之樹脂組成物等的溶解性、以及從塗布面之面質改善的觀點適當選擇，可單獨使用亦可混合2種以上使用。 Examples of the organic solvent used in forming the undercoat layer include hydrocarbons such as toluene, xylene, cyclohexane, Solvesso 100 (trade name, manufactured by Exxon mobile Chemical); alcohols such as methanol, ethanol, isopropanol, and butyl alcohol Types; butyl cellosolve, tetrahydrofuran, methyl cellosolve acetate and other ethers; ethyl acetate, acetate-n-butyl acetate, isobutyl acetate, isobutyl isobutyrate and other esters; methyl ethyl ketone, methyl isobutyl Ketones such as ketones and cyclohexanone are not limited thereto. These organic solvents are appropriately selected depending on the solubility of the resin composition and the like used to provide the undercoat layer, and from the viewpoint of improving the surface quality of the coating surface, and they can be used alone or in combination of two or more.
為使塗布於塑膠基材上之底塗層樹脂組成物硬化，雖亦可在常溫使其自然乾燥，但以加熱促進硬化者為較佳。加熱溫度係以高者為較佳，但溫度太高時恐有基材變形之虞，故必須在基材不變形之溫度的範圍進行加熱。通常係在60至80℃進行20至120分鐘左右的加熱。 In order to harden the undercoat resin composition applied on the plastic substrate, although it can be allowed to dry naturally at normal temperature, it is preferable to use heating to promote hardening. The heating temperature is preferably higher, but if the temperature is too high, the substrate may be deformed. Therefore, it is necessary to heat the substrate in a temperature range in which the substrate is not deformed. It is usually heated at 60 to 80 ° C for about 20 to 120 minutes.
本發明之塑膠形成品係在設置於塑膠基材上之底塗層上具有無電解銀鍍覆層。形成無電解銀鍍覆層之較佳方法，係在形成無電解銀鍍覆層之底塗層的表面，以含有氯化亞錫之銀鏡用活性化處理液處理而使亞錫離子擔載於底塗層之表面，在經此活性化處理之底塗層上藉由銀鏡反應形成無電解銀鍍覆層之方法。 The plastic forming product of the present invention has an electroless silver plating layer on an undercoat layer provided on a plastic substrate. A preferred method for forming an electroless silver plating layer is to form a tin mirror containing stannous chloride on the surface of the undercoat layer forming the electroless silver plating layer with an activating treatment solution, so that stannous ions are carried on the surface. A method for forming an electroless silver plating layer on the surface of the undercoat layer by a silver mirror reaction on the activated undercoat layer.
含有氯化亞錫之銀鏡用活性化處理液，可舉例如日本特開2007-197743號公報、日本特開2006-274400號公報等記載之活性化處理液等。在底塗層之表面以含有氯化亞錫之銀鏡用活性化處理液處理之方法，有將底塗層之表面浸漬於銀鏡用活性化處理液中之方法、在底塗層之表面塗佈含有氯化亞錫等之銀鏡用活性化處理液之方法等。塗布方法係以不選擇基材形狀的噴塗塗布為特別適宜。更佳係將過剩附著於表面之活性化處理液 以去離子水或精製蒸餾水洗淨。 Examples of the activated treatment liquid for silver mirrors containing stannous chloride include those described in Japanese Patent Application Laid-Open No. 2007-197743 and Japanese Patent Application Laid-Open No. 2006-274400. The method of treating the surface of the undercoat layer with an activating treatment solution for silver mirrors containing stannous chloride includes a method of dipping the surface of the undercoat layer in an activating treatment solution for silver mirrors, and coating the surface of the undercoat layer. Method for activating treatment solution for silver mirror containing stannous chloride and the like. The coating method is particularly suitable for spray coating in which the shape of the substrate is not selected. More preferably, the excess activated treatment solution adhered to the surface is washed with deionized water or purified distilled water.
在以銀鏡用活性化處理液處理之步驟後，亦可設置以銀離子進行活性化處理之步驟。以銀離子進行活性化處理例如可例示使用含有硝酸銀之處理液的處理。在此步驟使用之硝酸銀水溶液的濃度以0.1mol/L以下的稀薄溶液為較佳，使此液接觸以氯化錫活性化處理後的底塗層。進行此銀離子處理時，在銀離子處理後預先以去離子水洗淨為較佳。在此等活性化處理中係以常供給新液之噴塗塗布為適宜。 After the step of treating the silver mirror with an activating treatment solution, a step of activating the treatment with silver ions may be provided. The activation treatment with silver ions is, for example, a treatment using a treatment solution containing silver nitrate. The concentration of the silver nitrate aqueous solution used in this step is preferably a dilute solution of 0.1 mol / L or less, and this solution is brought into contact with the undercoat layer after being activated with tin chloride. When performing this silver ion treatment, it is preferable to wash it with deionized water before the silver ion treatment. In these activation treatments, it is appropriate to apply spray coating, which is often supplied with a new liquid.
以銀鏡反應進行無電解銀鍍覆層之形成，係以在上述經活性化處理之底塗層表面上混合之方式塗布含有硝酸銀及氨之氨性硝酸銀溶液與含有還原劑及強鹼成分之還原劑溶液等2液。藉此，產生氧化還原反應而析出金屬銀形成銀被膜，成為無電解銀鍍覆層。 The formation of the electroless silver plating layer is performed by a silver mirror reaction, and the ammoniated silver nitrate solution containing silver nitrate and ammonia is coated in a mixed manner on the surface of the above-mentioned activated undercoat layer, and the reducing agent containing the reducing agent and the strong alkali component is reduced. Agent solution and 2 liquids. Thereby, a redox reaction occurs, metallic silver is deposited to form a silver film, and an electroless silver plating layer is formed.
前述還原劑溶液可舉例如葡萄糖、乙二醛等含有醛化合物之水溶液；硫酸聯胺、碳酸聯胺或聯胺水合物等含有聯胺化合物的水溶液；含有亞硫酸鈉或硫代硫酸鈉等之水溶液。 Examples of the reducing agent solution include aqueous solutions containing aldehyde compounds such as glucose and glyoxal; aqueous solutions containing hydrazine compounds such as hydrazine sulfate, hydrazine carbonate or hydrazine hydrate; and aqueous solutions containing sodium sulfite or sodium thiosulfate.
在氨性硝酸銀溶液中，為生成良好的銀亦可加入一些添加劑。例如，單乙醇胺、參(羥基甲基)胺基甲烷、2-胺基-2-羥基甲基-1,3-丙二醇、1-胺基-2-丙醇、2-胺基-1-丙醇、二乙醇胺、二異丙醇胺、三乙醇胺、三異丙醇胺等胺基醇化合物；甘氨酸、丙胺酸、甘氨酸鈉等胺基酸或其鹽等，但無特別限定。 In ammonia silver nitrate solution, some additives can also be added to produce good silver. For example, monoethanolamine, gins (hydroxymethyl) aminomethane, 2-amino-2-hydroxymethyl-1,3-propanediol, 1-amino-2-propanol, 2-amino-1-propane Amino alcohol compounds such as alcohol, diethanolamine, diisopropanolamine, triethanolamine, and triisopropanolamine; amino acids such as glycine, alanine, and sodium glycine, or salts thereof, are not particularly limited.
以在形成無電解銀鍍覆層之底塗層表面上混合的方式塗布前述氨性硝酸銀溶液與還原劑溶液等2液的方法，有預先混合2種溶液後使用噴塗槍等將此混合液噴附於底塗層表面之方法；使用在噴塗槍之頭內具有混合2種溶液後立即噴出之構造的同芯噴塗槍使其噴附之方法；從具有2個噴嘴之雙頭噴塗槍分別噴出2種溶液使其噴附之方法；使用2個各別噴塗槍而同時噴出2種溶液使其噴附之方法等。此等可依據狀況任意選擇。 The method of applying the two liquids such as the ammonia silver nitrate solution and the reducing agent solution in a mixed manner on the surface of the undercoat layer forming the electroless silver plating layer. There are two methods in which the mixed solution is sprayed with a spray gun or the like beforehand. Method for attaching to the surface of the undercoating layer; spraying method using the same core spray gun having a structure that sprays out two kinds of solutions immediately after mixing in the spray gun head; spraying from a double-head spray gun with two nozzles separately A method for spraying two kinds of solutions; a method for spraying two kinds of solutions simultaneously using two separate spray guns, and the like. These can be arbitrarily selected according to the situation.
繼而，使用去離子水或精製蒸留水水洗無電解銀鍍覆層之表面，除去殘留在其表面上之銀鏡反應後的溶液等為較佳。又，在無電解銀鍍覆層上設置前述上塗層之前，以使所析出之金屬銀安定化為目的，可進行在含有與銀具有反應或親和性之有機化合物的溶液中浸漬或塗佈該溶液等表面處理。 Next, it is preferable to wash the surface of the electroless silver plating layer with deionized water or purified distilled water, and remove the silver mirror reaction solution and the like remaining on the surface. In addition, before the above-mentioned coating layer is provided on the electroless silver plating layer, in order to stabilize the precipitated metallic silver, it is possible to perform immersion or coating in a solution containing an organic compound having a reaction or affinity with silver. This solution is surface-treated.
與銀具有反應或親和性之有機化合物，係可有效使用具有硫醇基或硫酮基之含氮雜環化合物。該含氮雜環化合物具有之雜環係有咪唑環、咪唑啉環、噻唑環、噻唑啉環、唑環、唑啉環、吡唑啉環、三唑環、噻二唑環、噻二唑環、四唑環、吡啶環、嘧啶環、嗒環、吡環、三環、喹啉環等，其中，以咪唑環、三唑環、四唑環為較佳。具體例係可舉例如2-氫硫基-4-苯基咪唑、2-氫硫基-1-苯甲基咪唑、2-氫硫基-苯并咪唑、1-乙基-2-氫硫基-苯并咪唑、2-氫硫基-1-丁基-苯并咪唑、1,3-二乙基-苯并咪唑啉-2-硫酮、1,3-二苯甲基-咪唑啶-2-硫酮、2-氫硫 基-4-苯基噻唑、2-氫硫基-苯并噻唑、2-氫硫基萘并噻唑、3-乙基-苯并噻唑啉-2-硫酮、3-十二碳基-苯并噻唑啉-2-硫酮、2-氫硫基-4,5-二苯基唑、2-氫硫基苯并唑、3-戊基-苯并唑啉-2-硫酮、1-苯基-3-甲基吡唑啉-5-硫酮、3-氫硫基-4-烯丙基-5-十五碳基-1,2,4-三唑、3-氫硫基-5-壬基-1,2,4-三唑、3-氫硫基-4-乙醯胺-5-庚基-1,2,4-三唑、3-氫硫基-4-胺基-5-十七碳基-1,2,4-三唑、2-氫硫基-5-苯基-1,3,4-噻二唑、2-氫硫基-5-正庚基-噻二唑、2-氫硫基-5-正庚基-二唑、2-氫硫基-5-苯基-1,3,4-二唑、5-氫硫基-1-苯基-四唑、2-氫硫基-5-硝基吡啶、1-甲基-喹啉-2(1H)-硫酮、3-氫硫基-4-甲基-6-苯基-嗒、2-氫硫基-5,6-二苯基-吡、2-氫硫基-4,6-二苯基-1,3,5-三、2-胺基-4-氫硫基-6-苯甲基-1,3,5-三、1,5-二氫硫基-3,7-二苯基-s-三唑啉基[1,2-a]-s-三唑啉等。 An organic compound having a reaction or affinity with silver is a nitrogen-containing heterocyclic compound having a thiol group or a thioketone group. The nitrogen-containing heterocyclic compound has an imidazole ring, an imidazoline ring, a thiazole ring, a thiazoline ring, Azole ring, Oxazoline ring, pyrazoline ring, triazole ring, thiadiazole ring, thiadiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, Ring, pyridine Ring, three Among the cyclic and quinoline rings, an imidazole ring, a triazole ring, and a tetrazole ring are preferred. Specific examples are, for example, 2-hydrothio-4-phenylimidazole, 2-hydrothio-1-benzylimidazole, 2-hydrothio-benzimidazole, 1-ethyl-2-hydrosulfide -Benzimidazole, 2-hydrothio-1-butyl-benzimidazole, 1,3-diethyl-benzimidazoline-2-thione, 1,3-benzyl-imidazolidine 2-thione, 2-hydrothio-4-phenylthiazole, 2-hydrothio-benzothiazole, 2-hydrothionaphthothiazole, 3-ethyl-benzothiazoline-2-sulfide Ketone, 3-dodecyl-benzothiazoline-2-thione, 2-hydrothio-4,5-diphenyl Azole, 2-hydrothiobenzo Azole, 3-pentyl-benzo Oxazoline-2-thione, 1-phenyl-3-methylpyrazolin-5-thione, 3-hydrothio-4-allyl-5-pentadecyl-1,2,4 -Triazole, 3-hydrothio-5-nonyl-1,2,4-triazole, 3-hydrothio-4-acetamidin-5-heptyl-1,2,4-triazole, 3-hydrothio-4-amino-5-heptadecanyl-1,2,4-triazole, 2-hydrothio-5-phenyl-1,3,4-thiadiazole, 2- Hydrogenthio-5-n-heptyl-thiadiazole, 2-hydrothio-5-n-heptyl- Diazole, 2-hydrothio-5-phenyl-1,3,4- Diazole, 5-hydrothio-1-phenyl-tetrazole, 2-hydrothio-5-nitropyridine, 1-methyl-quinoline-2 (1H) -thione, 3-hydrothio 4-methyl-6-phenyl-da , 2-hydrothio-5,6-diphenyl-pyridine , 2-hydrothio-4,6-diphenyl-1,3,5-tri , 2-amino-4-hydrothio-6-benzyl-1,3,5-tri , 1,5-dihydrothio-3,7-diphenyl-s-triazolinyl [1,2-a] -s-triazoline and the like.
本發明之塑膠成形品，係於無電解銀鍍覆層上具有含有胺基甲酸酯樹脂作為主成分之上塗層。在此含有所謂之胺基甲酸酯樹脂作為主成分，係意指胺基甲酸酯樹脂對上塗層之全固體成分之比例為60質量%以上，較佳為80質量%以上，更佳為95質量%以上。藉此，可以優異的塗裝作業性獲得耐久性優異的上塗層。 The plastic molded product of the present invention has an overcoat layer containing a urethane resin as a main component on the electroless silver plating layer. The inclusion of a so-called urethane resin as a main component herein means that the ratio of the urethane resin to the total solid content of the overcoat layer is 60% by mass or more, preferably 80% by mass or more, and more preferably 95% by mass or more. This makes it possible to obtain a coating having excellent durability with excellent coating workability.
上塗層含有之胺基甲酸酯樹脂，可舉例如醇酸多元醇、聚酯多元醇、丙烯酸多元醇、聚醚多元醇、聚碳酸酯多元醇、聚丁內酯多元醇等在末端具有羥基之聚合物或寡聚物；以及混合異氰酸酯化合物作為硬化劑所得 之胺基甲酸酯樹脂。其中，以混合丙烯酸多元醇與異氰酸酯化合物所得之胺基甲酸酯樹脂為較佳。藉此可獲得耐久性特別優異的上塗層。 The urethane resin contained in the overcoat layer may be, for example, alkyd polyol, polyester polyol, acrylic polyol, polyether polyol, polycarbonate polyol, polybutyrolactone polyol, etc. at the end. A polymer or oligomer of a hydroxyl group; and a urethane resin obtained by mixing an isocyanate compound as a hardener. Among them, a urethane resin obtained by mixing an acrylic polyol and an isocyanate compound is preferable. This makes it possible to obtain a top coat having particularly excellent durability.
使用作為硬化劑之異氰酸酯化合物，可使用縮脲型、三聚異氰酸酯型、加成型、二官能型之任一種聚異氰酸酯化合物。又以使用無黃變型之異氰酸酯化合物為較佳。 As the isocyanate compound used as a curing agent, any of a polyurea type, a trimeric isocyanate type, an addition molding, and a difunctional type can be used. It is also preferable to use a non-yellowing type isocyanate compound.
上述之胺基甲酸酯樹脂亦可利用購入之市售品。可使用市售之所謂2液胺基甲酸酯透明塗料作為本發明之胺基甲酸酯樹脂，在本發明中可較佳使用之丙烯酸多元醇與異氰酸酯化合物，前者例如由大橋化學工業股份有限公司販售之Polynal 800系列，後者例如由大橋化學工業股份有限公司販售之硬化劑DN-60，可購入此等後利用。 The above-mentioned urethane resin can also use a commercially available product. A commercially available so-called two-liquid urethane transparent coating can be used as the urethane resin of the present invention, and the acrylic polyol and isocyanate compound that can be preferably used in the present invention, the former is, for example, limited by Daqiao Chemical Industry The Polynal 800 series sold by the company, such as the hardener DN-60 sold by Daqiao Chemical Industry Co., Ltd., can be purchased and used later.
用以在無電解銀鍍覆層上設置上塗層之方法，一般有將上述之丙烯酸多元醇與異氰酸酯化合物溶解或稀釋在有機溶劑後塗佈於無電解銀鍍覆層上之方法。如此之有機溶劑，可使用與形成前述底塗層時使用之有機溶劑同種者。此等有機溶劑可依樹脂組成物之溶解性、以及從塗布面之面質改善等觀點適當選擇，雖可單獨使用，但較多為混合2種以上使用。用以設置上塗層所使用之樹脂組成物的塗布方法，只要使用以往公知之塗布方法即可，可舉例如凹版輥塗布、逆式輥塗布、浸漬輥塗布、桿塗佈器塗布、刮刀塗佈器塗布、噴氣式噴塗塗布、無氣噴塗塗布、浸漬塗布等。其中，以在複雜的表面形狀亦可塗佈之 無氣噴塗為較佳。 The method for providing an overcoat layer on the electroless silver plating layer generally includes a method of dissolving or diluting the above-mentioned acrylic polyol and isocyanate compound in an organic solvent and coating the electroless silver plating layer. As such an organic solvent, the same kind as the organic solvent used when forming the aforementioned undercoat layer can be used. These organic solvents can be appropriately selected depending on the solubility of the resin composition and the improvement of the surface quality of the coating surface, and although they can be used alone, they are often used in combination of two or more kinds. The coating method for setting the resin composition used for the overcoat layer may be a conventionally known coating method, and examples thereof include gravure roll coating, reverse roll coating, dip roll coating, rod coater coating, and blade coating. Cloth coating, air-jet spray coating, airless spray coating, dip coating, etc. Among them, airless spraying, which can also be applied to complex surface shapes, is preferred.
為了使塗佈在無電解銀鍍覆層上之上塗層樹脂組成物硬化，亦可在常溫進行自然乾燥，但以加熱促進硬化者為較佳。加熱溫度愈高愈佳，但溫度太高時基材有變形之虞，故必須在基材不變形之溫度範圍加熱。通常在60至80℃進行20至120分鐘左右的加熱。 In order to harden the coating resin composition applied on the electroless silver plating layer, it may be naturally dried at normal temperature, but it is preferable to use heating to promote hardening. The higher the heating temperature, the better, but the substrate may be deformed when the temperature is too high, so it must be heated in a temperature range where the substrate is not deformed. Heating is usually performed at 60 to 80 ° C for about 20 to 120 minutes.
上塗層之厚度以10至25μm之範圍為較佳。該層太薄時無法獲得保護無電解銀鍍覆層之角色的機能，又有時無法使其形成均勻的塗裝膜。反之，太厚時光之穿透距離變長、光之損失增加，故有時降低銀鍍覆層之反射率。 The thickness of the overcoat layer is preferably in a range of 10 to 25 μm. When the layer is too thin, the function of protecting the role of the electroless silver plating layer cannot be obtained, and sometimes it cannot form a uniform coating film. Conversely, when the thickness is too thick, the penetration distance of light becomes longer and the loss of light increases, so the reflectivity of the silver plating layer is sometimes reduced.
上塗層為了提高設計性，可含有顏料、染料等色材。顏料可舉例如碳黑、喹吖酮、萘酚紅、花青藍、花青綠、漢薩黃等有機顏料；氧化鈦、氧化鋁、碳酸鈣、硫酸鋇、雲母、氧化鐵紅、複合金屬氧化物等無機顏料，但不限定於此等。可將選自此等顏料之1種或2種以上組合使用。顏料為了獲得鮮明的發色以被分散為佳。顏料之分散方法並無特別限定，通常之方法可使用例如藉由臥式砂磨機(Dyno-mill)、塗料搖混機、砂磨機、球粒研磨機、捏合機、輥、溶解桿、均質機、超音波振動、攪拌子等使顏料粉直接分散之方法等。其時，可使用分散劑、分散助劑、增黏劑、偶合劑等。顏料之添加量因依顏料之種類而遮蔽性各異，故無特別限定，但通常相對於上塗層含有之樹脂成分的固體成分為0.1至5質量%。 The top coat may contain color materials such as pigments and dyes in order to improve design. Examples of the pigment include organic pigments such as carbon black, quinacridone, naphthol red, cyanine blue, cyanine green, and Hansa yellow; titanium oxide, aluminum oxide, calcium carbonate, barium sulfate, mica, iron oxide red, and composite metal oxidation But not limited to these. One kind or two or more kinds selected from these pigments can be used in combination. The pigment is preferably dispersed in order to obtain a clear hair color. The method for dispersing the pigment is not particularly limited. Generally, for example, a horizontal sand mill (Dyno-mill), a paint shaker, a sand mill, a pellet mill, a kneader, a roll, a dissolving rod, Homogenizer, ultrasonic vibration, stirrer and other methods to directly disperse pigment powder. In this case, a dispersant, a dispersing assistant, a tackifier, a coupling agent, and the like can be used. The addition amount of the pigment is not particularly limited because it has different shielding properties depending on the type of the pigment, but it is usually 0.1 to 5% by mass based on the solid content of the resin component contained in the overcoat layer.
染料可舉例如偶氮系、蒽醌系、靛類物系、硫化物系、三苯基甲烷系、二苯并吡喃系、茜素系、吖啶系、醌亞胺系、噻唑系、次甲基系、硝基系、亞硝基系等染料，但不限定於此等。可自此等染料選擇1種或組合2種以上使用。染料之添加量因係依染料之種類而遮蔽性各異，故無特別限定，但通常相對於上塗層含有之樹脂成分的固體成分為0.1至5質量%。 Examples of the dye include azo-based, anthraquinone-based, indigo-based, sulfide-based, triphenylmethane-based, dibenzopyran-based, alizarin-based, acridine-based, quinimine-based, thiazole-based, The dyes such as methine-based, nitro-based, and nitroso-based are not limited thereto. These dyes can be used singly or in combination of two or more kinds. The amount of the dye added is not particularly limited because it has different shielding properties depending on the type of dye, but it is usually 0.1 to 5% by mass based on the solid content of the resin component contained in the top coat.
在上塗層可進一步含有調平劑、金屬粉、玻璃粉、抗菌劑、抗氧化劑、紫外線吸收劑、光安定化劑等作為添加劑。又，為提升上塗層與無電解銀鍍覆層之密著性，可含有日本特開2012-206326號公報或日本特開2014-65268號公報記載之硫醇類、矽烷偶合劑等化合物。 The top coating layer may further contain a leveling agent, metal powder, glass powder, antibacterial agent, antioxidant, ultraviolet absorber, light stabilizer, and the like as additives. In addition, in order to improve the adhesion between the top coat and the electroless silver plating layer, compounds such as thiols and silane coupling agents described in Japanese Patent Application Laid-Open No. 2012-206326 or Japanese Patent Application Laid-Open No. 2014-65268 may be contained.
本發明之塑膠成形品的塑膠基材，可舉例如聚碳酸酯樹脂、丙烯酸樹脂、ABS樹脂、氯乙烯樹脂、環氧樹脂、酚樹脂、聚對苯二甲酸乙二酯(PET)樹脂或聚對苯二甲酸丁二酯(PBT)樹脂等聚酯樹脂、氟樹脂、聚丙烯(PP)樹脂、及將此等複合化而成之樹脂、以及玻璃纖維或碳纖維等無機纖維及尼龍纖維或紙漿纖維等有機纖維強化而成的纖維強化塑膠(FRP)等。塑膠基材較佳係具有可保持形狀之程度的厚度。塑膠基材之厚度若太薄，有時不僅無法保持形狀而且光澤降低，故雖亦需依其材質而定，但以0.5mm以上為較佳。 Examples of the plastic substrate of the plastic molded article of the present invention include polycarbonate resin, acrylic resin, ABS resin, vinyl chloride resin, epoxy resin, phenol resin, polyethylene terephthalate (PET) resin, or poly (ethylene terephthalate) resin. Polyester resins such as butylene terephthalate (PBT) resins, fluororesins, polypropylene (PP) resins, and resins compounded from these, and inorganic fibers such as glass fibers or carbon fibers, and nylon fibers or pulp Fiber-reinforced plastic (FRP) and the like reinforced with organic fibers such as fibers. The plastic substrate preferably has a thickness to such an extent that the shape can be maintained. If the thickness of the plastic substrate is too thin, sometimes it can not only maintain the shape but also reduce the gloss. Although it depends on its material, it is better to be 0.5mm or more.
本發明之塑膠成形品在塑膠基材上具有底塗層，但有時依據塑膠基材之種類而底塗層與塑膠基材之 接著不充分。如此之情形，為了提高塑膠基材與底塗層密著性之目的，亦可對塑膠基材施予前處理。前處理法可舉例如以清潔劑、溶劑、超音波等之洗淨處理等濕式處理、電暈處理或紫外線照射、電子線照射處理等乾式處理。又，依據塑膠基材之材質，例如在聚丙烯中為了改善接著性，亦可將底漆層設於塑膠基材與底塗層之間。 The plastic molded product of the present invention has an undercoat layer on a plastic substrate, but sometimes the adhesion between the undercoat layer and the plastic substrate is insufficient depending on the type of the plastic substrate. In this case, in order to improve the adhesion between the plastic substrate and the undercoating layer, a pretreatment may be applied to the plastic substrate. The pre-treatment method may include, for example, a wet process such as a cleaning process using a cleaning agent, a solvent, or an ultrasonic wave, a corona process, or a dry process such as ultraviolet irradiation or electron beam irradiation. In addition, according to the material of the plastic substrate, for example, in polypropylene, in order to improve adhesion, a primer layer may be provided between the plastic substrate and the primer layer.
以下，使用實施例說明本發明，但本發明不受此等記載之限定。 Hereinafter, the present invention will be described using examples, but the present invention is not limited by these descriptions.
在丙烯酸多元醇(大橋化學工業股份有限公司製Mirror shine透明底塗D-1)中分別以質量比5對1對5之比例混合異氰酸酯化合物(大橋化學工業股份有限公司製Mirror Shine底塗用硬化劑-N)及有機溶劑(將甲乙酮及環己酮以質量比1對1之比例混合而成者)。進一步在此混合液中相對於丙烯酸多元醇之固體成分添加調平劑(BYK股份有限公司製BYK-323)0.05質量%，獲得底塗層用之胺基甲酸酯樹脂塗料組成物。對以異丙醇洗淨表面並乾燥後之厚度1mm的ABS樹脂板，以噴塗槍塗布此塗料組成物之後，在70℃下加熱乾燥1小時，在ABS樹脂板表面形成厚度20μm之底塗層。 An isocyanate compound (Mirror Shine undercoat made by Ohashi Chemical Industry Co., Ltd.) is mixed with acrylic polyol (Mirror shine transparent primer D-1 manufactured by Ohashi Chemical Industry Co., Ltd.) in a mass ratio of 5 to 1 to 5. Agent-N) and an organic solvent (a mixture of methyl ethyl ketone and cyclohexanone in a mass ratio of 1: 1). A leveling agent (BYK-323 manufactured by BYK Co., Ltd.) was added at 0.05 mass% to the solid content of the acrylic polyol in this mixed solution to obtain a urethane resin coating composition for an undercoat layer. After the surface was washed with isopropyl alcohol and dried to a thickness of 1 mm, the coating composition was applied with a spray gun, and then dried at 70 ° C for 1 hour to form a primer layer having a thickness of 20 μm on the surface of the ABS resin plate. .
銀鏡用活性化處理液係將0.1莫耳之鹽酸及0.1莫耳之氯化亞錫添加於去離子水並使全體量成為 1000g，將此液以噴塗槍噴附在底塗層面進行活性化處理，然後以去離子水洗淨。繼而，將0.05莫耳之硝酸銀溶解於去離子水並使全體量成為1000g，將此液以噴塗槍噴附在底塗層面藉由銀離子進行活性化處理，然後以去離子水洗淨底塗層面。 0.1 mol of hydrochloric acid and 0.1 mol of stannous chloride are added to deionized water to make the total amount 1000 g, and this solution is sprayed on the surface of the undercoating layer with a spray gun to activate it. Treat and rinse with deionized water. Next, 0.05 mol of silver nitrate was dissolved in deionized water to make the total amount 1000 g. This solution was sprayed on the surface of the undercoating layer with a spray gun to perform activation treatment with silver ions, and then the bottom was washed with deionized water. Coated surface.
使用於銀鏡鍍覆之各種溶液係依如下之方式調製。調製使硝酸銀20g溶解於去離子水並使全體量成為1000g之硝酸銀溶液。調製在去離子水中添加濃度28質量%之氨水溶液100g後再溶解單乙醇胺5g並使全體量成為1000g之氨溶液。使用於銀鏡鍍覆之前，將此硝酸銀溶液與氨溶液以質量比1對1混合製成氨性硝酸銀溶液。其次，調製於去離子水中溶解硫酸聯胺10g、單乙醇胺5g及氫氧化鈉10g並使全體量成為1000g而成之還原劑溶液。 Various solutions used for silver mirror plating are prepared as follows. A silver nitrate solution was prepared by dissolving 20 g of silver nitrate in deionized water so that the total amount became 1,000 g. An ammonia solution having a concentration of 28% by mass in an aqueous ammonia solution of 28% by mass was added to deionized water, and then 5 g of monoethanolamine was dissolved, so that the entire amount became 1,000 g of an ammonia solution. Before using for silver mirror plating, this silver nitrate solution and ammonia solution are mixed at a mass ratio of 1: 1 to prepare an ammoniacal silver nitrate solution. Next, a reducing agent solution prepared by dissolving 10 g of hydrazine sulfate, 5 g of monoethanolamine, and 10 g of sodium hydroxide in deionized water and preparing an entire amount of 1,000 g was prepared.
將如此方式所得之氨性硝酸銀溶液與還原劑溶液，使用雙頭噴塗槍同時噴附於經銀離子進行活性化處理之底塗層面，藉銀鏡反應形成無電解銀鍍覆層。將無電解銀鍍覆層表面以去離子水洗淨，充分除去表面之水之後，在45℃下乾燥30分鐘。 The ammonia silver nitrate solution and the reducing agent solution obtained in this way were simultaneously sprayed on the surface of the undercoat layer subjected to activation treatment with silver ions using a double-head spray gun to form an electroless silver plating layer by a silver mirror reaction. The surface of the electroless silver plating layer was washed with deionized water, the surface water was sufficiently removed, and then dried at 45 ° C for 30 minutes.
進一步在銀鍍覆層上設置上塗層。在丙烯酸多元醇(大橋化學工業股份有限公司製Polynal 800(N))中將異氰酸酯化合物(大橋化學工業股份有限公司製硬化劑DN-60)與有機溶劑(大橋化學工業股份有限公司製Thinner No.6400)以質量比8對1對8之比例混合製成上塗層用之胺基甲酸酯樹脂塗料組成物，以噴塗槍塗佈於銀鍍 覆層面。在70℃加熱乾燥1小時後形成厚度15μm之上塗層。依此方式獲得ABS樹脂板表面被加飾成金屬調性之塑膠成形品。 Further, an overcoat layer is provided on the silver plating layer. In an acrylic polyol (Polynal 800 (N) manufactured by Ohashi Chemical Industry Co., Ltd.), an isocyanate compound (hardener DN-60 manufactured by Ohashi Chemical Industry Co., Ltd.) and an organic solvent (Thinner No. 6400) The urethane resin coating composition for the overcoat layer is mixed at a mass ratio of 8 to 1 to 8 and applied to the silver plating layer with a spray gun. After heating and drying at 70 ° C. for 1 hour, a 15 μm-thick top coat was formed. In this way, the surface of the ABS resin plate is decorated with a metal-toned plastic molded product.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為20質量%之方式含有球狀二氧化矽粒子(Admatechs股份有限公司製Admafine SC1050、平均粒徑250nm)以外，其餘係與比較例1同樣方式，獲得實施例1之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained spherical silica particles (except for the total solid content of the undercoat layer so that the solid content of the silica particles was 20% by mass). Except for Admafine SC1050 manufactured by Admatechs Co., Ltd. (average particle diameter: 250 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tones in Example 1 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為40質量%之方式含有球狀二氧化矽粒子(Admatechs股份有限公司製Admafine SC1050、平均粒徑250nm)以外，其餘係與比較例1同樣方式，獲得實施例2之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained spherical silica particles in a manner such that the solid content of the silica particles was 40% by mass relative to the total solid content of the undercoat layer ( Except for Admafine SC1050 manufactured by Admatechs Co., Ltd. (average particle size: 250 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tones in Example 2 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為50質量%之方式含有球狀二氧化矽粒子(Admatechs股 份有限公司製Admafine SC1050、平均粒徑250nm)以外，其餘係與比較例1同樣方式，獲得實施例3之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained spherical silica particles in addition to the total solid content of the undercoat layer such that the solid content of the silica particles was 50% by mass ( Except for Admafine SC1050 manufactured by Admatechs Co., Ltd. (average particle size: 250 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tones in Example 3 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為40質量%之方式含有球狀二氧化矽粒子(信越化學工業股份有限公司製QSG-100、平均粒徑110nm)以外，其餘係與比較例1同樣方式，獲得實施例4之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained spherical silica particles in a manner such that the solid content of the silica particles was 40% by mass relative to the total solid content of the undercoat layer ( Except for QSG-100 manufactured by Shin-Etsu Chemical Industry Co., Ltd. (average particle size: 110 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tones in Example 4 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為40質量%之方式含有球狀二氧化矽粒子(Admatechs股份有限公司製Admafine SC2050、平均粒徑500nm)以外，其餘係與比較例1同樣方式，獲得實施例5之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained spherical silica particles in a manner such that the solid content of the silica particles was 40% by mass relative to the total solid content of the undercoat layer ( Except for Admafine SC2050 manufactured by Admatechs Co., Ltd. (average particle diameter: 500 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tone in Example 5 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為40質量%之方式含有金紅石型二酸化鈦粒子(堺化學工 業股份有限公司製R-21、平均粒徑200nm)以外，其餘係與比較例1同樣方式，獲得實施例6之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained rutile-type titanium diacid particles so that the solid content of the silica particles was 40% by mass relative to the total solid content of the undercoat layer ( Except for R-21 manufactured by Sakai Chemical Industry Co., Ltd. (average particle diameter: 200 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tones in Example 6 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為40質量%之方式含有金紅石型二酸化鈦粒子(堺化學工業股份有限公司製R-62N、平均粒徑260nm)以外，其餘係與比較例1同樣方式，獲得實施例7之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained rutile-type titanium diacid particles so that the solid content of the silica particles was 40% by mass relative to the total solid content of the undercoat layer ( Except for R-62N (manufactured by Sakai Chemical Industry Co., Ltd., with an average particle diameter of 260 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tones in Example 7 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使硫酸鋇粒子之固體成分量成為40質量%之方式含有沈降性硫酸鋇粒子(堺化學工業股份有限公司製Bariace B-34、平均粒徑300nm)以外，其餘係與比較例1同樣方式，獲得實施例8之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained sedimentary barium sulfate particles (堺 Chemicals) so that the solid content of the barium sulfate particles was 40% by mass relative to the total solid content of the undercoat layer. Except for Bariace B-34 manufactured by Industrial Co., Ltd. (average particle diameter: 300 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tone in Example 8 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為70質量%之方式含有球狀二氧化矽粒子(Admatechs股 份有限公司製Admafine SC1050、平均粒徑250nm)以外，其餘係與比較例1同樣方式，獲得比較例2之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained spherical silica particles in addition to the total solid content of the undercoat layer so that the solid content of the silica particles became 70% by mass ( Except for Admafine SC1050 manufactured by Admatechs Co., Ltd. (average particle size: 250 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tone in Comparative Example 2 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為40質量%之方式含有二氧化矽粒子(日產化學工業股份有限公司製Organo二氧化矽溶膠EAC-ST、平均粒徑15nm)以外，其餘係與比較例1同樣方式，獲得比較例3之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained silicon dioxide particles so that the solid content of the silica particles was 40% by mass relative to the total solid content of the undercoat layer (Nissan Chemical Except for Organo Silica Sol EAC-ST (average particle diameter: 15 nm) manufactured by Industrial Co., Ltd., the rest was the same as in Comparative Example 1, and a plastic molded article decorated with metal tone in Comparative Example 3 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為40質量%之方式含有二氧化矽粒子(日產化學工業股份有限公司製Organo二氧化矽溶膠MEK-AC5140Z、平均粒徑90nm)以外，其餘係與比較例1同樣方式，獲得比較例4之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained silicon dioxide particles so that the solid content of the silica particles was 40% by mass relative to the total solid content of the undercoat layer (Nissan Chemical Except for Organo Silica Sol MEK-AC5140Z (average particle size: 90 nm) manufactured by Industrial Co., Ltd., the rest were the same as Comparative Example 1, and a plastic molded article decorated with metal tone in Comparative Example 4 was obtained.
在比較例1之底塗層用的塗料組成物中，除了相對於底塗層之全固體成分量以使二氧化矽粒子之固體成分量成為40質量%之方式含有球狀二氧化矽粒子(Admatechs股 份有限公司製SC4050、平均粒徑1100nm)以外，其餘係與比較例1同樣方式，獲得比較例5之被加飾成金屬調性之塑膠成形品。 The coating composition for the undercoat layer of Comparative Example 1 contained spherical silica particles in a manner such that the solid content of the silica particles was 40% by mass relative to the total solid content of the undercoat layer ( Except for SC4050 manufactured by Admatechs Co., Ltd. (average particle size: 1100 nm), the rest were the same as in Comparative Example 1, and a plastic molded article decorated with metal tone in Comparative Example 5 was obtained.
以目視判断所得之金屬調塑膠成形品的外觀優劣。在水平面上設置金屬調塑膠成形品，使具有銀鍍覆層之側的面向上，在具有銀鍍覆層之側的面使其反射從水平面以相對於上方為30度之角度發出的螢光燈光源，以目視觀察螢光燈之反射像及其周圍形成之白色或虹色之環，從彼等之觀察情形依據如下之基準評估光澤性。◎及○為可承受實際使用之良好結果。 The appearance of the obtained metal-plastic molded product was judged visually. A metal-plastic molded article is provided on a horizontal surface so that the side with the silver plating layer faces upward, and the surface with the silver plating layer reflects the fluorescent light emitted from the horizontal plane at an angle of 30 degrees from the top The lamp light source is used to visually observe the reflection image of the fluorescent lamp and the white or iridescent ring formed around it. From their observations, the gloss is evaluated based on the following criteria. ◎ and ○ are good results that can withstand actual use.
◎：可鮮明地看到螢光燈之反射像，在其周圍未看到白色或虹色之環而光澤性良好。 ：: The reflection image of the fluorescent lamp can be clearly seen, and no white or iridescent ring is seen around it, and the gloss is good.
○：可鮮明地看到螢光燈之反射像，在其周圍僅稍微看到白色或虹色之環，在實際使用上具有充分的光澤性。 ○: The reflection image of the fluorescent lamp can be clearly seen, and only a white or iridescent ring is seen around it, and it has sufficient glossiness in practical use.
△：可鮮明地看到螢光燈之反射像，在其周圍清楚可見白色或虹色之環。 △: The reflection image of the fluorescent lamp can be clearly seen, and a white or iridescent ring can be clearly seen around it.
×：螢光燈之反射像模糊或混濁。 ×: The reflection image of the fluorescent lamp is blurred or cloudy.
有關所得之金屬調塑膠成形品，使用促進耐候性試驗機(Suga試驗機股份有限公司製、Xeon Weather meter NX25 型)，在300至400nm光之照射強度60W/m2、黑色面板溫度63℃、相對濕度50%、槽內溫度38℃、60分鐘內包含降雨12分鐘之條件進行1000小時之耐候劣化試驗，從彼等光澤度之值依據如下之基準評估耐久性。又，光澤度係使用光澤度測定裝置(村上色彩技術研究所股份有限公司製、GM-26PRO)測定所得之金屬調性塑膠成形品具有銀鍍覆層之側的面之20度鏡面光澤度(依據JIS K5600-4-7)。 The obtained metal-plastic molded product was subjected to a weather resistance tester (manufactured by Suga Tester Co., Ltd., Xeon Weather meter NX25), and the irradiation intensity of light at 300 to 400 nm was 60 W / m 2 , the temperature of the black panel was 63 ° C, A weather resistance test was performed for 1000 hours under conditions of 50% relative humidity, 38 ° C in the tank temperature, and 12 minutes of rain within 60 minutes, and durability was evaluated from their gloss values according to the following criteria. In addition, the gloss is 20-degree specular gloss on the side of the metal-toned plastic molded product having a silver plating layer measured using a gloss measuring device (manufactured by Murakami Color Technology Research Institute Co., Ltd., GM-26PRO) ( (According to JIS K5600-4-7).
○為可承受實際使用之良好結果。 ○ is a good result that can withstand actual use.
○：試驗後之光澤度的值為試驗前之光澤度的值之90%以上。 ○: The gloss value after the test is 90% or more of the gloss value before the test.
△：試驗後之光澤度的值低於試驗前之光澤度的值之90%但為80%以上。 △: The gloss value after the test is lower than 90% but 80% or more of the gloss value before the test.
×：試驗後之光澤度的值低於試驗前之光澤度的值之80%。 ×: The gloss value after the test was lower than 80% of the gloss value before the test.
將上述評估試驗之結果表示於表1中。 The results of the above evaluation tests are shown in Table 1.
從表1明顯可知，依據本發明，可提供藉由銀鍍覆而具有高光澤性且具有充分耐久性之被加飾成金屬調性之塑膠成形品。特別是在實施例2、3、5、6、7、8，因底塗層含有相對於底塗層之全固體成分量以固體成分量計為30質量%以上之平均粒徑為155nm以上之無機微粒子，故具有極高光澤性。 It is clear from Table 1 that according to the present invention, a plastic molded article decorated with metal tones having high gloss and sufficient durability by silver plating can be provided. In particular, in Examples 2, 3, 5, 6, 7, and 8, the undercoat layer contained an average particle diameter of 155 nm or more based on the total solid content of the undercoat layer in terms of solid content of 30% by mass or more. Inorganic fine particles have extremely high gloss.
但是比較例1因底塗層不含有無機微粒子，故光澤性低。比較例2因底塗層之無機微粒子含量過多，故光澤性極低之外，耐久性亦低。又，比較例3係因底塗層含有之無機微粒子的平均粒徑太小，故光澤性極低之外，耐久性亦低。比較例4係因底塗層含有之無機微粒子的平均粒徑小，故光澤性低。比較例5因底塗層含有之無機微粒子的平均粒徑過大，故光澤性極低。 However, Comparative Example 1 has low gloss because the undercoat layer does not contain inorganic fine particles. In Comparative Example 2, since the content of the inorganic fine particles in the undercoat layer was excessive, the gloss was extremely low and the durability was also low. In Comparative Example 3, since the average particle diameter of the inorganic fine particles contained in the undercoat layer was too small, the gloss was extremely low and the durability was also low. In Comparative Example 4, the average particle diameter of the inorganic fine particles contained in the undercoat layer was small, and thus the gloss was low. In Comparative Example 5, since the average particle diameter of the inorganic fine particles contained in the undercoat layer was too large, the gloss was extremely low.
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| CN110777385A (en) * | 2019-11-12 | 2020-02-11 | 上海志行合力网络技术有限公司 | Preparation method of primary-color silver |
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| JP2007023087A (en) | 2005-07-13 | 2007-02-01 | Arakawa Chem Ind Co Ltd | Primer resin for silver mirror plating and primer composition for silver mirror plating containing the resin |
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