CN104619783B - 热塑性树脂组合物、树脂成型品和带镀层的树脂成型品的制造方法 - Google Patents
热塑性树脂组合物、树脂成型品和带镀层的树脂成型品的制造方法 Download PDFInfo
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- CN104619783B CN104619783B CN201380043368.XA CN201380043368A CN104619783B CN 104619783 B CN104619783 B CN 104619783B CN 201380043368 A CN201380043368 A CN 201380043368A CN 104619783 B CN104619783 B CN 104619783B
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 230000001404 mediated effect Effects 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
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- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
- UTGPYHWDXYRYGT-UHFFFAOYSA-N tetratriacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTGPYHWDXYRYGT-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- KNXVOGGZOFOROK-UHFFFAOYSA-N trimagnesium;dioxido(oxo)silane;hydroxy-oxido-oxosilane Chemical compound [Mg+2].[Mg+2].[Mg+2].O[Si]([O-])=O.O[Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O KNXVOGGZOFOROK-UHFFFAOYSA-N 0.000 description 1
- NLSFXUALGZKXNV-UHFFFAOYSA-N trimethoxy(3-propoxypropyl)silane Chemical compound CCCOCCC[Si](OC)(OC)OC NLSFXUALGZKXNV-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
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Abstract
本发明提供能够以宽泛的激光照射条件在树脂成型品的表面适当地形成镀层的热塑性树脂组合物。一种热塑性树脂组合物,其包含热塑性树脂、相对于热塑性树脂100重量份为1~30重量份的激光直接成型添加剂以及0.1~10重量份的激光标记用添加剂,激光直接成型添加剂包含70重量%以上的氧化锡。
Description
技术领域
本发明涉及热塑性树脂组合物。进而,涉及将该热塑性树脂组合物成型而成的树脂成型品以及在该树脂成型品的表面形成有镀层的带镀层的树脂成型品的制造方法。
背景技术
近年来,随着包括智能手机在内的移动电话的开发,正在研究各种在移动电话的内部制造天线的方法。尤其是,对于移动电话而言,要求制造能够进行三维设计的天线的方法。作为形成这样的三维天线的技术之一,激光直接成型(以下,有时称为“LDS”)技术受到瞩目。LDS技术为下述技术:例如,对包含LDS添加剂的树脂成型品的表面照射激光,仅使照射了激光的部分活化,并对该活化的部分适用金属,由此形成镀层。该技术的特征在于不使用粘接剂等而能够在树脂基材表面直接制造天线等金属结构体。该LDS技术例如公开于专利文献1~3等。
现有技术文献
专利文献
专利文献1:日本特表2000-503817号公报
专利文献2:日本特表2004-534408号公报
专利文献3:国际公开WO2009/141800号小册子
发明内容
发明要解决的问题
然而,即使在将热塑性树脂组合物成型而成的树脂成型品的表面形成镀层的情况下,也要求生产率的提高。即,要求以宽泛的激光照射条件适当地形成镀层。
本发明的目的在于解决所述现有技术的问题点,其目的在于,提供能够以宽泛的激光照射条件在树脂成型品的表面适当地形成镀层的热塑性树脂组合物。
用于解决问题的方案
基于所述状况,本发明人进行了深入研究,结果发现:对于热塑性树脂而言,通过向热塑性树脂中配混包含70重量%以上氧化锡的LDS添加剂和激光标记用添加剂,能够解决上述课题,从而完成了本发明。具体而言,通过以下的手段<1>、优选通过<2>~<14>来解决上述课题。
<1>一种热塑性树脂组合物,其包含热塑性树脂、相对于该热塑性树脂100重量份为1~30重量份的激光直接成型添加剂以及0.1~10重量份的激光标记用添加剂,前述激光直接成型添加剂包含70重量%以上的氧化锡。
<2>根据<1>所述的热塑性树脂组合物,其中,相对于前述热塑性树脂100重量份,包含10~200重量份的无机纤维。
<3>根据<2>所述的热塑性树脂组合物,其中,前述无机纤维为玻璃纤维。
<4>根据<1>~<3>中任一项所述的热塑性树脂组合物,其中,前述激光标记用添加剂含有选自包含铜和钼的氧化物、或者、包含铋和镓和/或钕的氧化物中的至少1种。
<5>根据<4>所述的热塑性树脂组合物,其中,前述激光标记用添加剂为包含铜和钼的氧化物。
<6>根据<1>~<4>中任一项所述的热塑性树脂组合物,其中,前述热塑性树脂为聚酰胺树脂。
<7>根据<1>~<6>中任一项所述的热塑性树脂组合物,其中,前述激光直接成型添加剂含有选自包含锑和锡的氧化物、以及、包含铝和锌的氧化物中的至少1种。
<8>一种树脂成型品,其是将<1>~<7>中任一项所述的热塑性树脂组合物成型而成的。
<9>根据<8>所述的树脂成型品,其在表面具有镀层。
<10>根据<8>或<9>所述的树脂成型品,其为便携式电子设备部件。
<11>根据<9>或<10>所述的树脂成型品,其中,前述镀层具有作为天线的性能。
<12>一种带镀层的树脂成型品的制造方法,其包括:对将<1>~<7>中任一项所述的热塑性树脂组合物成型而成的树脂成型品的表面照射激光后,利用金属形成镀层。
<13>根据<12>所述的带镀层的树脂成型品的制造方法,其中,前述镀层为铜镀层。
<14>一种具有天线的便携式电子设备部件的制造方法,其包括<12>或<13>所述的具有镀层的树脂成型品的制造方法。
发明的效果
根据本发明,可提供能够以宽泛的激光照射条件在树脂成型品的表面适当地形成镀层的热塑性树脂组合物。因此,能够提高在将本发明中得到的热塑性树脂组合物成型而成的树脂成型品的表面形成镀层时的生产率。
附图说明
图1是示出在树脂成型品的表面设置镀层的工序的示意图。
具体实施方式
以下,对本发明的内容进行详细说明。需要说明的是,本申请说明书中,“~”是以包含其前后所记载的数值作为下限值和上限值的含义使用。
<热塑性树脂组合物>
本发明的热塑性树脂组合物的特征在于,其包含热塑性树脂、相对于热塑性树脂100重量份为1~30重量份的LDS添加剂以及0.1~10重量份的激光标记用添加剂,LDS添加剂包含70重量%以上的氧化锡。
<热塑性树脂>
本发明的热塑性树脂组合物包含热塑性树脂。热塑性树脂的种类没有特别限定,例如可列举出聚碳酸酯树脂、聚苯醚树脂与聚苯乙烯系树脂的合金、聚苯醚树脂与聚酰胺树脂的合金、热塑性聚酯树脂、甲基丙烯酸甲酯/丙烯腈/丁二烯/苯乙烯共聚树脂、甲基丙烯酸甲酯/苯乙烯共聚树脂、甲基丙烯酸甲酯树脂、橡胶强化甲基丙烯酸甲酯树脂、聚酰胺树脂、聚缩醛树脂、聚乳酸系树脂、聚烯烃树脂等。
本发明中,优选使用聚酰胺树脂、热塑性聚酯树脂,进一步优选为聚酰胺树脂。热塑性树脂可以仅使用一种,也可以组合使用两种以上。
聚酰胺树脂是在其分子中具有酰胺基(-CONH-)且能够加热熔融的聚酰胺聚合物。具体而言,为内酰胺的缩聚物、二胺化合物与二羧酸化合物的缩聚物、ω-氨基羧酸的缩聚物等各种聚酰胺树脂;或者它们的共聚聚酰胺树脂、共混物等。
作为聚酰胺树脂的缩聚原料即内酰胺,例如可列举出ε-己内酰胺、ω-十一内酰胺等。
作为二胺化合物,例如可列举出四亚甲基二胺、六亚甲基二胺、十一亚甲基二胺、十二亚甲基二胺、2-甲基五亚甲基二胺、(2,2,4-或2,4,4-)三甲基六亚甲基二胺、5-甲基九亚甲基二胺、间苯二甲胺(MXDA)、对苯二甲胺、1,3-双(氨基甲基)环己烷、1,4-双(氨基甲基)环己烷、1-氨基-3-氨基甲基-3,5,5-三甲基环己烷、双(4-氨基环己基)甲烷、双(3-甲基-4-氨基环己基)甲烷、2,2-双(4-氨基环己基)丙烷、双(氨基丙基)哌嗪、氨基乙基哌嗪等脂肪族、脂环式、芳香族的二胺等。
作为二羧酸化合物,例如可列举出己二酸、辛二酸、壬二酸、癸二酸、十二烷二酸、对苯二甲酸、间苯二甲酸、2-氯代对苯二甲酸、2-甲基对苯二甲酸、5-甲基间苯二甲酸、间苯二甲酸-5-磺酸钠、六氢对苯二甲酸、六氢间苯二甲酸等脂肪族、脂环式、芳香族的二羧酸等。
作为ω-氨基羧酸,例如可列举出6-氨基己酸、11-氨基十一烷酸、12-氨基十二烷酸、对氨基甲基苯甲酸等氨基酸。
作为由这些原料缩聚而成的聚酰胺树脂的具体例,可列举出聚酰胺4、聚酰胺6、聚酰胺11、聚酰胺12、聚酰胺46、聚酰胺66、聚酰胺610、聚酰胺612、聚对苯二甲酰己二胺(聚酰胺6T)、聚间苯二甲酰己二胺(聚酰胺6I)、聚己二酰间苯二甲胺(聚酰胺MXD6)、聚十二酰间苯二甲胺、聚酰胺9T、聚酰胺9MT等。本发明中,可以分别单独使用或者以混合物的形式使用这些聚酰胺均聚物或共聚物。
在上述那样的聚酰胺树脂之中,从成型性、耐热性的观点出发,更优选使用聚酰胺6、聚酰胺66、或者由α,ω-直链脂肪族二元酸与苯二甲胺缩聚得到的苯二甲胺系聚酰胺树脂(MX尼龙)。这些之中,从耐热性、阻燃性的观点出发,进一步优选为MX尼龙。另外,聚酰胺树脂为混合物时,聚酰胺树脂中的MX尼龙的比率优选为50重量%以上,更优选为80重量%以上。
MX尼龙与聚酰胺66、聚酰胺6、聚酰胺46、聚酰胺9T等脂肪族系聚酰胺树脂相比,结晶化速度略慢,因此在使用MX尼龙的情况下,为了缩短成型周期,优选向MX尼龙中配混脂肪族系聚酰胺树脂来使用。作为出于缩短成型周期的目的而配混时使用的脂肪族系聚酰胺树脂,可列举出聚酰胺66、聚酰胺6、聚酰胺46、聚酰胺9T等结晶化速度快的聚酰胺树脂;聚酰胺66/6T、66/6T/6I等高熔点的聚酰胺树脂,从经济性的观点出发,优选为聚酰胺66或聚酰胺6。从成型性与物性的平衡出发,该脂肪族系聚酰胺树脂的含有率优 选不足全部聚酰胺树脂中的50重量%,更优选为1~20重量%。通过使脂肪族系聚酰胺树脂的含有率不足50重量%,能够更良好地保持耐热性。
在MX尼龙的原料即α,ω-直链脂肪族二元酸之中,可适合地使用碳原子数6~20的α,ω-直链脂肪族二元酸、例如己二酸、癸二酸、辛二酸、十二烷二酸、二十烷二酮酸等。在这些α,ω-直链脂肪族二元酸之中,考虑到成型性、成型品性能等的平衡,特别适合为癸二酸。
MX尼龙的另一个原料中使用的苯二甲胺是间苯二甲胺、或者对苯二甲胺与间苯二甲胺的混合苯二甲胺。混合苯二甲胺中的间苯二甲胺与对苯二甲胺的摩尔比率(间苯二甲胺/对苯二甲胺)优选为55/45~100/0,更优选为70/30~100/0。通过使对苯二甲胺的摩尔比率不足45摩尔%,能够将聚酰胺树脂的熔点保持为低,MX尼龙的聚合、包含MX尼龙的组合物的成型加工变得容易,故而优选。
作为热塑性聚酯树脂,能够参考日本特开2010-174223号公报第0013~0016段的记载,将它们的内容组入本申请说明书中。例如作为聚酯树脂,可列举出聚对苯二甲酸丁二醇酯树脂;聚对苯二甲酸丁二醇酯树脂占60重量%以上、优选占80重量%以上的混合物。
本发明的热塑性树脂组合物中的热塑性树脂的配混量以合计计优选为35重量%以上、更优选为40重量%以上。
<LDS添加剂>
本发明中的LDS添加剂是指下述化合物:相对于热塑性树脂(例如,后述实施例中合成的聚酰胺树脂)100重量份,添加认为是LDS添加剂的添加剂10重量份,使用波长1064nm的YAG激光,以输出功率13W、频率20kHz、扫描速度2m/s进行照射,之后的镀覆工序利用无电解的MacDermid公司制造的MIDCopper100XB Strike的镀槽实施,对该激光照射面适用金属时,能够形成镀层的化合物。本发明中使用的LDS添加剂可以是合成品,也可以使用 市售品。另外,市售品除了作为LDS添加剂而上市销售的物质之外,只要满足本发明中的LDS添加剂的条件,则也可以是作为其它用途销售的物质。
本发明中使用的LDS添加剂的第一实施方式可列举出:以氧化锡作为主成分,包含70重量%以上的氧化锡,包含75重量%以上的氧化锡。
作为第一实施方式的LDS添加剂,为包含锑和/或磷和锡的氧化物、优选为包含锑和锡的氧化物。通过使用这样的LDS添加剂,能够提高树脂成型品的镀覆特性,因此能够在树脂成型品的表面适当地形成镀层。LDS添加剂可以仅使用一种,也可以组合使用两种以上。
第一实施方式的LDS添加剂更优选为锡的配混量多于磷和/或锑的配混量,锡的量相对于锡与磷与锑的合计量更优选为80重量%以上。
尤其是,作为第一实施方式的LDS添加剂,优选为包含锑和锡的氧化物,更优选为锡的配混量多于锑的配混量,锡的量相对于锡与锑的合计量更优选为80重量%以上。
具体而言,作为第一实施方式的LDS添加剂,例如可列举出掺杂有锑的氧化锡、掺杂有氧化锑的氧化锡、掺杂有磷的氧化锡、掺杂有磷氧化物的氧化锡,优选为掺杂有锑的氧化锡、掺杂有氧化锑的氧化锡,更优选为掺杂有氧化锑的氧化锡。例如,在包含磷和氧化锡的LDS添加剂中,磷的含量优选为1~20重量%。另外,在包含锑和氧化锡的LDS添加剂中,锑的含量优选为1~20重量%。另外,在包含磷和锑和氧化锡的LDS添加剂中,磷的含量优选为0.5~10重量%、锑的含量优选为0.5~10重量%。
本发明的第二实施方式中使用的LDS添加剂优选的是,包含至少含有两种金属且电阻率为5×103Ω·cm以下的导电性氧化物。导电性氧化物的电阻率优选为8×102Ω·cm以下,更优选为7×102Ω·cm以下,进一步优选为5×102Ω·cm以下。针对下限没有特别限定,例如可以设为1×101Ω·cm以上、进而可以设为1×102Ω·cm以上。
本发明中的导电性氧化物的电阻率通常称为粉末电阻率,可以将导电性氧化物的微粉10g装入对内表面施加了特氟隆加工的内径25mm的圆筒内,加压至100kg/cm2(填充率为20%),用横河电机株式会社制造的“3223型”测试仪进行测定。
第二实施方式中使用的LDS添加剂只要包含电阻率为5×103Ω·cm以下的导电性氧化物就没有特别限定,优选包含至少2种金属,具体而言,优选包含元素周期表的n族(n为3~16的整数)金属和n+1族金属。n优选为10~13的整数,进一步优选为12或13。
关于第二实施方式中使用的LDS添加剂,将LDS添加剂中的元素周期表的n族(n为3~16的整数)金属含量与n+1族金属含量的合计记作100摩尔%时,一者的金属含量优选为15摩尔%以下,进一步优选为12摩尔%以下,特别优选为10摩尔%以下。对于下限没有特别限定,为0.0001摩尔%以上。通过将两种以上金属的含量设为这样的范围,能够提高镀覆性。本发明中,特别优选为掺杂有n+1族金属的n族金属氧化物。
进而,第二实施方式中使用的LDS添加剂优选的是,LDS添加剂中包含的金属成分的98重量%以上由上述元素周期表的n族金属的含量和n+1族金属构成。
作为元素周期表的n族金属,例如可列举出3族(钪、钇)、4族(钛、锆等)、5族(钒、铌等)、6族(铬、钼等)、7族(锰等)、8族(铁、钌等)、9族(钴、铑、铱等)、10族(镍、钯、铂)、11族(铜、银、金等)、12族(锌、镉等)、13族(铝、镓、铟等)、14族(锗、锡等)、15族(砷、锑等)、16族(硒、碲等)、它们的金属氧化物等。其中,优选为12族(n=12)的金属或金属氧化物,更优选为锌。
作为元素周期表的n+1族金属,例如可列举出4族(钛、锆等)、5族(钒、铌等)、6族(铬、钼等)、7族(锰等)、8族(铁、钌等)、9族(钴、铑、铱 等)、10族(镍、钯、铂)、11族(铜、银、金等)、12族(锌、镉等)、13族(铝、镓、铟等)、14族(锗、锡等)、15族(砷、锑等)、16族(硒、碲等)、它们的金属氧化物等。其中,优选为13族(n+1=13)的金属或金属氧化物,更优选为铝或镓,进一步优选为铝。
第二实施方式中使用的LDS添加剂可以含有除了导电性金属氧化物之外的金属。作为除了导电性氧化物之外的金属,可例示出锑、钛、铟、铁、钴、镍、镉、银、铋、砷、锰、铬、镁、钙等。这些金属可以以氧化物的形式存在。这些金属的含量相对于LDS添加剂分别优选为0.01重量%以下。
需要说明的是,关于第二实施方式中使用的LDS添加剂,从提高L值的观点出发,锑的含量相对于LDS添加剂优选为3重量%以下,更优选为1重量%以下,进一步优选为0.01重量%以下,特别优选实质上不含有。实质上不含有是指在对本发明效果造成影响的范围内不含有。
本发明中使用的LDS添加剂的平均粒径优选为0.01~100μm,更优选为0.05~10μm。通过设为这样的平均粒径,能够使适应于镀覆时的镀覆表面状态的均匀性变得更良好。
本发明的热塑性树脂组合物中的LDS添加剂的配混量相对于热塑性树脂100重量份为1~30重量份,优选为2~25重量份,更优选为10~22重量份。通过使LDS添加剂的配混量为这样的范围,能够使镀覆特性变得更良好。另外,如后所述,通过将滑石与LDS添加剂一并使用,即使在减少LDS添加剂的添加量的情况下,也能够形成镀层。
<激光标记用添加剂>
本发明的热塑性树脂组合物包含激光标记用添加剂。本发明的热塑性树脂组合物通过共同配混LDS添加剂和激光标记用添加剂,与不含激光标记用添加剂的热塑性树脂组合物相比,容易吸收激光。因此,本发明的热塑性树脂组合物在制成树脂成型品时,照射了激光的树脂成型品的表面部分的树脂 被去除,LDS添加剂能够露出至表面。露出至表面的LDS添加剂容易被照射激光,作为结果,本发明的热塑性树脂组合物即使以宽于以往的激光照射条件也能够在树脂成型品的表面适当地形成镀层。尤其是,即使激光的照射量少也能够形成镀层,因此能够提高生产率。
本发明中使用的激光标记用添加剂没有特别限定。例如可列举出如下物质:向后述实施例中采用的PAMP6树脂中添加可认为是激光标记添加剂的添加剂2重量份,通过压制来成型为200μm厚度的薄膜,在所得薄膜下铺展添加有炭黑的板,照射规定条件的激光时,能够实现可在薄膜表面进行印刷且添加了炭黑的板上未被印刷的物质。
作为这样的激光标记用添加剂,具体而言,可列举出:包含铜和钼的氧化物;包含铋和镓和/或钕的氧化物;对云母的薄片状基质覆盖了掺杂有锑、砷、铋、铜、镓、锗或它们的氧化物的氧化锡而成的颜料;添加有氢氧化铜一磷酸盐或氧化钼的高分子物质。另外,激光标记用添加剂可以仅使用一种,也可以组合使用两种以上。
这些激光标记用添加剂之中,优选为含有选自包含铜和钼的氧化物、以及、包含铋和镓和/或钕的氧化物中的至少1种,特别优选为包含铜和钼的氧化物。作为包含铜和钼的氧化物,优选为CuMoO4。另外,作为包含铋和镓和/或钕的氧化物,优选为下述通式(1)所示的氧化物。
Bi(1-x)MxOy通式(1)
(式(1)中,M为镓和/或钕,x和y分别为具有0.001<x<0.5、1<y<2.5的关系的值。)
除了上述之外,作为本发明中使用的激光标记用添加剂,可列举出日本特开2007-146059号公报、日本特开2008-045051号公报、日本特开2009-102541号公报、日本特开2010-095396号公报、日本特开2010-194906号公报等中记载的添加剂,将它们的内容组入本申请说明书中。
本发明中使用的激光标记用添加剂的平均粒径优选为0.01~50μm,更优选为0.1~10μm。
本发明的热塑性树脂组合物中的激光标记用添加剂的配混量相对于热塑性树脂100重量份通常为0.05~10重量份,优选为0.1~8重量份,更优选为0.5~6重量份。
<无机纤维>
本发明的热塑性树脂组合物还可以包含无机纤维。通过配混无机纤维,能够进一步提高机械强度。另外,通过配混无机纤维,还能够进一步提高尺寸精度。无机纤维可以仅使用一种,也可以组合使用两种以上。
作为无机纤维,例如可列举出玻璃纤维、磨碎纤维、氧化铝纤维、钛酸钾晶须等,作为金属纤维,可列举出钢纤维、不锈钢纤维等,特别优选为玻璃纤维。
本发明中优选使用的玻璃纤维的平均直径优选为20μm以下,从进一步提高物性平衡(强度、刚性、耐热刚性、冲击强度)的观点和进一步降低成型翘曲的观点出发,平均直径进一步优选为1~15μm。另外,大多一般使用通常剖面形状为圆形的玻璃纤维,但在本发明中,没有特别限定,例如即使剖面形状为眉形、椭圆形、矩形的形状也可以同样地使用。
玻璃纤维的长度没有特别限定,可以从长纤维类型(粗纱)、短纤维类型(短切原丝)等中选择并使用。这种类型的玻璃纤维中的集束根数优选为100~5000根左右。另外,只要将热塑性树脂组合物混炼后的热塑性树脂组合物中的玻璃纤维能够获得平均0.1mm以上的长度,则也可以是所谓的磨碎纤维、被称为玻璃粉末的股线的粉碎品,另外,玻璃纤维还可以是连续单纤维系的棉条。
原料玻璃的组成优选为无碱的组成,例如可列举出E玻璃、C玻璃、S玻璃等,在本发明中,优选为E玻璃。玻璃纤维优选用例如γ-甲基丙烯酰氧基 丙基三甲氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、γ-氨基丙基三乙氧基硅烷等硅烷偶联剂进行了表面处理,其附着量通常为玻璃纤维重量的0.01~1重量%。进而根据需要,也可以使用用脂肪酸酰胺化合物、硅油等润滑剂、季铵盐等抗静电剂、环氧树脂、聚氨酯树脂等具有覆膜形成能力的树脂、具有覆膜形成能力的树脂与热稳定剂、阻燃剂等的混合物进行表面处理而成的物质。
本发明的热塑性树脂组合物中的无机纤维的配混量相对于热塑性树脂100重量份,通常为10~200重量份,优选为20~180重量份,更优选为30~150重量份。另外,本发明的热塑性树脂组合物中,热塑性树脂与无机纤维优选占全部成分的80重量%以上。
<滑石>
本发明的热塑性树脂组合物还可以包含滑石。通过配混滑石,能够使尺寸稳定性、制品外观变得良好,另外,即使减少LDS添加剂的添加量,也能够使树脂成型品的镀覆特性变得良好,能够在树脂成型品上形成适当的镀层。滑石可以使用用选自聚有机氢硅氧烷类和有机聚硅氧烷类中的至少一种化合物进行了表面处理而成的物质。此时,滑石中的硅氧烷化合物的附着量优选为滑石的0.1~5重量%。
本发明的热塑性树脂组合物中的滑石的配混量相对于热塑性树脂组合物100重量份优选为0.1~50重量份、更优选为1~30重量份、进一步优选为5~15重量份。另外,滑石用硅氧烷化合物进行了表面处理时,用硅氧烷化合物进行了表面处理的滑石的配混量优选在上述范围内。
<弹性体>
本发明的热塑性树脂组合物还可以包含弹性体。像这样,通过含有弹性体,能够提高热塑性树脂组合物的耐冲击性。
本发明中使用的弹性体优选为向橡胶成分上接枝共聚有能够与其共聚 的单体成分而成的接枝共聚物。作为接枝共聚物的制造方法,可以是块状聚合、溶液聚合、悬浮聚合、乳液聚合等中的任意制造方法,共聚的方式可以是一段接枝也可以是多段接枝。
橡胶成分的玻璃化转变温度通常为0℃以下、其中优选为-20℃以下、进一步优选为-30℃以下。作为橡胶成分的具体例,可列举出聚丁二烯橡胶、聚异戊二烯橡胶、聚丙烯酸丁酯、聚(丙烯酸2-乙基己酯)、丙烯酸丁酯·丙烯酸2-乙基己酯共聚物等聚丙烯酸烷基酯橡胶;聚有机硅氧烷橡胶等有机硅系橡胶、丁二烯-丙烯酸类复合橡胶、包含聚有机硅氧烷橡胶与聚丙烯酸烷基酯橡胶的IPN(Interpenetrating Polymer Network,互穿聚合物网状组织)型复合橡胶、苯乙烯-丁二烯橡胶、乙烯-丙烯橡胶、乙烯-丁烯橡胶、乙烯-辛烯橡胶等乙烯-α-烯烃系橡胶;乙烯-丙烯酸类橡胶、氟橡胶等。它们可以单独使用,也可以混合两种以上使用。这些之中,从机械特性、表面外观的方面出发,优选为聚丁二烯橡胶、聚丙烯酸烷基酯橡胶、聚有机硅氧烷橡胶、包含聚有机硅氧烷橡胶和聚丙烯酸烷基酯橡胶的IPN型复合橡胶、苯乙烯-丁二烯橡胶。
作为能够与橡胶成分进行接枝共聚的单体成分的具体例,可列举出芳香族乙烯基化合物、氰化乙烯基化合物、(甲基)丙烯酸酯化合物、(甲基)丙烯酸化合物、(甲基)丙烯酸缩水甘油酯等含环氧基(甲基)丙烯酸酯化合物;马来酰亚胺、N-甲基马来酰亚胺、N-苯基马来酰亚胺等马来酰亚胺化合物;马来酸、邻苯二甲酸、衣康酸等α,β-不饱和羧酸化合物、它们的酸酐(例如马来酸酐等)等。这些单体成分可以单独使用1种,也可以组合使用两种以上。这些之中,从机械特性、表面外观的方面出发,优选为芳香族乙烯基化合物、氰化乙烯基化合物、(甲基)丙烯酸酯化合物、(甲基)丙烯酸化合物,更优选为(甲基)丙烯酸酯化合物。作为(甲基)丙烯酸酯化合物的具体例,可列举出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸 丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸辛酯等。
共聚有橡胶成分的接枝共聚物从耐冲击性、表面外观的观点出发,优选为芯/壳型接枝共聚物类型。其中,特别优选为包含芯层和壳层的芯/壳型接枝共聚物,其中,以选自含聚丁二烯橡胶、含聚丙烯酸丁酯橡胶、聚有机硅氧烷橡胶、包含聚有机硅氧烷橡胶和聚丙烯酸烷基酯橡胶的IPN型复合橡胶中的至少1种橡胶成分作为芯层,并在其周围共聚(甲基)丙烯酸酯而形成壳层。在芯/壳型接枝共聚物中,优选含有40质量%以上的橡胶成分,进一步优选含有60质量%以上。另外,优选含有10质量%以上的(甲基)丙烯酸。需要说明的是,本发明中的芯/壳型不一定需要可明确地区分成芯层和壳层,是指广泛包括在成为芯的部分的周围接枝聚合有橡胶成分而得到的化合物。
作为这些芯/壳型接枝共聚物的优选具体例,可列举出甲基丙烯酸甲酯-丁二烯-苯乙烯共聚物(MBS)、甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯共聚物(MABS)、甲基丙烯酸甲酯-丁二烯共聚物(MB)、甲基丙烯酸甲酯-丙烯酸类橡胶共聚物(MA)、甲基丙烯酸甲酯-丙烯酸类橡胶-苯乙烯共聚物(MAS)、甲基丙烯酸甲酯-丙烯酸类·丁二烯橡胶共聚物、甲基丙烯酸甲酯-丙烯酸类·丁二烯橡胶-苯乙烯共聚物、甲基丙烯酸甲酯-(丙烯酸类·有机硅IPN橡胶)共聚物、苯乙烯-乙烯-丁二烯-苯乙烯共聚物等。这种橡胶性聚合物可以单独使用1种,也可以组合使用两种以上。
本发明的热塑性树脂组合物中的弹性体的含量优选为0.1~40重量%、更优选为0.5~25重量%、进一步优选为1~10重量%。
<脱模剂>
本发明的热塑性树脂组合物还可以含有脱模剂。脱模剂主要是为了提高树脂组合物的成型时的生产率而使用的。作为脱模剂,例如可列举出脂肪族羧酸酰胺系、脂肪族羧酸、脂肪族羧酸与醇的酯、数均分子量为200~15000的脂肪族烃化合物、聚硅氧烷系硅油等。在这些脱模剂之中,特别优选为羧 酸酰胺系化合物。
作为脂肪族羧酸酰胺系,例如可列举出通过高级脂肪族单羧酸和/或多元酸与二胺的脱水反应而得到的化合物。
作为高级脂肪族单羧酸,优选为碳原子数16以上的饱和脂肪族单羧酸和羟基羧酸,例如可列举出棕榈酸、硬脂酸、山嵛酸、褐煤酸、12-羟基硬脂酸等。
作为多元酸,例如可列举出丙二酸、琥珀酸、己二酸、癸二酸、庚二酸、壬二酸等脂肪族二羧酸;邻苯二甲酸、对苯二甲酸等芳香族二羧酸;环己烷二羧酸、环己基琥珀酸等脂环族二羧酸等。
作为二胺,例如可列举出乙二胺、1,3-二氨基丙烷、1,4-二氨基丁烷、六亚甲基二胺、间苯二甲胺、甲苯二胺、对苯二甲胺、苯二胺、异佛尔酮二胺等。
作为羧酸酰胺系化合物,优选为将硬脂酸与癸二酸与乙二胺缩聚而成的化合物,进一步优选为将2摩尔硬脂酸与1摩尔癸二酸与2摩尔乙二胺缩聚而成的化合物。另外,除了N,N'-亚甲基双硬脂酸酰胺、N,N'-亚乙基双硬脂酸酰胺之类的使二胺与脂肪族羧酸发生反应而得到的双酰胺系化合物之外,还可适合地使用N,N'-双十八烷基对苯二甲酸酰胺等二羧酸酰胺化合物。
作为脂肪族羧酸,例如可列举出饱和或不饱和的脂肪族一元、二元或三元羧酸。此处,脂肪族羧酸还包含脂环式的羧酸。这些之中,脂肪族羧酸优选为碳原子数6~36的一元羧酸或二元羧酸,进一步优选为碳原子数6~36的脂肪族饱和一元羧酸。作为所述脂肪族羧酸的具体例,可列举出棕榈酸、硬脂酸、己酸、癸酸、月桂酸、花生酸、山嵛酸、二十四烷酸、蜡酸、蜂花酸、三十四烷酸、褐煤酸、己二酸、壬二酸等。
作为脂肪族羧酸与醇的酯中的脂肪族羧酸,例如可以使用与脂肪族羧酸相同的物质。另一方面,作为醇,例如可列举出饱和或不饱和的一元或多元 醇。这些醇可以具有氟原子、芳基等取代基。这些之中,优选为碳原子数30以下的一元或多元的饱和醇,进一步优选为碳原子数30以下的脂肪族或脂环式饱和一元醇或脂肪族饱和多元醇。
作为所述醇的具体例,可列举出辛醇、癸醇、十二醇、硬脂醇、山嵛醇、乙二醇、二乙二醇、甘油、季戊四醇、2,2-二羟基全氟丙醇、新戊二醇、双三羟甲基丙烷、双季戊四醇等。
作为脂肪族羧酸与醇的酯的具体例,可列举出蜜蜡(以棕榈酸蜂花酯作为主成分的混合物)、硬脂酸硬脂酯、山嵛酸山嵛酯、山嵛酸硬脂酯、甘油单棕榈酸酯、甘油单硬脂酸酯、甘油二硬脂酸酯、甘油三硬脂酸酯、季戊四醇单棕榈酸酯、季戊四醇单硬脂酸酯、季戊四醇二硬脂酸酯、季戊四醇三硬脂酸酯、季戊四醇四硬脂酸酯等。
作为数均分子量为200~15000的脂肪族烃,例如可列举出液体石蜡、固体石蜡、微晶蜡、聚乙烯蜡、费托蜡、碳原子数3~12的α-烯烃低聚物等。需要说明的是,此处,作为脂肪族烃,还包括脂环式烃。另外,脂肪族烃的数均分子量优选为5000以下。
脱模剂的含量相对于热塑性树脂与玻璃纤维的合计100重量份,通常为0.001重量份以上、优选为0.01重量份以上,另外,通常为2重量份以下、优选为1.5重量份以下。通过将脱模剂的含量相对于热塑性树脂与玻璃纤维的合计100重量份设为0.001重量份以上,能够使脱模性变得良好。另外,通过将脱模剂的含量相对于热塑性树脂与玻璃纤维的合计100重量份设为2重量份以下,能够防止耐水解性的降低,另外,能够防止注射成型时的模具污染。
<碱>
本发明的热塑性树脂组合物还可以包含碱。本发明中使用的LDS添加剂为酸性物质(例如,pH6以下)时,通过组合而使自身发生还原,从而有时颜色会变成斑点模样,通过添加碱,能够使所得树脂成型品的颜色变得更均 匀。
碱的种类没有特别限定,例如可以使用氢氧化钙(Ca(OH)2)、氢氧化镁(Mg(OH)2)。碱可以仅使用一种,也可以组合使用两种以上。
本发明的热塑性树脂组合物中的碱的配混量还因LDS添加剂的种类和碱的种类而异,优选为LDS添加剂的配混量的0.01~15重量%,更优选为LDS添加剂的配混量的1~10重量%。
<其它添加剂>
本发明的热塑性树脂组合物在不损害本发明效果的范围内还可以含有各种添加剂。作为这样的添加剂,可列举出热稳定剂、阻燃剂、光稳定剂、抗氧化剂、紫外线吸收剂、染料颜料、荧光增白剂、抗滴落剂、抗静电剂、防雾剂、润滑剂、抗粘连剂、流动性改良剂、增塑剂、分散剂、抗菌剂等。这些成分可以仅使用一种,也可以组合使用两种以上。
<热塑性树脂组合物的制造方法>
作为本发明的热塑性树脂组合物的制造方法,可以采用任意的方法。例如可列举出如下方法:使用V型混合器等混合手段将热塑性树脂与LDS添加剂与玻璃纤维进行混合,调整成共混品后,用带排气孔的挤出机进行熔融混炼而制成粒料化的方法。另外,可列举出如下方法:作为二阶段投入法,预先对除了玻璃纤维之外的成分等进行充分混合后,用带排气孔的挤出机进行熔融混炼而制造粒料后,将该粒料与玻璃纤维进行混合后,用带排气孔的挤出机进行熔融混炼的方法。
进而,可列举出如下方法:预先制备用V型混合器等对除了玻璃纤维之外的成分等进行充分混合而成的物质,将该混合物由带排气孔的双螺杆挤出机的第一斜槽进行供给,将玻璃纤维由挤出机途中的第二斜槽供给并进行熔融混炼、粒料化的方法。
挤出机的混炼区的螺杆构成优选将促进混炼的元件配置在上游侧、将具 有升压能力的元件配置在下游侧。
作为促进混炼的元件,可列举出正向捏合盘元件、正交捏合盘元件、宽捏合盘元件和正向混合螺杆元件等。
熔融混炼时的加热温度通常可以从180~360℃的范围中适当选择。若温度过高,则容易产生分解气体,有时会成为不透明化的原因。因此,期望考虑剪切发热等来选择螺杆构成。另外,从抑制混炼时、后工序的成型时的分解的观点出发,期望使用抗氧化剂、热稳定剂。
树脂成型品的制造方法没有特别限定,能够任意采用对于热塑性树脂组合物而言通常采用的成型法。若举出其例,则可列举出注射成型法、超高速注射成型法、注射压缩成型法、双色成型法、气体辅助等中空成型法、使用绝热模具的成型法、使用急速加热模具的成型法、发泡成型(还包括超临界流体)、嵌入成型、IMC(模内涂布成型)成型法、挤出成型法、片状成型法、热成型法、旋转成型法、层积成型法、压制成型法、吹塑成型法等。另外,还可以利用使用了热流道方式的成型法。
<带镀层的树脂成型品的制造方法>
接着,根据图1来说明本发明的带镀层的树脂成型品的制造方法,具体而言,说明在将本发明的热塑性树脂组合物成型而成的树脂成型品的表面设置镀层的工序。
图1是示出利用激光直接成型技术在树脂成型品1的表面形成镀层的工序的示意图。图1中,树脂成型品1是平坦的基板,但未必需要为平坦的基板,也可以是一部分或全部为曲面的树脂成型品。另外,树脂成型品1不限于最终制品,还包括各种部件。
作为本发明中的树脂成型品1,优选为便携式电子设备部件。便携式电子设备部件兼具高耐冲击特性和刚性、以及优异的耐热性,而且具有各向异性小、翘曲小的特征,作为电子笔记本、便携用计算机等PDA、呼叫机、移 动电话、PHS等的内部结构物和壳体极其有效。特别适合于成型品除去棱之后的平均厚度为1.2mm以下(下限值没有特别限定,例如为0.4mm以上)的平板形状的便携式电子设备用部件,其中特别适合作为壳体。
再返回到图1,在本发明的带镀层的树脂成型品的制造方法中,对树脂成型品1照射激光2。
激光2没有特别限定,可以从YAG激光、准分子激光、电磁辐射等公知的激光中适当选择,特别优选为YGA激光。另外,激光2的波长也没有特别限定。激光2的波长范围优选为200nm~1200nm,特别优选为800~1200nm。
激光2照射至树脂成型品1时,仅被照射激光2的部分3的树脂成型品1被活化。在这种被活化的状态下,将树脂成型品1适用于镀覆液4。作为镀覆液4,没有特别限定,可以广泛采用公知的镀覆液,作为金属成分,优选为混合了铜、镍、金、银、钯的金属成分,更优选为铜。
关于将树脂成型品1适用于镀覆液4的方法,没有特别限定,例如可列举出将树脂成型品1投入至配混了镀覆液的液体中的方法。适用了镀覆液后的树脂成型品1仅在照射了激光2的部分形成镀层5。
在本发明的方法中,能够形成1mm以下、进而150μm以下的宽度的电路间隔(下限值没有特别限定,例如为30μm以上)。该电路优选用作便携式电子设备部件的天线。即,作为本发明的树脂成型品1的优选实施方式的一例,可列举出在便携式电子设备部件的表面设置的镀层具有作为天线的性能的树脂成型品。
除此之外,可以在不脱离本发明主旨的范围内参考日本特开2011-219620号公报、日本特开2011-195820号公报、日本特开2011-178873号公报、日本特开2011-168705号公报、日本特开2011-148267号公报的记载。
实施例
以下,列举出实施例来更具体地说明本发明。以下的实施例示出的材料、 用量、比例、处理内容、处理步骤等只要不脱离本发明的主旨则能够适宜变更。因此,本发明的范围不限定于以下所示的具体例。
<聚酰胺树脂>
(聚酰胺(PAMP10)的合成)
将癸二酸在氮气气氛下的反应罐内加热溶解后,一边搅拌内容物,一边在加压(0.35Mpa)下以二胺与癸二酸的摩尔比约为1:1的方式缓慢地滴加对苯二甲胺(三菱瓦斯化学株式会社制)与间苯二甲胺(三菱瓦斯化学株式会社制)的摩尔比为3:7的混合二胺,同时使温度上升至235℃。滴加结束后,持续反应60分钟,制备成分子量为1000以下的成分量。反应结束后,将内容物取出成股线状,用造粒机进行粒料化,得到聚酰胺。以下称为“PAMP10”。
(聚酰胺(PAMP6)的合成)
将己二酸在氮气气氛下的反应罐内加热溶解后,一边搅拌内容物,一边在加压(0.35Mpa)下以二胺与己二酸(Rhodia公司制)的摩尔比约为1:1的方式缓慢滴加对苯二甲胺(三菱瓦斯化学株式会社制)与间苯二甲胺(三菱瓦斯化学株式会社制)的摩尔比为3:7的混合二胺,同时使温度上升至270℃。滴加结束后,滴加结束后,减压至0.06MPa,持续反应10分钟,制备成分子量为1,000以下的成分量。其后,将内容物取出至股线状,用造粒机进行粒料化,得到聚酰胺。以下称为“PAMP6”。熔点为256℃。
<LDS添加剂>
T-1-20L:锡-锑氧化物(SnO2:80%、Sb2O5:20%、锑含量:15.1重量%)、水分率1.5%、pH=3.4)(Mitsubishi Materials Corporation制)
23K:Hakusuitech Co.,Ltd.制、铝掺杂氧化锌、电阻率(制品规格值)100~500Ω·cm
<激光标记用添加剂>
42-903A:包含铜和钼的氧化物(CuMoO4)、粒径1.5μm(Tokan MaterialTechnology Co.,Ltd.公司制)
42-920A:包含铋和钕的氧化物(Bi2O3:98~99%、Nd2O3:0.3~1%)、粒径1.0μm(Tokan Material Technology Co.,Ltd.公司制)
<无机纤维>
03T-296GH:玻璃纤维(日本电气硝子株式会社制)
<滑石>
MICRON WHITE 5000S(林化成株式会社制)
<弹性体>
SEBS:FT1901GT(Kraton公司制)
<脱模剂>
CS8CP(日东化成工业株式会社制)
<碱>
Ca(OH)2
<滑石>
MW5000S:滑石、林化成株式会社制
<混合>
以形成后述的表中所示组成的方式分别称量各成分,利用滚筒来共混除了无机纤维之外的成分,从双螺杆挤出机(东芝机械公司制、TEM26SS)的根部投入,熔融后,侧进料无机纤维而制作树脂粒料。挤出机的温度设定以280℃来实施。
<镀覆特性(实施例1~3、比较例1)>
向作为模具的60×60mm且厚度为2mm的模腔中,以树脂温度280℃、模具温度110℃从宽度60mm、1.5mm厚度的扇形闸门填充树脂并进行成型。切割闸门部分,得到板试验片。
在所得板试验片的10×10mm的范围内,使用Trumpf公司制造的VMc1的 激光照射装置(波长为1064nm的YAG激光最大输出功率15W),以输出功率(Power)6W或8W、频率(Frequency)60kHz或80kHz、扫描速度4m/s进行照射。之后的镀覆工序用无电解的Enthone公司制造的ENPLATE LDS CU 400PC的48℃的镀槽来实施。镀覆性能是通过目视判断20分钟内所镀覆的铜的厚度。
镀覆特性针对激光条件幅度和镀覆外观如下所示地评价。将结果示于下述表1。
<<激光条件幅度>>
○:在任何条件下均会均匀地附着镀层
△:在部分条件下不会均匀地附着镀层(实用水平)
×:在一半以上的条件下不会均匀地附着镀层
<<镀覆(Plating)外观>>
针对上述4个条件(关于激光照射条件的输出功率和频率,输出功率6W且频率60kHz、输出功率6W且频率80kHz、输出功率8W且频率60kHz、输出功率8W且频率80kHz)之中外观最良好的样品,进行如下评价。
○:良好的外观(确认到铜的颜色深、镀层较厚地附着的样子)
△:镀层附着,但略薄的样子(实用水平)
×:镀层完全不附着的样子
<镀覆特性(实施例4、5、比较例2)>
向作为模具的60×60mm且厚度为2mm的模腔中,以树脂温度280℃、模具温度110℃从宽度60mm、1.5mm厚度的扇形闸门填充树脂并进行成型。切割闸门部分,得到板试验片。
使用上述2mmt的板试验片评价镀覆性。使用SUNX株式会社制造的LP-ZSERIES的激光照射装置(波长1064nm的YAG激光最大输出功率13W),以(1)输出功率20%、脉冲周期20μs(微秒)、(2)输出功率20%、脉冲周期50μs、 (3)输出功率80%、脉冲周期20μs、(4)输出功率80%、脉冲周期50μs、扫描速度2m/s对5mm×5mm的范围进行照射。之后的镀覆工序使用无电解的MacDermid公司制造的MIDCopper100XB Strike,用60℃的镀槽实施60分钟。
与上述同样地评价激光条件幅度和镀覆外观。
[表1]
[表2]
由表1的结果明确可知:实施例1~3中得到的热塑性树脂组合物包含热塑性树脂、相对于热塑性树脂100重量份为1~30重量份的LDS添加剂以及0.1~10重量份的激光标记用添加剂,LDS添加剂包含70重量%以上的氧化锡,因此能够以宽泛的照射条件形成镀层,实现了优异的镀覆外观。
另一方面可知:比较例1中得到的热塑性树脂组合物不含有激光标记用添加剂,因此与实施例1~3相比,能够适当地形成镀层的照射条件的限制大。
由表2的结果明确可知:实施例4、5中得到的热塑性树脂组合物包含热塑性树脂、相对于热塑性树脂100重量份为1~30重量份的LDS添加剂以及 0.1~10重量份的激光标记用添加剂,LDS添加剂包含70重量%以上的氧化锡,因此能够以比较宽泛的照射条件形成镀层,实现了优异的镀覆外观。
另一方面可知:比较例2中得到的热塑性树脂组合物不含有激光标记用添加剂,因此与实施例4、5相比,能够适当地形成镀层的照射条件的限制大。
像这样可知:根据本发明,可提供能够以更宽泛的照射条件在树脂成型品的表面适当地形成镀层的热塑性树脂组合物。因此,能够提高在将本发明的热塑性树脂组合物成型而成的树脂成型品的表面形成镀层时的生产率。
附图标记说明
1树脂成型品、2激光、3照射了激光的部分、4镀覆液、5镀层。
Claims (12)
1.一种热塑性树脂组合物,其包含:热塑性树脂、相对于该热塑性树脂100重量份为1~30重量份的激光直接成型添加剂以及0.1~10重量份的激光标记用添加剂,
所述激光直接成型添加剂包含70重量%以上的氧化锡,
所述激光标记用添加剂含有选自包含铜和钼的氧化物、以及包含铋和钕的氧化物中的至少1种,
所述激光直接成型添加剂含有包含锑和锡的氧化物。
2.根据权利要求1所述的热塑性树脂组合物,其中,相对于所述热塑性树脂100重量份,包含10~200重量份的无机纤维。
3.根据权利要求2所述的热塑性树脂组合物,其中,所述无机纤维为玻璃纤维。
4.根据权利要求1~3中任一项所述的热塑性树脂组合物,其中,所述激光标记用添加剂为包含铜和钼的氧化物。
5.根据权利要求1~3中任一项所述的热塑性树脂组合物,其中,所述热塑性树脂为聚酰胺树脂。
6.一种树脂成型品,其是将权利要求1~5中任一项所述的热塑性树脂组合物成型而成的。
7.根据权利要求6所述的树脂成型品,其在表面具有镀层。
8.根据权利要求7所述的树脂成型品,其为便携式电子设备部件。
9.根据权利要求7或8所述的树脂成型品,其中,所述镀层具有作为天线的性能。
10.一种带镀层的树脂成型品的制造方法,其包括:对将权利要求1~5中任一项所述的热塑性树脂组合物成型而成的树脂成型品的表面照射激光后,利用金属形成镀层。
11.根据权利要求10所述的带镀层的树脂成型品的制造方法,其中,所述镀层为铜镀层。
12.一种具有天线的便携式电子设备部件的制造方法,其包括权利要求10或11所述的带镀层的树脂成型品的制造方法。
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EP2899235A4 (en) | 2016-05-11 |
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US20150244066A1 (en) | 2015-08-27 |
US10148006B2 (en) | 2018-12-04 |
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