JP2007031491A - Resin composition for laser welding - Google Patents
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Abstract
Description
本発明は、レーザー溶着用樹脂組成物に関する。 The present invention relates to a resin composition for laser welding.
一般的にレーザー溶着は、レーザーを透過する部材とレーザーを吸収する部材とを、両者の接着したい部分を重ね合わせ、レーザーを透過する部材側からレーザー光を当てて吸収側の部材を溶融させて透過側の部材と接着させる手法である。 In general, laser welding involves laminating a laser transmitting member and a laser absorbing member by superimposing the parts to be bonded together, and applying laser light from the laser transmitting member side to melt the absorbing member. This is a technique of adhering to a member on the transmission side.
このレーザー吸収部材には、レーザーマーキング用吸収剤として特許文献１に記載のカーボンブラックやグラファイトを用いるのが有名であり、特許文献２において銅化合物の使用が明記されている。その他、各種の添加剤が公開されているが、カーボンブラックは黒色であり、また、その他の添加剤も、不透明乃至何かしらの色が付いている。
上記従来技術のレーザー溶着用樹脂組成物は、主として黒色を呈しており、従来の方法では黒色乃至暗色以外のレーザー溶着成形物を得ることができなかった。
従って本発明は、透明乃至半透明であり、必要に応じて白色や鮮明な色彩に着色可能なレーザー溶着用樹脂組成物を提供することである。
The laser welding resin composition of the above prior art mainly exhibits black color, and a laser welding molded product other than black or dark color cannot be obtained by the conventional method.
Accordingly, an object of the present invention is to provide a laser welding resin composition that is transparent or translucent and can be colored in white or clear colors as necessary.
上記目的は以下の本発明によって達成される。すなわち、本発明は、熱可塑性樹脂中に、酸化チタン、酸化鉄、酸化スズ、酸化スズ／アンチモンなどの金属酸化物の少なくとも１種にて被覆されたマイカを含有することを特徴とするレーザー溶着用樹脂組成物を提供する。 The above object is achieved by the present invention described below. That is, the present invention includes laser welding characterized in that mica coated with at least one metal oxide such as titanium oxide, iron oxide, tin oxide, tin oxide / antimony is contained in the thermoplastic resin. A resin composition is provided.
本発明によれば、透明乃至半透明であり、必要に応じて白色や鮮明な色彩に着色可能なレーザー溶着用樹脂組成物が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the resin composition for laser welding which is transparent thru | or translucent and can be colored in white or a clear color as needed is provided.
次に好ましい実施の形態を挙げて本発明をさらに詳しく説明する。
本発明で使用する熱可塑性樹脂は、後述の表面被覆マイカを配合し得る樹脂であれば特に限定されず、例えば、ポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体、ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂、ポリカーボネート、ポリアミド、ポリエステル、ポリオキシメチレン、ポリエーテルスルホン、ポリエーテルエーテルケトン、アクリル樹脂など各種樹脂が挙げられる。特にレーザー吸収能が低いポリエチレン、ポリプロピレン、エチレン−酢酸ビニル共重合体、ポリオキシメチレン、アクリル樹脂などが有効である。
Next, the present invention will be described in more detail with reference to preferred embodiments.
The thermoplastic resin used in the present invention is not particularly limited as long as it can be blended with the below-described surface-coated mica. For example, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polystyrene, AS resin, ABS resin, Various resins such as polycarbonate, polyamide, polyester, polyoxymethylene, polyethersulfone, polyetheretherketone, and acrylic resin can be used. In particular, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polyoxymethylene, acrylic resin and the like having low laser absorption ability are effective.
本発明において、上記熱可塑性樹脂に添加するマイカは、酸化チタン、酸化鉄、酸化スズ、酸化スズ／アンチモンなどの金属酸化物の少なくとも１種にて被覆されたマイカである。このような表面被覆マイカはメルク社製から商品名「レーザーフレアＬＳ８２０」（被覆金属酸化物：酸化チタン、酸化ケイ素、酸化アンチモンドープ酸化スズ）、「レーザーフレアＬＳ８２５」（被覆金属酸化物：酸化アンチモンドープ酸化スズ）、「レーザーフレアＬＳ８３０」（被覆金属酸化物：酸化チタン、酸化鉄黒）および「レーザーフレアＬＳ８３５」（被覆金属酸化物：酸化鉄黒）などを入手して本発明で使用できる。 In the present invention, mica added to the thermoplastic resin is mica coated with at least one metal oxide such as titanium oxide, iron oxide, tin oxide, tin oxide / antimony. Such surface-coated mica is manufactured by Merck Co., Ltd. under the trade name “Laser Flare LS820” (coated metal oxide: titanium oxide, silicon oxide, antimony oxide doped tin oxide), “Laser Flare LS825” (coated metal oxide: antimony oxide). Doped tin oxide), “Laser Flare LS830” (coated metal oxide: titanium oxide, iron oxide black), “Laser Flare LS835” (coated metal oxide: iron oxide black), and the like can be obtained and used in the present invention.
上記表面被覆マイカの熱可塑性樹脂に対する添加量は、熱可塑性樹脂１００質量部あたり約０．０１〜１．０質量部の範囲であることが好ましい。表面被覆マイカの添加量が０．０１質量部未満であるとレーザーの吸収力が弱く、十分な溶着が行なえないなどの不都合を生じる場合があり、一方、表面被覆マイカの添加量が１．０質量部を超えるとレーザーの吸収力が強過ぎ、溶着成形品にヤケおよびスジが起こり外観不良になりやすく、また、表面被覆マイカ自体が表面に現れ、見た目があまり良好とはいえないなどの不都合を生じる場合がある。 The amount of the surface-coated mica added to the thermoplastic resin is preferably in the range of about 0.01 to 1.0 part by mass per 100 parts by mass of the thermoplastic resin. If the addition amount of the surface coating mica is less than 0.01 parts by mass, there are cases where the laser absorbency is weak and inadequate welding may occur, while the addition amount of the surface coating mica is 1.0. If it exceeds the mass part, the laser absorbency is too strong, and the welded molded product may be burned and streaked, and the appearance may be poor, and the surface coating mica itself will appear on the surface and the appearance may not be very good May occur.
本発明の樹脂組成物は、含有している表面被覆マイカに透明性があるため、さらに無機系顔料、有機系顔料、有機染料などの各種着色剤を使用し、種々の色相に着色することも可能である。また、本発明の樹脂組成物には、その他の各種添加剤、例えば、安定剤、酸化防止剤、耐電防止剤、ワックス類、紫外線防止剤などを必要に応じて配合することができ、さらに、難燃剤および各種フィラーを必要に応じて配合することができる。 In the resin composition of the present invention, since the surface-coated mica contained therein is transparent, various colorants such as inorganic pigments, organic pigments, organic dyes and the like can be used to color the various hues. Is possible. In addition, the resin composition of the present invention may contain other various additives, for example, stabilizers, antioxidants, antistatic agents, waxes, UV inhibitors, and the like as necessary. A flame retardant and various fillers can be mix | blended as needed.
本発明のレーザー溶着用樹脂組成物は、熱可塑性樹脂粉末と表面被覆マイカ粉末との単なる混合物でもよいし、両者を溶融混練してペレット状に造粒したものでもよい。 The resin composition for laser welding of the present invention may be a simple mixture of thermoplastic resin powder and surface-coated mica powder, or may be obtained by melting and kneading both to form a pellet.
次に実施例および比較例を挙げて本発明をさらに具体的に説明する。なお、以下の文中における「％」は質量基準である。また、後述する溶着テストを行うに当たり透過樹脂部材としてランダムポリプロピレンのナチュラル樹脂を、平板金型を装着した射出成形機で成形して５０×９０×２ｍｍの成形品を作成し、透過側接着部材とした。 Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following text, “%” is based on mass. In addition, when performing a welding test to be described later, a random polypropylene natural resin is molded as a transparent resin member by an injection molding machine equipped with a flat plate mold to produce a molded product of 50 × 90 × 2 mm. did.
実施例１
ランダムポリプロピレン樹脂に、表面被覆マイカ（メルク社製レーザーフレアＬＳ８２０）を０．１％（実施例１−１）、０．３％（実施例１−２）および０．５％（実施例１−３）の割合でそれぞれ配合し、押出機により溶融混練して樹脂中に表面被覆マイカを十分分散し、３種のペレット状レーザー溶着用樹脂組成物を作成した。さらにこの組成物を平板金型を装着した射出成形機で成形して５０×９０×２ｍｍの成形品を作成し、実施例１−１〜３の評価プレートとした。
Example 1
To the random polypropylene resin, 0.1% (Example 1-1), 0.3% (Example 1-2) and 0.5% (Example 1) of surface-coated mica (Laser Flare LS820 manufactured by Merck) Each of them was blended at a ratio of 3) and melt-kneaded with an extruder to sufficiently disperse the surface-coated mica in the resin, thereby preparing three types of pelletized laser welding resin compositions. Further, this composition was molded by an injection molding machine equipped with a flat plate mold to prepare a molded product of 50 × 90 × 2 mm, and used as an evaluation plate of Examples 1-1 to 1-3.
実施例２
ランダムポリプロピレン樹脂に、表面被覆マイカ（メルク社製レーザーフレアＬＳ８２５）を０．１％（実施例２−１）、０．３％（実施例２−２）および０．５％実施例２−３）の割合で配合し、押出機により溶融混練して樹脂中に表面被覆マイカを十分分散し、ペレット状レーザー溶着組成物を作成した。さらに、この組成物を平板金型を装着した射出成形機で成形して５０×９０×２ｍｍの成形品を作成し、実施例２−１〜３の評価プレートとした。
Example 2
Random polypropylene resin was coated with 0.1% (Example 2-1), 0.3% (Example 2-2) and 0.5% Example 2-3 of surface coated mica (Laser Flare LS825 manufactured by Merck & Co., Inc.). ), And melt-kneaded with an extruder to sufficiently disperse the surface-coated mica in the resin to prepare a pellet-shaped laser welding composition. Further, this composition was molded by an injection molding machine equipped with a flat plate mold to prepare a molded product of 50 × 90 × 2 mm, and used as an evaluation plate of Examples 2-1 to 2-3.
比較例１
ランダムポリプロピレンのナチュラル樹脂を平板金型を装着した射出成形機で成形して５０×９０×２ｍｍの成形品を作成し、評価プレートとした。
Comparative Example 1
A random polypropylene natural resin was molded by an injection molding machine equipped with a flat plate mold to prepare a molded product of 50 × 90 × 2 mm, which was used as an evaluation plate.
実施例３
ランダムポリプロピレン樹脂に、表面被覆マイカ（メルク社製レーザーフレアＬＳ８２５）を０．１％（実施例３−１）、０．３％（実施例３−２）および０．５％（実施例３−３）の割合で配合し、さらにそれぞれの配合物に白色顔料（酸化チタン）を１％配合し、それぞれ押出機により溶融混練して樹脂中に表面被覆マイカと白色顔料とを十分分散し、ペレット状レーザー溶着組成物を作成した。さらに、この組成物を平板金型を装着した射出成形機で成形して５０×９０×２ｍｍの成形品を作成し、実施例３−１〜３の評価プレートとした。
Example 3
To the random polypropylene resin, 0.1% (Example 3-1), 0.3% (Example 3-2), and 0.5% (Example 3-) of surface-coated mica (Laser Flare LS825 manufactured by Merck) 3) In addition, 1% of white pigment (titanium oxide) is further blended in each blend, melted and kneaded with an extruder, and the surface-coated mica and white pigment are sufficiently dispersed in the resin. A laser welding composition was prepared. Further, this composition was molded by an injection molding machine equipped with a flat plate mold to prepare a molded product of 50 × 90 × 2 mm, and used as an evaluation plate of Examples 3-1 to 3-1.
実施例４
ランダムポリプロピレン樹脂に表面被覆マイカ（メルク社製レーザーフレアＬＳ８３０）を０．０３％（実施例４−１）、０．０５％（実施例４−２）、および０．０８％（実施例４−３）の割合で配合し、さらにそれぞれの配合物に白色顔料（酸化チタン）を１％配合し、それぞれ押出機により溶融混練して樹脂中に表面被覆マイカと白色顔料とを十分分散し、ペレット状レーザー溶着組成物を作成した。さらに、この組成物を平板金型を装着した射出成形機で成形して５０×９０×２ｍｍの成形品を作成し、実施例４−１〜３の評価プレートとした。
Example 4
0.03% (Example 4-1), 0.05% (Example 4-2), and 0.08% (Example 4-) of surface-coated mica (Laser Flare LS830 manufactured by Merck & Co., Inc.) on a random polypropylene resin 3) In addition, 1% of white pigment (titanium oxide) is further blended in each blend, melted and kneaded with an extruder, and the surface-coated mica and white pigment are sufficiently dispersed in the resin. A laser welding composition was prepared. Further, this composition was molded by an injection molding machine equipped with a flat plate mold to prepare a molded product of 50 × 90 × 2 mm, and used as an evaluation plate of Examples 4-1 to 3-1.
実施例５
ランダムポリプロピレン樹脂に表面被覆マイカ（メルク社製レーザーフレアＬＳ８３５）を０．０３％（実施例５−１）、０．０５％（実施例５−２）および０．０８％（実施例５−３）の割合で配合し、さらにそれぞれの配合物に白色顔料（酸化チタン）を１％配合し、それぞれ押出機により溶融混練して樹脂中に表面被覆マイカと白色顔料とを十分分散し、ペレット状レーザー溶着組成物を作成した。さらに、この組成物を平板金型を装着した射出成形機で成形して５０×９０×２ｍｍの成形品を作成し、実施例５−１〜３の評価プレートとした。
Example 5
0.03% (Example 5-1), 0.05% (Example 5-2) and 0.08% (Example 5-3) of surface-coated mica (Laser Flare LS835 manufactured by Merck & Co., Inc.) on a random polypropylene resin ) And 1% of white pigment (titanium oxide) in each compound, melted and kneaded with an extruder to sufficiently disperse the surface-coated mica and the white pigment in a pellet form. A laser welding composition was prepared. Further, this composition was molded by an injection molding machine equipped with a flat plate mold to prepare a molded product of 50 × 90 × 2 mm, and used as an evaluation plate of Examples 5-1 to 3-1.
比較例２
ランダムポリプロピレン樹脂に酸化チタンを０．５％（比較例２−１）、１．０％（比較例２−２）および１．５％（比較例２−３）の割合で配合し、押出機により溶融混練して樹脂中に酸化チタンを十分分散し、ペレット状組成物を作成した。さらに、この組成物を平板金型を装着した射出成形機で成形して５０×９０×２ｍｍの成形品を作成し、比較例２−１〜３の評価プレートとした。
Comparative Example 2
Random polypropylene resin was compounded with titanium oxide in proportions of 0.5% (Comparative Example 2-1), 1.0% (Comparative Example 2-2) and 1.5% (Comparative Example 2-3), and an extruder Was melt-kneaded to sufficiently disperse titanium oxide in the resin, thereby preparing a pellet-shaped composition. Further, this composition was molded by an injection molding machine equipped with a flat plate mold to prepare a molded product of 50 × 90 × 2 mm, and used as an evaluation plate of Comparative Examples 2-1 to 2-3.
評価例
以上で得られた実施例および比較例の評価プレートについて、レーザー溶着後のプレートの可視光領域の透過率（％）、溶着性および色調を評価して下記表１に示す結果が得られた。
Evaluation Example With respect to the evaluation plates of Examples and Comparative Examples obtained above, the transmittance (%), weldability and color tone of the plate after laser welding were evaluated, and the results shown in Table 1 below were obtained. It was.
＜レーザー溶着方法＞
レーザー透過用ナチュラル樹脂プレートを上に、そして表面被覆マイカ添加プレートを下に重ね合わせ、上からレーザーを当て上のナチュラル層はレーザーを透過し、下の表面被覆マイカ添加プレートにてレーザーが吸収され、熱エネルギーに変換され双方の重ね合わせ部分が溶融し接着される。溶着はレーザー波長８０８ｎｍ、９４０ｎｍにて行なった。
<Laser welding method>
The natural resin plate for laser transmission is placed on top and the surface-coated mica-added plate is placed on the bottom, the laser is applied from the top and the upper natural layer transmits the laser, and the lower surface-coated mica-added plate absorbs the laser. Then, it is converted into heat energy, and the overlapping portions of both are melted and bonded. Welding was performed at laser wavelengths of 808 nm and 940 nm.
＜可視領域の透過率の測定方法＞
作成した評価プレートを日本分光（株）社製Ｖ−５７０にて４００ｎｍ〜７００ｎｍの透過率を測定し、測定領域範囲平均値を用いた。
<Measurement method of transmittance in visible region>
The transmittance | permeability of 400 nm-700 nm was measured for the created evaluation plate by V-570 by JASCO Corporation, and the measurement area range average value was used.
＜溶着性の評価方法＞
○：溶着している 液状物（水）が溶着部分から漏れない。
△：溶着している様に見えるが、液状物（水）が漏れるか所がある。
×：溶着していない 液状物（水）が漏れる。
<Method for evaluating weldability>
○: The welded liquid (water) does not leak from the welded part.
Δ: Although it seems to be welded, there is a place where liquid (water) leaks.
X: Liquid material (water) not welded leaks.
＜色調の評価方法＞
目視にて判断した。
<Evaluation method of color tone>
Judgment was made visually.
上記表１から明らかであるように本発明のレーザー溶着用樹脂組成物からなる成形物は、酸化チタンを含有していない場合は、可視光領域における透過率が高く透明であり、溶着性にも優れている。また、成形物は実質的に無色であるので従来は困難であった白色成形物を得ることができ、さらに必要に応じて各種有彩色の着色剤を使用して任意の成形物とすることができる。 As apparent from Table 1 above, when the molded product made of the laser welding resin composition of the present invention does not contain titanium oxide, it has high transmittance in the visible light region and is transparent, and also has good weldability. Are better. In addition, since the molded product is substantially colorless, it is possible to obtain a white molded product that has been difficult in the past, and further, if necessary, various chromatic colorants can be used to obtain an arbitrary molded product. it can.
上記本発明によれば、透明乃至半透明であり、必要に応じて白色や鮮明な色彩に着色可能なレーザー溶着用樹脂組成物が提供される。 According to the said invention, the resin composition for laser welding which is transparent thru | or translucent and can be colored in white or a clear color as needed is provided.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103249572A (en) * | 2010-10-26 | 2013-08-14 | 沙特基础创新塑料Ip私人有限责任公司 | Laser direct structuring materials with all color capability |
| CN103756370A (en) * | 2014-01-10 | 2014-04-30 | 河北欧克精细化工股份有限公司 | Electro-conductive pearlescent pigment |
| JP2016052794A (en) * | 2011-07-21 | 2016-04-14 | エーエムエス−パテント アクチェンゲゼルシャフト | Laser beam weld method and molded component manufactured by the method |
| JP7175185B2 (en) | 2018-12-22 | 2022-11-18 | 太平化学製品株式会社 | Resin composition for laser marking and sheet for laser marking |
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| JP2002194238A (en) * | 2000-12-18 | 2002-07-10 | Merck Patent Gmbh | Laser-markable plastic, its preparation and its usage |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103249572A (en) * | 2010-10-26 | 2013-08-14 | 沙特基础创新塑料Ip私人有限责任公司 | Laser direct structuring materials with all color capability |
| JP2016052794A (en) * | 2011-07-21 | 2016-04-14 | エーエムエス−パテント アクチェンゲゼルシャフト | Laser beam weld method and molded component manufactured by the method |
| US9878490B2 (en) | 2011-07-21 | 2018-01-30 | Ems-Patent Ag | Laser beam welding method and molded components fabricated thereby |
| CN103756370A (en) * | 2014-01-10 | 2014-04-30 | 河北欧克精细化工股份有限公司 | Electro-conductive pearlescent pigment |
| JP7175185B2 (en) | 2018-12-22 | 2022-11-18 | 太平化学製品株式会社 | Resin composition for laser marking and sheet for laser marking |
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