JP2600033B2 - Epoxy resin composition suitable for carbon dioxide laser printing - Google Patents
Epoxy resin composition suitable for carbon dioxide laser printingInfo
- Publication number
- JP2600033B2 JP2600033B2 JP3275881A JP27588191A JP2600033B2 JP 2600033 B2 JP2600033 B2 JP 2600033B2 JP 3275881 A JP3275881 A JP 3275881A JP 27588191 A JP27588191 A JP 27588191A JP 2600033 B2 JP2600033 B2 JP 2600033B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- laser
- particle size
- coloring material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気電子部品の絶縁被
覆に用いられ、炭酸ガスレーザー（以下、ＣＯ2 レーザ
ーという）の照射によりその絶縁被覆表面に鮮明な印字
を施すことのできるＣＯ2 レーザー印字に適したエポキ
シ樹脂組成物に関するものである。The present invention relates are used in the insulating coating of the electric and electronic components, carbon dioxide laser (hereinafter, CO of 2 laser) capable of performing clear printing on the insulating coating surface by the irradiation of the CO 2 The present invention relates to an epoxy resin composition suitable for laser printing.
【０００２】[0002]
【従来の技術】従来、エポキシ樹脂組成物により絶縁被
覆された電気電子部品に特性や型番を明示するため印字
をする際、熱硬化性のインクや紫外線硬化性のインクが
用いられているが、工程の合理化を目的としてより短時
間で印字できる方法が要求されている。2. Description of the Related Art Conventionally, thermosetting inks and ultraviolet curable inks have been used for printing on electrical and electronic parts insulated with an epoxy resin composition to clearly indicate characteristics and model numbers. A method capable of printing in a shorter time is required for the purpose of streamlining the process.
【０００３】この対応方法の１つのとして、レーザーの
照射による印字システムが注目されている。このレーザ
ー印字システムは、文字やパターン状にレーザーを照射
された部分が熱エネルギーにより変色する、あるいは照
射された部分が昇華し表面粗化され、光の散乱によって
文字やパターンが識別できるものであり、この方法の印
字時間は0.01秒以下であり、従来の熱あるいは紫外線硬
化性のインクが硬化に数分〜数10分を必要とするのに比
べ、大幅に短縮されものである。[0003] As one of the methods for responding to this, a printing system using laser irradiation has attracted attention. In this laser printing system, the parts irradiated with laser in the form of letters or patterns are discolored by thermal energy, or the irradiated parts are sublimated and the surface is roughened, and letters and patterns can be identified by scattering of light. The printing time of this method is 0.01 second or less, which is much shorter than the conventional heat or ultraviolet curable ink which requires several minutes to several tens of minutes for curing.
【０００４】しかし、従来のエポキシ樹脂組成物の絶縁
被覆にレーザーを照射した場合、単に被覆表面を粗化す
るのみで、変色がおこらず、鮮明な文字やパターンを印
字することができなかった。However, when a conventional insulating coating of an epoxy resin composition is irradiated with a laser, the surface of the coating is simply roughened, discoloration does not occur, and clear characters and patterns cannot be printed.
【０００５】最近、従来のエポキシ樹脂組成物に黄色の
水酸化第二鉄を含有させるとレーザー照射によって黄色
から褐色に変色することが見出された（特開昭62-50360
号公報）。Recently, it has been found that when a conventional epoxy resin composition contains yellow ferric hydroxide, the color changes from yellow to brown by laser irradiation (Japanese Patent Laid-Open No. Sho 62-50360).
No.).
【０００６】水酸化第二鉄は黄色であるため、黄、橙色
のような色相にしか用いることができないが、塩基性炭
酸銅や塩基性炭酸鉛等を用いることによって青や緑色の
下地、特に淡色系の下地に黒色のレーザー印字を施すこ
とが可能になった。Since ferric hydroxide is yellow, it can be used only for a hue such as yellow or orange. However, by using basic copper carbonate or basic lead carbonate, a blue or green base, especially It became possible to apply black laser printing on a light-colored base.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、より低エネ
ルギーのＣＯ2 レーザー光で変色する樹脂組成物を得ん
として鋭意検討した結果、一次粒子の平均粒径が５μｍ
以下である微粒子のシュウ酸銅（II）等のレーザー発色
材を含有させると、従来、変色度の少なかった低エネル
ギーのＣＯ2 レーザー光でも明瞭に変色させられること
を見出し、更にこの知見に基づき種々研究を進めて本発
明を完成するに至ったものである。According to the present invention, as a result of intensive studies on obtaining a resin composition which changes color with a lower energy CO 2 laser beam, the average particle size of the primary particles is 5 μm.
It has been found that the addition of the following fine particles of a laser coloring material such as copper (II) oxalate can clearly change the color even with low-energy CO 2 laser light, which had a low degree of color change. The present inventors have completed various studies and completed the present invention.
【０００８】本発明の目的とするところは電気的特性及
び他の諸特性を低下させることなく、低エネルギーのＣ
Ｏ2 レーザー光でも照射により樹脂表面に鮮明な印字を
施すことのできる硬化物を与えるエポキシ樹脂組成物を
提供することにある。It is an object of the present invention to provide a low energy C without deteriorating electrical and other characteristics.
An object of the present invention is to provide an epoxy resin composition which gives a cured product capable of giving a clear print on a resin surface by irradiation even with O 2 laser light.
【０００９】[0009]
【課題を解決するための手段】本発明は、一次粒子の平
均粒径が５μｍ以下である微粒子のシュウ酸銅（II）等
のレーザー発色材を含有することを特徴とするＣＯ2 レ
ーザー印字に適したエポキシ樹脂組成物に関するもので
ある。According to the present invention, there is provided a CO 2 laser printing method characterized by containing a laser coloring material such as copper (II) oxalate of fine particles having an average primary particle size of 5 μm or less. It relates to a suitable epoxy resin composition.
【００１０】本発明のエポキシ樹脂組成物に、一次粒子
の平均粒径５μｍ以下の細かい発色材を用いる理由を、
発色材としてシュウ酸銅を用いた場合について以下に述
べる。シュウ酸銅（II）は淡青色の粉末であり、加熱す
ると200〜300℃で脱炭酸し酸化銅（II）に変化し、黒色
となる。The reason for using a fine coloring material having an average primary particle size of 5 μm or less in the epoxy resin composition of the present invention is as follows.
The case where copper oxalate is used as a coloring material will be described below. Copper (II) oxalate is a pale blue powder, and when heated, decarbonates at 200-300 ° C and changes to copper (II) oxide, turning black.
【００１１】従って、シュウ酸銅（II）を含有したエポ
キシ樹脂組成物に対し文字やパターン状にレーザーを照
射すると、樹脂表面がレーザーの熱エネルギーにより加
熱され、樹脂中に含有されたシュウ酸銅（II）が上記化
学反応を生じ黒色となる。この時、発色材が一次粒子の
平均粒径５μｍ以下の微粒子として含有されている場
合、シュウ酸銅（II）等のレーザー発色材の分散性が向
上するため、樹脂組成物中に均一にレーザー発色材を分
散させることができる。すなわち低エネルギーのＣＯ2
レーザー光でも文字やパターンを鮮明に印字することが
できる。Therefore, when the epoxy resin composition containing copper (II) oxalate is irradiated with a laser in the form of letters or patterns, the resin surface is heated by the thermal energy of the laser, and the copper oxalate contained in the resin is heated. (II) undergoes the above chemical reaction and turns black. At this time, if the coloring material is contained as fine particles having an average primary particle size of 5 μm or less, the dispersibility of the laser coloring material such as copper (II) oxalate is improved, so that the laser is uniformly dispersed in the resin composition. A coloring material can be dispersed. That is, low energy CO 2
Characters and patterns can be printed clearly even with laser light.
【００１２】本発明に用いられるシュウ酸銅（II）など
の発色材の粒度は、一次粒子の平均粒径が５μｍ以下で
あるが、好ましくは１μｍである。その理由はエポキシ
樹脂組成物に発色材を混合分散させた際、一次粒子が５
μm以上の平均粒径では電子電気部品に被覆させた際表
面に斑点状となり、部品の商品価値を低下させるばかり
でなく、分散が不充分となりやすくレーザーが照射され
た際、発色材が存在しない部分では変色がおこらず、文
字やパターンがとぎれ鮮明な印字ができなくなる場合が
ある。なお、この平均粒径の測定法は特に限定されない
が、電子顕微鏡などにより容易に測定することができ
る。The particle size of the coloring material such as copper (II) oxalate used in the present invention is such that the average particle size of the primary particles is 5 μm or less, preferably 1 μm. The reason is that when the color former is mixed and dispersed in the epoxy resin composition,
With an average particle size of μm or more, when coated on electronic and electrical parts, the surface becomes spot-like, not only lowering the commercial value of the part, but also dispersing becomes insufficient and there is no coloring material when irradiated with laser. In some parts, discoloration does not occur, and characters and patterns may be interrupted to make clear printing impossible. The method for measuring the average particle size is not particularly limited, but can be easily measured with an electron microscope or the like.
【００１３】発色材の含有量は 0.5〜20重量％が好まし
い。この理由は、含有量が 0.5重量％以下では、レーザ
ーが照射されても変色する度合が小さく鮮明な印字とな
りにくい。一方、20重量％を越えると、樹脂組成物の電
気絶縁性が低下し、電子電気部品用絶縁材料としての本
来の性能を満足しにくくなるためである。The content of the coloring material is preferably 0.5 to 20% by weight. The reason is that when the content is 0.5% by weight or less, the degree of discoloration is small even when irradiated with a laser, and it is difficult to obtain clear printing. On the other hand, if the content exceeds 20% by weight, the electrical insulation of the resin composition is reduced, and it is difficult to satisfy the original performance as an insulating material for electronic and electrical parts.
【００１４】本発明に用いられるエポキシ樹脂として
は、例えばビスフェノールＡ型エポキシ樹脂、ビスフェ
ノールＦ型エポキシ樹脂等のジグリシジルエーテル型エ
ポキシ樹脂、フェノールノボラック型エポキシ樹脂、ク
レゾールノボラック型エポキシ樹脂等のノボラック型エ
ポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリ
シジルアミン型エポキシ樹脂、線状脂肪族型エポキシ樹
脂、被素環型エポキシ樹脂、ハロゲン化エポキシ樹脂等
があげられるが、これらに限定されるものではない。The epoxy resin used in the present invention includes, for example, diglycidyl ether type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin. Examples thereof include, but are not limited to, resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, linear aliphatic type epoxy resins, elementary ring type epoxy resins, and halogenated epoxy resins.
【００１５】本発明に用いられる硬化剤及び硬化促進剤
としては、酸無水物、ポリアミン、ノボラック型フェノ
ール樹脂、第３級アミン、イミダゾール化合物等がある
が、いずれを用いてもよい。As the curing agent and curing accelerator used in the present invention, there are acid anhydride, polyamine, novolak type phenol resin, tertiary amine, imidazole compound and the like, and any of them may be used.
【００１６】無機充填剤としては、例えばジルコン粉
末、タルク粉末、結晶シリカ粉末、溶融シリカ粉末、炭
酸カルシウム粉末、マグネシア粉末、ケイ酸カルシウム
粉末、水和アルミナ粉末、アルミナ粉末等が挙げられ
る。かかる無機充填剤は平均粒径が10μｍ以下のものが
発色材の分散を良好にし鮮明な発色のために好ましい。Examples of the inorganic filler include zircon powder, talc powder, crystalline silica powder, fused silica powder, calcium carbonate powder, magnesia powder, calcium silicate powder, hydrated alumina powder, and alumina powder. Such an inorganic filler having an average particle size of 10 μm or less is preferable for good dispersion of the coloring material and for vivid color formation.
【００１７】本発明により得られる樹脂組成物はシュウ
酸銅（II）の場合、その色調により通常淡青色を呈する
が、赤、青、緑、黒、白色等の顔料を併用してもよい。
本発明の樹脂組成物は注型材料等の液状、粉体塗料等の
粉状、成型材料等の顆粒状、塊状等いずれの状態でもよ
い。In the case of copper (II) oxalate, the resin composition obtained by the present invention usually exhibits a light blue color depending on the color tone, but a pigment such as red, blue, green, black or white may be used in combination.
The resin composition of the present invention may be in any state such as a liquid state such as a casting material, a powder state such as a powder coating, a granular state such as a molding material, and a lump.
【００１８】本発明のエポキシ樹脂組成物を製造する方
法として、例えば粉体塗料の場合をあげると、所定の割
合で秤量した原料成分をミキサーによって充分混合した
のち、エクストルーダー、コニーダーあるいはロール等
で溶融混練し、次いで粉砕機にて粉砕する方法等があ
る。上記方法により得られる粉体塗料により電子電気部
品の絶縁被覆を行う方法としては、流動浸漬法、静電流
動浸漬法、ころがし法、ふりかけ法、ホットスプレー
法、静電スプレー法等、一般の粉体塗装方法が用いられ
る。As a method of producing the epoxy resin composition of the present invention, for example, in the case of a powder coating, a raw material component weighed at a predetermined ratio is sufficiently mixed by a mixer, and then mixed with an extruder, a co-kneader or a roll. There is a method of melt-kneading and then pulverizing with a pulverizer. Examples of a method for performing insulation coating of electronic / electric parts with the powder coating obtained by the above method include general powders such as a fluid immersion method, an electrostatic fluid immersion method, a rolling method, a sprinkling method, a hot spray method, and an electrostatic spray method. A body painting method is used.
【００１９】又、注型材料、成型材料の場合についても
公知の技術で製造でき、絶縁材料として使用できる。Also, casting materials and molding materials can be manufactured by known techniques and used as insulating materials.
【００２０】[0020]
【実施例】次に本発明を実施例により更に詳しく説明す
る。Next, the present invention will be described in more detail with reference to examples.
【００２１】実施例１ ビスフェノールＡ型エポキシ樹脂（エポキシ当量950) ５０重量部 シュウ酸銅（II）（一次粒子の平均粒径0.8μｍ、平均粒径15μｍ） ５重量部 炭酸カルシウム粉末（平均粒径 7μｍ） ５０重量部 ２−メチルイミダゾール １重量部 上記組成物を配合し、ヘンシェルミキサーでブレンド
し、コニーダーにて溶融混練した後、粉砕機で粉砕する
ことにより平均粒径60〜70μｍのエポキシ樹脂組成物の
粉体塗料を得た。Example 1 Bisphenol A type epoxy resin (epoxy equivalent: 950) 50 parts by weight Copper (II) oxalate (average particle size of primary particles 0.8 μm, average particle size 15 μm) 5 parts by weight Calcium carbonate powder (average particle size) 7 μm) 50 parts by weight 2-methylimidazole 1 part by weight The above composition is blended, blended by a Henschel mixer, melt-kneaded by a co-kneader, and then pulverized by a pulverizer to obtain an epoxy resin composition having an average particle size of 60 to 70 μm. A powder coating was obtained.
【００２２】実施例２ 実施例１において、発色材として一次粒子の平均粒径３
μｍ、平均粒径15μｍのシュウ酸銅（II）を使用し、他
は同様の方法にて平均粒径60〜70μｍのエポキシ樹脂組
成物の粉体塗料を得た。Example 2 In Example 1, the average particle size of the primary particles was 3 as the coloring material.
A powder coating of an epoxy resin composition having an average particle size of 60 to 70 μm was obtained in the same manner except that copper (II) oxalate having an average particle size of 15 μm was used.
【００２３】比較例１ 実施例１において、発色材として一次粒子の平均粒径10
μｍのシュウ酸銅（II）を使用し、他は同様の方法にて
平均粒径60〜70μｍのエポキシ樹脂組成物の粉体塗料を
得た。Comparative Example 1 In Example 1, the average particle size of primary particles was 10 as a coloring material.
A powder coating of an epoxy resin composition having an average particle size of 60 to 70 μm was obtained in the same manner except that copper (II) oxalate of μm was used.
【００２４】比較例２ 実施例１において、発色材として一次粒子の平均粒径20
μｍのシュウ酸銅（II）を使用し、他は同様の方法にて
平均粒径60〜70μｍのエポキシ樹脂組成物の粉体塗料を
得た。Comparative Example 2 In Example 1, the average particle size of the primary particles was 20 as the coloring material.
A powder coating of an epoxy resin composition having an average particle size of 60 to 70 μm was obtained in the same manner except that copper (II) oxalate of μm was used.
【００２５】実施例１、２及び比較例１、２の樹脂組成
物について 100℃で２時間硬化させた。この試料に炭酸
ガスレーザー（ウシオ電機（株）製 400型レーザーマー
ク、エネルギー密度４Joule/cm2 及び６Joule/cm2）を
用いて、100万分の１秒間所定のマスクを通してレーザ
ーを照射して、硬化物の表面にマーキングを施した。ま
た、上記硬化物の絶縁被覆電圧をJIS K 6911により測定
した。結果を表１に示す。The resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were cured at 100 ° C. for 2 hours. Using a carbon dioxide laser (Ushio Inc. 400 type laser mark, energy density 4 Joule / cm 2 and 6 Joule / cm 2 ), the sample is irradiated with a laser through a predetermined mask for 1 / 1,000,000 second for curing. The surface of the object was marked. The insulation coating voltage of the cured product was measured according to JIS K 6911. Table 1 shows the results.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明のレーザー印字に適したエポキシ
樹脂組成物を絶縁被覆材として用いた場合、電気的特性
及び他の特性を低下させることなく、低エネルギーのレ
ーザーの照射により樹脂表面に鮮明な印字を施すことの
できる被覆を与えることができる。従って、従来より非
常に短時間で印字できるため、電気電子部品の生産工程
の合理化をはかることができる。According to the present invention, when the epoxy resin composition suitable for laser printing according to the present invention is used as an insulating coating material, the surface of the resin can be sharpened by irradiating a low-energy laser without deteriorating electrical characteristics and other characteristics. And a coating that can be applied to the printing. Therefore, since printing can be performed in a much shorter time than in the past, the production process of electric and electronic components can be rationalized.
Claims (2)
なるエポキシ樹脂組成物において、シュウ酸銅（II）等
のレーザー発色材を有し、かつ該発色材の一次粒子の平
均粒径が５μｍ以下であることを特徴とするエポキシ樹
脂組成物。1. An epoxy resin composition comprising an epoxy resin, a curing agent, a filler, and the like, comprising a laser coloring material such as copper (II) oxalate, and wherein the primary particles of the coloring material have an average particle size of 5 μm. An epoxy resin composition characterized by the following.
量部含有することを特徴とする請求項１記載のエポキシ
樹脂組成物。2. The epoxy resin composition according to claim 1, wherein the coloring material is contained in an amount of 0.5 to 20 parts by weight based on the composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3275881A JP2600033B2 (en) | 1991-10-24 | 1991-10-24 | Epoxy resin composition suitable for carbon dioxide laser printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3275881A JP2600033B2 (en) | 1991-10-24 | 1991-10-24 | Epoxy resin composition suitable for carbon dioxide laser printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05117497A JPH05117497A (en) | 1993-05-14 |
| JP2600033B2 true JP2600033B2 (en) | 1997-04-16 |
Family
ID=17561738
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3275881A Expired - Lifetime JP2600033B2 (en) | 1991-10-24 | 1991-10-24 | Epoxy resin composition suitable for carbon dioxide laser printing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2600033B2 (en) |
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| JPS6381117A (en) * | 1986-09-25 | 1988-04-12 | Toshiba Corp | Epoxy resin composition and resin-sealed type semiconductor device using said composition |
| JPS63239059A (en) * | 1986-11-14 | 1988-10-05 | Mitsubishi Electric Corp | Laser marking method |
| JPH0352945A (en) * | 1989-07-20 | 1991-03-07 | Sumitomo Bakelite Co Ltd | Epoxy resin composition suitable for laser printing |
-
1991
- 1991-10-24 JP JP3275881A patent/JP2600033B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6250360A (en) * | 1985-08-30 | 1987-03-05 | Sumitomo Bakelite Co Ltd | Epoxy resin composition suitable for use in laser-beam printing |
| JPS62136861A (en) * | 1985-12-10 | 1987-06-19 | Nitto Electric Ind Co Ltd | Resin sealed semiconductor device |
| JPS6381117A (en) * | 1986-09-25 | 1988-04-12 | Toshiba Corp | Epoxy resin composition and resin-sealed type semiconductor device using said composition |
| JPS63239059A (en) * | 1986-11-14 | 1988-10-05 | Mitsubishi Electric Corp | Laser marking method |
| JPH0352945A (en) * | 1989-07-20 | 1991-03-07 | Sumitomo Bakelite Co Ltd | Epoxy resin composition suitable for laser printing |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05117497A (en) | 1993-05-14 |
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