JP2600029B2 - Epoxy resin composition suitable for carbon dioxide laser printing - Google Patents
Epoxy resin composition suitable for carbon dioxide laser printingInfo
- Publication number
- JP2600029B2 JP2600029B2 JP3153498A JP15349891A JP2600029B2 JP 2600029 B2 JP2600029 B2 JP 2600029B2 JP 3153498 A JP3153498 A JP 3153498A JP 15349891 A JP15349891 A JP 15349891A JP 2600029 B2 JP2600029 B2 JP 2600029B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- laser
- average particle
- powder
- 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
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- 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、シュウ酸銅（II）等のレーザ
ー発色材の他に平均粒径が10μｍ以下と細かい充填剤を
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。DISCLOSURE OF THE INVENTION The present invention has been studied intensively to obtain a resin composition which changes color with lower energy CO 2 laser light. It has been found that the addition of a fine filler having an average particle size of 10 μm or less can clearly change the color even with low-energy CO 2 laser light, which had a low degree of color change in the past. The invention has been completed.
【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、シュウ酸銅
（II）等のレーザー発色材の他に、平均粒径が10μｍ以
下と細かい充填剤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。SUMMARY OF THE INVENTION The present invention provides a CO 2 laser printing method characterized by containing, in addition to a laser coloring material such as copper (II) oxalate, a fine filler having an average particle size of 10 μm or less. The present invention relates to an epoxy resin composition suitable for:
【００１０】本発明のエポキシ樹脂組成物に平均粒径10
μｍ以下の細かい充填剤を用いる理由を、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 epoxy resin composition of the present invention has an average particle size of 10
The reason why a fine filler having a size of not more than μm is used will be described below in the case where copper oxalate is used as a coloring material. Copper (II) oxalate is a pale blue powder that can be heated to 200-300
Decarboxylates at ℃ and changes to copper (II) oxide and turns 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、樹脂組成物に平均粒
径が10μｍ以下の細かい充填剤が含有されていると、シ
ュウ酸銅（II）等のレーザー発色材の分散を促す効果が
あるため、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 resin composition contains a fine filler having an average particle diameter of 10 μm or less, it has an effect of promoting the dispersion of the laser coloring material such as copper oxalate (II). Can be dispersed with a laser coloring material. That is, characters and patterns can be clearly printed even with low energy CO 2 laser light.
【００１２】本発明に用いられるシュウ酸銅（II）など
の発色材の粒度は平均粒径が 100μｍ以下であることが
好ましい。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、100μm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
変色がおさらず、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。The particle size of the coloring material such as copper oxalate (II) used in the present invention is preferably an average particle size of 100 μm or less. The reason is that when the coloring material is mixed and dispersed in the epoxy resin composition, if the average particle diameter is 100 μm or more, when coated on an electronic / electric part, the surface becomes spot-like, which not only reduces the commercial value of the part, but also reduces the dispersion. When laser irradiation is performed, discoloration does not occur in portions where no coloring material is present, and characters and patterns may be cut off to make clear printing impossible.
【００１３】なお、この平均粒径はコールターカウンタ
ー（日科機(株)製）により得られる粒度分布を重量平均
することにより求めるのが適当であるが、コールターカ
ウンター以外の測定方法により求めてもよい。The average particle size is suitably determined by weight-averaging the particle size distribution obtained with a Coulter counter (manufactured by Nikkaki Co., Ltd.), but may also be determined by a measuring method other than the Coulter counter. Good.
【００１４】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
らない。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 clear printing is not obtained. 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.
【００１５】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 is, for example, a diglycidyl ether type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a novolak type epoxy resin such as 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.
【００１６】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。無機充填剤としては、平均
粒径が10μｍ以下のもので、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。The curing agent and curing accelerator used in the present invention include acid anhydrides, polyamines, novolak type phenol resins, tertiary amines, imidazole compounds and the like, and any of them may be used. As the inorganic filler, those having an average particle size of 10 μm or less, for example, zircon powder, talc powder, crystalline silica powder, fused silica powder, calcium carbonate powder, magnesia powder, calcium silicate powder, hydrated alumina powder, alumina powder And the like.
【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）（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 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 was blended, blended with a Henschel mixer, melt-kneaded with a co-kneader, and then pulverized with a pulverizer to obtain a powder coating of an epoxy resin composition having an average particle size of 60 to 70 μm.
【００２２】実施例２ 実施例１において、無機充填剤を炭酸カルシウム粉末
（平均粒径 8μｍ）に替え、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 A powder coating of an epoxy resin composition having an average particle size of 60 to 70 μm was prepared in the same manner as in Example 1, except that the inorganic filler was changed to calcium carbonate powder (average particle size: 8 μm). Obtained.
【００２３】比較例１ 実施例１において、無機充填剤を炭酸カルシウム粉末
（平均粒径17μｍ）に替え、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 A powder coating of an epoxy resin composition having an average particle size of 60 to 70 μm was prepared in the same manner as in Example 1 except that the inorganic filler was changed to calcium carbonate powder (average particle size: 17 μm). Obtained.
【００２４】比較例２ 実施例１において、無機充填剤を炭酸カルシウム粉末
（平均粒径30μｍ）に替え、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 A powder coating of an epoxy resin composition having an average particle diameter of 60 to 70 μm was prepared in the same manner as in Example 1 except that the inorganic filler was changed to calcium carbonate powder (average particle diameter: 30 μm). Obtained.
【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、かつ前記充填剤の平均粒径が
１０μｍ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, having a laser coloring material such as copper (II) oxalate, and the filler having an average particle size of 10 μm or less. An epoxy resin composition, characterized in that:
５〜２０重量部含有することを特徴とする請求項１又は
２記載のエポキシ樹脂組成物。2. Copper (II) oxalate is added to the composition in an amount of 0,1%.
The epoxy resin composition according to claim 1, wherein the epoxy resin composition is contained in an amount of 5 to 20 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3153498A JP2600029B2 (en) | 1991-06-25 | 1991-06-25 | Epoxy resin composition suitable for carbon dioxide laser printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3153498A JP2600029B2 (en) | 1991-06-25 | 1991-06-25 | Epoxy resin composition suitable for carbon dioxide laser printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH051204A JPH051204A (en) | 1993-01-08 |
| JP2600029B2 true JP2600029B2 (en) | 1997-04-16 |
Family
ID=15563878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3153498A Expired - Lifetime JP2600029B2 (en) | 1991-06-25 | 1991-06-25 | Epoxy resin composition suitable for carbon dioxide laser printing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2600029B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013149737A (en) * | 2012-01-18 | 2013-08-01 | Nitto Denko Corp | Flip-chip semiconductor device manufacturing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6018556A (en) * | 1983-07-12 | 1985-01-30 | Somar Corp | Powder coating composition |
| JPS62136861A (en) * | 1985-12-10 | 1987-06-19 | Nitto Electric Ind Co Ltd | Resin sealed semiconductor device |
| JPS641771A (en) * | 1987-06-25 | 1989-01-06 | Somar Corp | Epoxy resin powder coating composition |
| JPH0352945A (en) * | 1989-07-20 | 1991-03-07 | Sumitomo Bakelite Co Ltd | Epoxy resin composition suitable for laser printing |
-
1991
- 1991-06-25 JP JP3153498A patent/JP2600029B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6018556A (en) * | 1983-07-12 | 1985-01-30 | Somar Corp | Powder coating composition |
| JPS62136861A (en) * | 1985-12-10 | 1987-06-19 | Nitto Electric Ind Co Ltd | Resin sealed semiconductor device |
| JPS641771A (en) * | 1987-06-25 | 1989-01-06 | Somar Corp | Epoxy resin powder coating composition |
| 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 |
|---|---|
| JPH051204A (en) | 1993-01-08 |
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