JPH0583581B2 - - Google Patents
Info
- Publication number
- JPH0583581B2 JPH0583581B2 JP2132643A JP13264390A JPH0583581B2 JP H0583581 B2 JPH0583581 B2 JP H0583581B2 JP 2132643 A JP2132643 A JP 2132643A JP 13264390 A JP13264390 A JP 13264390A JP H0583581 B2 JPH0583581 B2 JP H0583581B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- resin composition
- laser
- copper oxalate
- 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 - Fee Related
Links
- 239000003822 epoxy resin Substances 0.000 claims description 33
- 229920000647 polyepoxide Polymers 0.000 claims description 33
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000004566 IR spectroscopy Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- 239000000843 powder Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 5
- 230000002745 absorbent Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000007648 laser printing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229940043256 calcium pyrophosphate Drugs 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LPDWOEAWNMGOAO-UHFFFAOYSA-N (4,7,8-trimethylquinolin-2-yl)hydrazine Chemical compound CC1=CC(NN)=NC2=C(C)C(C)=CC=C21 LPDWOEAWNMGOAO-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910008284 Si—F Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940074568 calcium hexafluorosilicate Drugs 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- -1 glycidyl ester Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010330 laser marking Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
〔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、レーザー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。
〔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。
この対応方法の1つとして、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、光の散乱によつ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
幅に短縮されるものである。
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つた。
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つて黄
色から褐色に変色することが見い出された(特開
昭62−50360号公報)。
しかし、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ず、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、これからの課題とされてき
た。
〔発明が解決しようとする課題〕
本発明は、従来不可能であつた青や緑の明色か
らレーザーにより黒色に変色する樹脂組成物を得
んとして鋭意検討した結果、シユウ酸銅()を
含有させるとレーザーを照射した際淡青色から黒
色に変色すること、更に炭酸ガスレーザーにおい
ては赤外分光測定で特性吸収ピークを920〜970cm
-1の波数域をもつ化合物(以下、吸収剤と呼ぶ)
を加えることにより変色の度合をより上げられる
ことを見出した。
本発明の目的とするところは電気的特性および
他の諸特性を低下させることなく、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。
〔課題を解決するための手段〕
本発明は、シユウ酸銅()及び吸収剤を含有
することを特徴とする炭酸ガスレーザー印字に適
したエポキシ樹脂組成物に関するものである。
本発明のエポキシ樹脂組成物にシユウ酸銅
()を用いる理由を以下に述べる。
シユウ酸銅()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()に変色
し、黒色となる。
従つて、シユウ酸銅()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ユウ酸銅
()が上記化学反応を生じ黒色となる。すなわ
ちレーザーに照射された部分のみ黒色となり、照
射されない部分は淡青色のままのため、淡青色の
下地に黒色の文字やパターンを鮮明に印字するこ
とができる。
更に炭酸ガスレーザの場合、シユウ酸銅()
に吸収剤を併用すると発色の度合を強めることが
できる。炭酸ガスレーザ光の波数は943cm-1であ
るため、この波数の光をよく吸収する物質が樹脂
組成物中に存在すると、レーザ光のエネルギーを
樹脂組成物中に取り込む割合が増加する。吸収し
たエネルギーは吸収剤の分子内振動により熱に変
えられるため吸収剤が存在しない場合に比べると
樹脂組成物の温度がより上がり分解反応を促進す
るためである。
本発明に用いられるシユウ酸銅()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シユウ酸銅()
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、シユウ酸銅()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。
シユウ酸銅()の含有量としては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ず、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。
本発明に用いられる吸収剤としてはピロリン酸
カルシウムやトリフエニルホスフイン等のP−
O、P−Ph(P:リン、O:酸素、Ph:フエニル
基)結合をもつ化合物やヘキサフルオロケイ酸カ
ルシウム等のSi−F(Si:ケイ素、F:フツ素)
結合をもつ化合物等が上げられるが、これらに限
定されるものではない。
本発明に用いられるエポキシ樹脂としては、例
えばビスフエノールA型エポキシ樹脂、ビスフエ
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、フエノールボラツク型エポキ
シ樹脂、クレゾールノボラツク型エポキシ樹脂等
のノボラツク型エポキシ樹脂、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、複素環型エポ
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。
本発明に用いられる硬化剤および硬化促進剤と
しては、酸無水物、ポリアミン、ノボラツク型フ
エノール樹脂、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。又必要に
より公知の無機充填剤、たとえばジルコン粉末、
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
等を配合してもよい。
本発明により得られる樹脂組成物はシユウ酸銅
()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。
本発明の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つて充分混合した
のち、エキストルーダー、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
方法がある。上記方法により得られた粉体塗料に
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、ホツトスプレー法、静電スプレー法
等一般の粉体塗装方法が用いられる。
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。
〔実施例〕
次に本発明を実施例により更に詳しく説明す
る。
実施例 1
ビスフエノールA型エポキシ樹脂
(エポキシ当量950) 50重量部
シユウ酸銅()(平均粒径15μm) 5重量部
結晶シリン粉末 50重量部
2メチルイミダゾール 1重量部
ピロリン酸カルシウム 1重量部
上記組成物を配合し、ヘンシエルミキサーでブ
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。
実施例 2
実施例1において、シユウ酸銅()の添加量
を20重量部に替え、他は同様にして平均粒径60〜
70μmのエポキシ樹脂組成物の粉体塗料を得た。
比較例 1
実施例1においてピロリン酸カルシウムを除
き、他は同様にして平均粒径60〜70μmのエポキ
シ樹脂組成物の粉体塗料を得た。
比較例 2
実施例1において、シユウ酸銅()の添加量
を0.1重量部に替え、他は同様にして平均粒径60
〜70μmのエポキシ樹脂組成物の粉体塗料を得た。
比較例 3
実施例1において、シユウ酸銅()の添加量
を50重量部に替え、他は同様にして平均粒径60〜
70μmのエポキシ樹脂組成物の粉体塗料を得た。
実施例1、2及び比較例1〜3の樹脂組成物に
ついて硬化物を作製した。
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JISK6911
により測定した。結果を表−1に示す。
[Industrial Application Field] The present invention relates to an epoxy resin composition suitable for laser printing, which is used for insulating coatings of electrical and electronic components, and is capable of making clear markings on the surface of the insulating coating by laser irradiation. be. [Prior Art] Conventionally, thermosetting inks and ultraviolet curable inks have been used to print on electrical and electronic components coated with epoxy resin compositions to clearly indicate their characteristics and model numbers. For the purpose of streamlining the process, there is a need for a method that can print in a shorter time. As one method for dealing with this problem, a printing system using laser irradiation is attracting attention. In this laser printing system, the part of the text or pattern that is irradiated with the laser changes color due to thermal energy, or the part that is irradiated sublimates and becomes roughened, and the text or pattern can be identified by the scattering of light. The printing time of this method is 0.01 seconds or less, which is significantly shorter than the conventional heat or ultraviolet curable ink, which takes several minutes to several tens of minutes to cure. However, when a conventional insulating coating of an epoxy resin composition is irradiated with a laser, the coating surface is merely roughened, no discoloration occurs, and clear characters or patterns cannot be printed. Recently, it has been discovered that when a conventional epoxy resin composition contains yellow ferric hydroxide, the composition changes color from yellow to brown upon laser irradiation (Japanese Patent Laid-Open Publication No. 50360/1983). However, since ferric hydroxide is yellow, yellow,
It can only be used for hues such as orange, and a future challenge has been to apply black laser printing to blue or green bases, especially light-colored bases. [Problems to be Solved by the Invention] As a result of extensive research in an effort to obtain a resin composition that changes color from bright blue or green colors to black by laser, which was previously impossible, the present invention has developed a method using copper oxalate (). If it is included, the color will change from pale blue to black when irradiated with laser, and in addition, when carbon dioxide laser is used, the characteristic absorption peak will be 920 to 970 cm in infrared spectroscopy.
Compounds with a wavenumber range of -1 (hereinafter referred to as absorbers)
It has been found that the degree of discoloration can be further increased by adding . An object of the present invention is to provide an epoxy resin composition that provides a cured product that can be clearly printed on the resin surface by laser irradiation without degrading electrical properties or other properties. be. [Means for Solving the Problems] The present invention relates to an epoxy resin composition suitable for carbon dioxide laser printing, which is characterized by containing copper oxalate (2) and an absorbent. The reason for using copper oxalate () in the epoxy resin composition of the present invention will be described below. Copper oxalate () is a pale blue powder, and when heated, it decarboxylates at 200-300°C and changes color to copper oxide (), turning black. Therefore, when an epoxy resin composition containing copper oxalate (2) is irradiated with a laser in the form of letters or patterns, the resin surface is heated by the laser's thermal energy, and the copper oxalate (2) contained in the resin is heated. The above chemical reaction occurs and the color turns black. In other words, only the parts irradiated by the laser turn black, and the parts not irradiated remain pale blue, making it possible to clearly print black characters and patterns on a pale blue background. Furthermore, in the case of carbon dioxide laser, copper oxalate ()
The degree of color development can be intensified by using an absorbent in combination. Since the wave number of carbon dioxide laser light is 943 cm -1 , if a substance that well absorbs light with this wave number is present in the resin composition, the rate at which the energy of the laser light is taken into the resin composition increases. This is because the absorbed energy is converted into heat by the intramolecular vibrations of the absorbent, which raises the temperature of the resin composition more than in the case where no absorbent is present, promoting the decomposition reaction. The average particle size of the copper oxalate used in the present invention is preferably 100 μm or less. The reason is that copper oxalate () is added to the epoxy resin composition.
When mixed and dispersed, if the average particle size is 100 μm or more, it will not only cause spots on the surface when coated on electronic and electrical parts, but also reduce the commercial value of the parts.
Dispersion tends to be insufficient, and when irradiated with a laser, discoloration does not occur in areas where copper oxalate () is not present, and characters and patterns may be interrupted, making it impossible to print clearly. The average particle diameter is suitably determined by weight-averaging the particle size distribution obtained using a Coulter Counter (manufactured by Nikkaki Co., Ltd.), but may be determined by a measuring method other than the Coulter Counter. The content of copper oxalate is preferably 0.5 to 20% by weight. The reason for this is that when the content is less than 0.5% by weight, the degree of discoloration is small even when irradiated with a laser, and clear printing cannot be achieved.
This is because if it exceeds this, the electrical insulation properties of the resin composition will decrease and it will become difficult to satisfy the original performance as an insulating material for electronic and electrical parts. Absorbents used in the present invention include P-calcium pyrophosphate and triphenylphosphine.
Compounds with O, P-Ph (P: phosphorus, O: oxygen, Ph: phenyl group) bonds and Si-F (Si: silicon, F: fluorine) such as calcium hexafluorosilicate
Examples include, but are not limited to, compounds having a bond. Examples of the epoxy resin used in the present invention include diglycidyl ether type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, novolak type epoxy resins such as phenol volak type epoxy resin, and cresol novolak type epoxy resin. Examples include, but are not limited to, epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, linear aliphatic type epoxy resins, heterocyclic type epoxy resins, and halogenated epoxy resins. The curing agent and curing accelerator used in the present invention include acid anhydrides, polyamines, novolac type phenolic resins, tertiary amines, imidazole compounds, etc., and any of them may be used. Also, if necessary, known inorganic fillers such as zircon powder,
Talc powder, crystalline silica powder, fused silica powder,
Calcium carbonate powder, magnesia powder, calcium silicate powder, hydrated alumina powder, alumina powder, etc. may be blended. The resin composition obtained by the present invention usually exhibits a light blue color due to the color tone of copper oxalate (), but red,
Pigments of blue, green, black, white, etc. may be used in combination. The resin composition of the present invention may be in any form, such as liquid as a casting material, powder as in a powder coating, granule or block as in a molding material. As a method for producing the resin composition of the present invention, for example, in the case of powder coating, raw ingredients weighed in a predetermined ratio are sufficiently mixed in a mixer, and then melt-kneaded in an extruder, co-kneader, roll, etc. Then, there is a method of pulverizing it using a pulverizer. Methods for insulating coating electronic and electrical parts with the powder coating obtained by the above method include fluid dipping method, electrostatic dynamic dipping method, rolling method,
General powder coating methods such as sprinkle method, hot spray method, and electrostatic spray method are used. In addition, casting materials and molding materials can also be manufactured using known techniques, and can be used as insulating materials. [Example] Next, the present invention will be explained in more detail with reference to Examples. Example 1 Bisphenol A type epoxy resin (epoxy equivalent: 950) 50 parts by weight Copper oxalate (average particle size 15 μm) 5 parts by weight Crystalline syrin powder 50 parts by weight 2 Methylimidazole 1 part by weight Calcium pyrophosphate 1 part by weight Above composition The materials were blended using a Henschel mixer, melt-kneaded using a co-kneader, and then ground using a grinder to obtain a powder coating of an epoxy resin composition having an average particle size of 60 to 70 μm. Example 2 In Example 1, the amount of copper oxalate () added was changed to 20 parts by weight, and the other things were the same, but the average particle size was 60~
A powder coating of 70 μm epoxy resin composition was obtained. Comparative Example 1 A powder coating of an epoxy resin composition having an average particle size of 60 to 70 μm was obtained in the same manner as in Example 1 except that calcium pyrophosphate was removed. Comparative Example 2 In Example 1, the amount of copper oxalate () added was changed to 0.1 part by weight, and the other things were the same, but the average particle size was 60.
A powder coating of ~70μm epoxy resin composition was obtained. Comparative Example 3 In Example 1, the amount of copper oxalate () added was changed to 50 parts by weight, and the other things were the same, but the average particle size was 60~
A powder coating of 70 μm epoxy resin composition was obtained. Cured products were prepared from the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3. A carbon dioxide laser (manufactured by Ushio Inc.) was applied to this sample.
400 type laser mark, energy density 6Joule/
cm 2 ) and irradiated a laser through a predetermined mask for 1/1 million seconds to mark the surface of the cured product. In addition, the insulation coating voltage of the above cured product was determined according to JISK6911.
It was measured by The results are shown in Table-1.
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
および他の特性を低下させることなく、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。従つて、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。
When the epoxy resin composition suitable for laser marking of the present invention is used as an insulating coating material, the coating allows clear markings to be made on the resin surface by laser irradiation without degrading electrical properties or other properties. can be given. Therefore, since printing can be performed in a much shorter time than conventionally, it is possible to rationalize the production process of electrical and electronic parts.
Claims (1)
エポキシ樹脂組成物において、シユウ酸銅()
及び赤外分光測定で特性吸収ピークを920〜970cm
-1の波数域にもつ化合物を含有することを特徴と
するエポキシ樹脂組成物。 2 シユウ酸銅()の平均粒径が100μm以下で
あ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。 3 シユウ酸銅()を組成物に対して0.5〜20
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。[Claims] 1. In an epoxy resin composition comprising an epoxy resin, a curing agent, a filler, etc., copper oxalate ()
and characteristic absorption peak of 920 to 970 cm in infrared spectroscopy.
An epoxy resin composition characterized by containing a compound having a wave number range of -1 . 2. The epoxy resin composition according to claim 1, wherein the average particle size of the copper oxalate (2) is 100 μm or less. 3 Copper oxalate () to the composition 0.5 to 20
Claim 1 or 2, characterized in that it contains parts by weight.
The epoxy resin composition described.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2132643A JPH0428758A (en) | 1990-05-24 | 1990-05-24 | Epoxy resin composition suitable for laser printing |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2132643A JPH0428758A (en) | 1990-05-24 | 1990-05-24 | Epoxy resin composition suitable for laser printing |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0428758A JPH0428758A (en) | 1992-01-31 |
JPH0583581B2 true JPH0583581B2 (en) | 1993-11-26 |
Family
ID=15086123
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2132643A Granted JPH0428758A (en) | 1990-05-24 | 1990-05-24 | Epoxy resin composition suitable for laser printing |
Country Status (1)
Country | Link |
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JP (1) | JPH0428758A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006191724A (en) * | 2005-01-05 | 2006-07-20 | Tokyo Micro:Kk | Small stepping motor and its manufacturing process |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59111892A (en) * | 1982-11-26 | 1984-06-28 | ヴアヴイン・ベスロ−テム・ヴエンノツトシヤツプ | Method of marking article |
JPS63179921A (en) * | 1987-01-21 | 1988-07-23 | Toshiba Corp | Sealing 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 |
JPH0211438A (en) * | 1988-06-27 | 1990-01-16 | Clarion Co Ltd | Device for reading information outside vehicle |
JPH0248984A (en) * | 1988-05-31 | 1990-02-19 | Dainippon Ink & Chem Inc | Laser marking method and resin composition for laser marking |
JPH0352945A (en) * | 1989-07-20 | 1991-03-07 | Sumitomo Bakelite Co Ltd | Epoxy resin composition suitable for laser printing |
-
1990
- 1990-05-24 JP JP2132643A patent/JPH0428758A/en active Granted
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59111892A (en) * | 1982-11-26 | 1984-06-28 | ヴアヴイン・ベスロ−テム・ヴエンノツトシヤツプ | Method of marking article |
JPS63239059A (en) * | 1986-11-14 | 1988-10-05 | Mitsubishi Electric Corp | Laser marking method |
JPS63179921A (en) * | 1987-01-21 | 1988-07-23 | Toshiba Corp | Sealing resin composition and resin-sealed type semiconductor device using said composition |
JPH0248984A (en) * | 1988-05-31 | 1990-02-19 | Dainippon Ink & Chem Inc | Laser marking method and resin composition for laser marking |
JPH0211438A (en) * | 1988-06-27 | 1990-01-16 | Clarion Co Ltd | Device for reading information outside vehicle |
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 |
---|---|
JPH0428758A (en) | 1992-01-31 |
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