JPH0313258B2 - - Google Patents
Info
- Publication number
- JPH0313258B2 JPH0313258B2 JP13562386A JP13562386A JPH0313258B2 JP H0313258 B2 JPH0313258 B2 JP H0313258B2 JP 13562386 A JP13562386 A JP 13562386A JP 13562386 A JP13562386 A JP 13562386A JP H0313258 B2 JPH0313258 B2 JP H0313258B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- laminates
- parts
- weight
- formula
- 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
Links
- 239000003822 epoxy resin Substances 0.000 claims description 17
- 229920000647 polyepoxide Polymers 0.000 claims description 17
- -1 aromatic phosphoric acid ester Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000011342 resin composition Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 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 4
- 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 3
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
〔産業上の利用分野〕
この発明は積層板用エポキシ樹脂組成物に関す
るものである。
〔従来の技術〕
近年、プリント回路板の製造の自動化や実装の
高密度化に伴つて、加工工程中にそりまたはねじ
れ等が発生せず寸法安定性の良好な銅張り積層板
が強く要望されるようになつた。従来から用いら
れているガラス基材エポキシ樹脂銅張り積層板は
加工工程における前記そり、ねじれ、寸法安定性
など優れてはいるものの、高価でありまた穴あけ
加工もドリルを使用するため生産性が悪いなどの
欠点を有する。一方紙基材エポキシ樹脂積層板は
ガラス基材のものに比べて安価であり、かつ穴あ
け加工も打抜きが可能であることから生産性も良
好であるが、吸湿によるそり、ねじれが大きいた
めパターン印刷時に多くの支障を生じたり、また
吸湿による寸法変動が印刷精度の低下または部品
挿入時の不都合を招来することになる。
一般にエポキシ樹脂は架橋密度の高い三次元網
目構造を有し、この構造内に水分子が浸入したと
きは、分子塑性が非常に小さい硬化エポキシ樹脂
は膨潤し、これが片面銅張り積層板のそり、ねじ
れなどの原因になると考えられることから、エポ
キシ樹脂の可塑剤としてエポキシ化ダイマー酸、
エポキシ化アマニ油、長鎖型エポキシ樹脂等が用
いられて来た。しかし、エポキシ化ダイマー酸お
よび長鎖型エポキシ樹脂は吸湿時のそり、ねじれ
に対しては優れた効果を示すものの、半田耐熱性
の低下が著しく、またエポキシ化アマニ油のそ
り、ねじれに対する効果も満足できるものではな
い。
〔発明が解決しようとする問題点〕
以上のように従来技術における積層板用エポキ
シ樹脂組成物には、加工性が優れ、安価である積
層板の製作が可能であつても、その積層板の吸湿
によるそり、ねじれおよび寸法変動等積層板の特
性を悪化させる現象を防ぐうえで満足できるもの
はないという問題点があつた。
〔問題点を解決するための手段〕
上記の問題点を解決するために、この発明は積
層板用のエポキシ樹脂組成物を100重量部のエポ
キシ樹脂に対して５〜30重量部の一般式（）す
なわち（PhO）3P＝Ｏ〔式中Phは芳香族基を示す〕
で表わされる芳香族リン酸エステル類および硬化
剤を配合した組成物とする手段を採用したもので
ある。以下その詳細を述べる。
まず、この発明のエポキシ樹脂にはビスフエノ
ールＡ型、ノボラツク型、グリシジルエステル型
またはこれらのハロゲン化型など通常広く用いら
れているすべての型のエポキシ樹脂を適用するこ
とができ、硬化剤には酸無水物、脂肪族ポリアミ
ン、ポリアミド樹脂、芳香族ジアミン、その他ア
ミン系化合物、ルイス酸錯化合物、フエノール樹
脂、イソシアネート等の架橋剤などを例示するこ
とができる。
つぎにこの発明における芳香族リン酸エステル
類とはクレジルジフエニルフオスフエート、トリ
フエニルフオスフエート、トリタレジルフオスフ
エート等芳香族基（Ph−）を有するリン酸エス
テル類であり、芳香族基として
[Industrial Field of Application] This invention relates to an epoxy resin composition for laminates. [Prior Art] In recent years, with the automation of printed circuit board manufacturing and the increasing density of packaging, there has been a strong demand for copper-clad laminates that do not warp or twist during the processing process and have good dimensional stability. I started to do that. Traditionally used glass-based epoxy resin copper-clad laminates have excellent dimensional stability against warping and twisting during the processing process, but they are expensive and have low productivity because they use a drill to make holes. It has the following disadvantages. On the other hand, paper-based epoxy resin laminates are cheaper than glass-based ones, and have good productivity because they can be punched and punched, but they are prone to warping and twisting due to moisture absorption, so pattern printing is difficult. Sometimes, many troubles occur, and dimensional fluctuations due to moisture absorption lead to a decrease in printing accuracy or inconvenience when inserting parts. Generally, epoxy resins have a three-dimensional network structure with high crosslinking density, and when water molecules penetrate into this structure, the cured epoxy resin, which has very low molecular plasticity, swells, causing warping of the single-sided copper-clad laminate. Epoxidized dimer acid, as a plasticizer for epoxy resin, is considered to cause twisting, etc.
Epoxidized linseed oil, long chain epoxy resins, etc. have been used. However, although epoxidized dimer acids and long-chain epoxy resins have excellent effects on warping and twisting when moisture is absorbed, the soldering heat resistance is significantly reduced, and epoxidized linseed oil has no effect on warping and twisting. It's not satisfying. [Problems to be Solved by the Invention] As described above, although the epoxy resin compositions for laminates in the prior art have excellent processability and can produce laminates at low cost, There is a problem in that there is no satisfactory method for preventing phenomena that deteriorate the properties of the laminate, such as warping, twisting, and dimensional fluctuations due to moisture absorption. [Means for Solving the Problems] In order to solve the above problems, the present invention provides an epoxy resin composition for laminates containing 5 to 30 parts by weight of the general formula ( ), that is, (PhO) 3 P=O [In the formula, Ph represents an aromatic group]
This method employs a method of preparing a composition containing an aromatic phosphoric acid ester represented by the formula and a curing agent. The details will be described below. First, the epoxy resin of the present invention can be any type of epoxy resin commonly used, such as bisphenol A type, novolac type, glycidyl ester type, or halogenated types of these. Examples include crosslinking agents such as acid anhydrides, aliphatic polyamines, polyamide resins, aromatic diamines, other amine compounds, Lewis acid complex compounds, phenolic resins, and isocyanates. Next, the aromatic phosphoric acid esters in this invention are phosphoric acid esters having an aromatic group (Ph-) such as cresyl diphenyl phosphate, triphenyl phosphate, tritalesyl phosphate, etc. as an aromatic group
【式】【formula】
【式】【formula】
この発明の芳香族リン酸エステル類はエポキシ
樹脂本来の架橋による三次元網目構造の密度を低
下させ、分子鎖塑性によつて吸湿による体積変化
を緩和し、片面金属張り積層板のそり、ねじれな
どを起こさせないようにする働きをするものと考
えられる。
〔実施例〕
実施例 １〜３：
臭素化ビスフエノールＡ型のエポキシ樹脂（ダ
ウケミカル社製：DER−511）100重量部、硬化
剤としてヘキサヒドロ無水フタル酸20重量部、硬
化促進剤としてベンジルジメチルアミン0.3重量
部とを配合し、これに芳香族リン酸エステルとし
てクレジルジフエニルホスフエートを第１表に示
す割合（重量部）で配合し、さらにアセトンを加
えて積層板用のエポキシ樹脂組成物のワニス
The aromatic phosphoric acid esters of this invention reduce the density of the three-dimensional network structure due to the inherent crosslinking of epoxy resins, alleviate volume changes due to moisture absorption through molecular chain plasticity, and reduce warpage and twisting of single-sided metal-clad laminates. It is thought that the function is to prevent this from occurring. [Examples] Examples 1 to 3: 100 parts by weight of brominated bisphenol A type epoxy resin (manufactured by Dow Chemical Company: DER-511), 20 parts by weight of hexahydrophthalic anhydride as a curing agent, and benzyl dimethyl as a curing accelerator. 0.3 parts by weight of amine, and cresyl diphenyl phosphate as an aromatic phosphoric acid ester in the proportions (parts by weight) shown in Table 1, and further acetone were added to form an epoxy resin composition for laminates. varnish of things
【表】
を調製した。ついでこのワニスを厚さ0.2mmのリ
ンター紙に含浸塗布した後乾燥させ、樹脂分50％
のプリプレグを得た。このプリプレグ８枚とその
片側に厚さ0.035mmの銅箔とを重ねて160℃、150
分間、70Kg・ｆ／cm2の条件で加熱加圧し積層体の
一体成形を行ない、厚さ1.6mmの片面銅張り積層
板を作製した。得られた積層板について半田耐熱
性（260℃の溶融半田上に浮かし、脹れが発生す
るまでの経過秒数で表わす）、吸湿時における基
板横方向の寸法変化（加熱加圧成形直後を常態値
とし、Ｃ−1000／23／90処理後の寸法を常態値に
対する変化率％で表わす）および吸湿時の基板横
方向の反り変動量（加熱加圧成形直後の基板反り
を常態とし、Ｃ−1000／23／90処理後の反り変動
量を試料長さに対する変化率％で表わす）を測定
し、得られた結果を第１表にまとめた。[Table] was prepared. Next, this varnish was impregnated and coated on linter paper with a thickness of 0.2 mm, and then dried to reduce the resin content to 50%.
prepreg was obtained. Eight sheets of this prepreg were stacked with copper foil 0.035 mm thick on one side and heated to 160℃ and 150℃.
The laminate was integrally molded by heating and pressing at 70 kg·f/cm 2 for 1 minute to produce a single-sided copper-clad laminate with a thickness of 1.6 mm. The obtained laminate has soldering heat resistance (expressed as the number of seconds elapsed until bulging occurs when floating on molten solder at 260°C), dimensional change in the lateral direction of the board when moisture is absorbed (normal condition immediately after hot-pressure molding) (The dimensions after C-1000/23/90 processing are expressed as a percentage change from the normal value) and the amount of variation in lateral warpage of the substrate upon moisture absorption (with the substrate warpage immediately after hot-pressure molding being the normal state, C- The amount of variation in warpage after the 1000/23/90 treatment (expressed as a percentage change with respect to the sample length) was measured, and the obtained results are summarized in Table 1.
この発明のエポキシ樹脂組成物によつて、基材
として加工性が優れ、安価である紙を使用し、し
かも吸湿による影響を受けにくく、吸湿時におい
ても寸法変化率および反り変動率の著しく小さい
片面銅張り積層体が一体成形できることから、こ
の発明の意義はきわめて大きいといえる。
By using the epoxy resin composition of the present invention, paper, which has excellent processability and is inexpensive, can be used as a base material, and is not easily affected by moisture absorption, and even when moisture is absorbed, the dimensional change rate and warp fluctuation rate are extremely small. Since the copper-clad laminate can be integrally molded, it can be said that the significance of this invention is extremely large.
Claims (1)
量部の一般式（）で示される芳香族リン酸エス
テル類および硬化剤を配合したことを特徴とする
積層板用エポキシ樹脂組成物。 一般式（） （PhO）3P＝Ｏ 〔式中Phは芳香族基を示す〕[Claims] 1. An epoxy for laminates, characterized in that 5 to 30 parts by weight of an aromatic phosphoric acid ester represented by the general formula () and a curing agent are blended with 100 parts by weight of an epoxy resin. Resin composition. General formula () (PhO) 3 P=O [In the formula, Ph represents an aromatic group]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13562386A JPS62290719A (en) | 1986-06-10 | 1986-06-10 | Epoxy resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13562386A JPS62290719A (en) | 1986-06-10 | 1986-06-10 | Epoxy resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62290719A JPS62290719A (en) | 1987-12-17 |
| JPH0313258B2 true JPH0313258B2 (en) | 1991-02-22 |
Family
ID=15156133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13562386A Granted JPS62290719A (en) | 1986-06-10 | 1986-06-10 | Epoxy resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62290719A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0812883A4 (en) * | 1995-12-28 | 2001-05-16 | Toray Industries | Epoxy resin composition |
-
1986
- 1986-06-10 JP JP13562386A patent/JPS62290719A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62290719A (en) | 1987-12-17 |
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