JP3089947B2 - Manufacturing method of metal foil clad laminate - Google Patents
Manufacturing method of metal foil clad laminateInfo
- Publication number
- JP3089947B2 JP3089947B2 JP06108825A JP10882594A JP3089947B2 JP 3089947 B2 JP3089947 B2 JP 3089947B2 JP 06108825 A JP06108825 A JP 06108825A JP 10882594 A JP10882594 A JP 10882594A JP 3089947 B2 JP3089947 B2 JP 3089947B2
- Authority
- JP
- Japan
- Prior art keywords
- organopolysiloxane
- epoxy resin
- metal foil
- clad laminate
- molecule
- 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
- 239000002184 metal Substances 0.000 title claims description 17
- 229910052751 metal Inorganic materials 0.000 title claims description 17
- 239000011888 foil Substances 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 33
- 239000003822 epoxy resin Substances 0.000 claims description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 28
- 125000003277 amino group Chemical group 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 125000000524 functional group Chemical group 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000002966 varnish Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- GYPCWHHQAVLMKO-XXKQIVDLSA-N (7s,9s)-7-[(2r,4s,5s,6s)-4-amino-5-hydroxy-6-methyloxan-2-yl]oxy-6,9,11-trihydroxy-9-[(e)-n-[(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ylidene)amino]-c-methylcarbonimidoyl]-4-methoxy-8,10-dihydro-7h-tetracene-5,12-dione;hydrochloride Chemical group Cl.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(\C)=N\N=C1CC(C)(C)N(O)C(C)(C)C1)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 GYPCWHHQAVLMKO-XXKQIVDLSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- -1 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Reinforced Plastic Materials (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、プリント配線板とし
て、熱膨張率が小さく、実装部品の接続信頼性を確保で
きる金属箔張り積層板の製造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a metal foil-clad laminate as a printed wiring board, which has a low coefficient of thermal expansion and can ensure the connection reliability of mounted components.
【０００２】[0002]
【従来の技術】近年、電子機器は、小型化、多機能化、
高速化が要求されている。これらの要求に対して、ＬＳ
Ｉは微細配線化とチップサイズの大型化、パッケージ外
形の小型化あるいはベアチップ実装へと向かい、半導体
素材であるシリコンにより近い熱膨張率の部品となって
きた。このため、これを搭載するプリント配線板にも、
接続信頼性の面から、前記部品の熱膨張率に合わせた低
い熱膨張率が要求されている。従来、その要求に対応す
るため、セラミック基板、セラミック−樹脂複合基板、
低熱膨張繊維基材複合の樹脂基板等が開発されている
が、これらは、低熱膨張率、加工性、寸法安定性の全て
を満足するものではない。そこで、エポキシ樹脂を含浸
したシート状基材を金属箔と共に加熱加圧成形した積層
板をプリント配線板に用いるが、エポキシ樹脂には、ブ
タジエン・ニトリルゴム、分子鎖の一端にヒドロキシル
基を有するオルガノポリシロキサンなどの可撓化剤を添
加して樹脂の弾性率を低下させ、プリント配線板として
実装部品の接続信頼性を確保しようとする技術が提案さ
れている。しかし、ブタジエン・ニトリルゴムを添加し
た場合、耐熱性が低下するという問題がある。また、前
記オルガノポリシロキサンを添加した場合（特開平３−
９１２８８号公報）、耐熱性は良好であるもののエポキ
シ樹脂との反応性に乏しいので、オルガノポリシロキサ
ンが積層板表面にブリードする（オルガノポリシロキサ
ンの層が積層板表面に浮き出す）という問題がある。2. Description of the Related Art In recent years, electronic equipment has been reduced in size and function, and
Higher speed is required. For these requests, LS
I has become a component having a coefficient of thermal expansion closer to that of silicon, which is a semiconductor material, due to the trend toward smaller wiring, larger chip size, smaller package outer shape, or bare chip mounting. For this reason, the printed wiring board on which this is
From the viewpoint of connection reliability, a low coefficient of thermal expansion matching the coefficient of thermal expansion of the component is required. Conventionally, ceramic substrates, ceramic-resin composite substrates,
Although low thermal expansion fiber-based composite resin substrates and the like have been developed, they do not satisfy all of low thermal expansion coefficient, workability, and dimensional stability. Therefore, a laminate made by heating and pressing a sheet-like base material impregnated with an epoxy resin together with a metal foil is used for a printed wiring board. A technique has been proposed in which a flexible agent such as polysiloxane is added to lower the elastic modulus of a resin to secure connection reliability of a mounted component as a printed wiring board. However, when butadiene / nitrile rubber is added, there is a problem that heat resistance is reduced. When the above-mentioned organopolysiloxane is added (Japanese Unexamined Patent Publication No.
No. 91288), although the heat resistance is good, the reactivity with the epoxy resin is poor, so that there is a problem that the organopolysiloxane bleeds on the surface of the laminate (the organopolysiloxane layer emerges on the surface of the laminate). .
【０００３】[0003]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、オルガノポリシロキサンを配合したエポキ
シ樹脂を含浸したシート状基材を金属箔と共に加熱加圧
成形した積層板をプリント配線板に用いて、熱膨張率を
小さく、実装部品の接続信頼性を確保することである。
そして、積層板の成形時に、オルガノポリシロキサンが
積層板表面にブリードするのを抑制することである。The problem to be solved by the present invention is to provide a printed wiring board by laminating a sheet-like substrate impregnated with an epoxy resin containing an organopolysiloxane together with a metal foil under heat and pressure. The purpose is to reduce the coefficient of thermal expansion and ensure the connection reliability of the mounted components.
Then, it is to suppress the bleeding of the organopolysiloxane on the surface of the laminate during molding of the laminate.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
に、本発明に係る製造法は、エポキシ樹脂を含浸したシ
ート状基材を金属箔と共に加熱加圧成形する積層板の製
造において、エポキシ基、アミノ基、カルボキシル基の
いずれかを１分子中に２個以上有するオルガノポリシロ
キサンを、エポキシ樹脂とその硬化剤を合わせた固形重
量１００に対し０．１〜３０配合することを特徴とす
る。前記オルガノポリシロキサンは、（化１）または
（化２）で示されるようなものであり、官能基Ｒ’は、
エポキシ基、アミノ基、カルボキシル基から選ばれる
が、中でもアミノ基が好ましい。また、（化１）、（化
２）で示される化学構造式において、官能基Ｒ’の位置
は限定されるものではなく、分子鎖の両末端と側鎖のい
ずれかに位置してもよいし、分子鎖の末端と側鎖の両方
に位置してもよい。In order to solve the above-mentioned problems, a manufacturing method according to the present invention relates to a method of manufacturing a laminated board in which a sheet-like substrate impregnated with an epoxy resin is heated and pressed together with a metal foil. Group, amino group, carboxyl group
An organopolysiloxane having at least two either in one molecule, a solid weight 100 of the combined epoxy resin and its curing agent to be characterized in that 0.1 to 30 weight. The organopolysiloxane is represented by the following formula (1) or (2), and the functional group R ′ is
It is selected from an epoxy group, an amino group, and a carboxyl group , and among them, an amino group is preferable. Further, in the chemical structural formulas represented by (Chemical Formula 1) and (Chemical Formula 2), the position of the functional group R ′ is not limited, and may be located at either end of the molecular chain or at any of the side chains. However, it may be located at both the terminal and the side chain of the molecular chain.
【０００５】[0005]
【化１】 Embedded image
【０００６】[0006]
【化２】 Embedded image
【０００７】また、本発明に係る別の製造法は、エポキ
シ樹脂を含浸したシート状基材を金属箔と共に加熱加圧
成形する積層板の製造において、エポキシ樹脂として、
エポキシ基、アミノ基、カルボキシル基のいずれかを１
分子中に２個以上有するオルガノポリシロキサンとエポ
キシ樹脂とを予備反応させたものを使用し、前記予備反
応させるオルガノポリシロキサンの量を、オルガノポリ
シロキサンと反応させるエポキシ樹脂と予備反応物に配
合する硬化剤を合わせた固形重量１００に対し０．１〜
３０重量部とすることを特徴とする。Another manufacturing method according to the present invention is a method for manufacturing a laminate in which a sheet-like substrate impregnated with an epoxy resin is heated and pressed together with a metal foil.
Any one of epoxy group, amino group and carboxyl group
Using a pre-reacted organopolysiloxane having two or more molecules in the molecule and an epoxy resin, the amount of the pre-reacted organopolysiloxane is blended with the epoxy resin and the pre-reacted product to be reacted with the organopolysiloxane. 0.1 to 100 based on the total solid weight of the curing agent
It is characterized by 30 parts by weight.
【０００８】[0008]
【作用】本発明に係る方法で製造した積層板は、樹脂成
分が海島構造（海：エポキシ樹脂，島：オルガノポリシ
ロキサン）を形成しているため、島であるオルガノポリ
シロキサンが、高温時のエポキシ樹脂の膨張による発生
応力を吸収緩和して、膨張率を小さく抑えている。エポ
キシ樹脂に配合したオルガノポリシロキサンは、１分子
内に反応性の官能基Ｒ’（エポキシ基、アミノ基、カル
ボキシル基から選ばれる）を２個以上有しているので、
積層板の加熱加圧成形時にエポキシ樹脂硬化の架橋の中
に良好に取り込まれ、積層板表面にブリードするのを抑
制される。Ｒ’がエポキシ基の場合は、硬化剤としてヒ
ドロキシル基を有するものを選択しそのヒドロキシル基
と反応させることができる。また、Ｒ’がアミノ基、カ
ルボキシル基の場合は、エポキシ樹脂のエポキシ基と反
応させることができる。このような反応によって、オル
ガノポリシロキサンを硬化樹脂の分子中に取り込むこと
ができる。また、予備反応させた場合は、オルガノポリ
シロキサンの官能基とエポキシ基（オルガノポリシロキ
サンの官能基がエポキシ基の場合はヒドロキシル基）を
確実に反応させることができるので未反応のシリコンの
残留が少なくなり、耐熱性を確保する上で効果的であ
る。In the laminated board manufactured by the method according to the present invention, the resin component forms a sea-island structure (sea: epoxy resin, island: organopolysiloxane). The stress generated by the expansion of the epoxy resin is absorbed and relaxed, and the expansion rate is kept low. Organopolysiloxane blended in the epoxy resin, the reactive functional group R '(epoxy groups in one molecule, an amino group, Cal
Selected from a boxyl group ),
When the laminate is heated and pressed, it is satisfactorily incorporated into the crosslinks of the cured epoxy resin, and bleeding on the surface of the laminate is suppressed. When R 'is an epoxy group, a curing agent having a hydroxyl group can be selected and reacted with the hydroxyl group. Also, R 'is an amino group, mosquitoes
In the case of a ruboxyl group, it can be reacted with an epoxy group of an epoxy resin. By such a reaction, the organopolysiloxane can be incorporated into the molecules of the cured resin. In addition, when pre-reacted, the functional group of the organopolysiloxane and the epoxy group (or the hydroxyl group when the functional group of the organopolysiloxane is an epoxy group) can be reliably reacted, so that unreacted silicon remains. This is effective in securing heat resistance.
【０００９】上記反応性の官能基Ｒ’がオルガノポリシ
ロキサンの１分子中に１個しかないと、反応性が低く分
子の片末端で架橋が止まってしまうのでブリードが発生
する。２個以上存在することにより初めて硬化樹脂の分
子中に良好に取り込まれることになる。オルガノポリシ
ロキサンの添加量は、エポキシ樹脂とその硬化剤を合わ
せた固形重量１００に対し０．１未満では低熱膨張化に
効果がなく、３０を越えるとオルガノポリシロキサンの
分散が不均一になり、また、積層板の表面にブリードし
て金属箔の引き剥がし強さが低下する。予備反応させた
場合、オルガノポリシロキサンの添加量は、エポキシ樹
脂とその硬化剤を合わせた固形重量１００に対し０．１
未満では低熱膨張化に効果がなく、３０を越えると反応
中にゲル化する。If there is only one reactive functional group R 'in one molecule of the organopolysiloxane, bleeding occurs because the reactivity is low and crosslinking stops at one end of the molecule. Only when there are two or more of them, will they be well incorporated into the molecules of the cured resin. If the addition amount of the organopolysiloxane is less than 0.1 with respect to the total solid weight of the epoxy resin and its curing agent of less than 0.1, there is no effect on low thermal expansion, and if it exceeds 30, the dispersion of the organopolysiloxane becomes uneven, In addition, the metal foil bleeds on the surface of the laminate and the peel strength of the metal foil is reduced. When pre-reacted, the organopolysiloxane is added in an amount of 0.1 to the total solid weight of the epoxy resin and its curing agent of 100.
If it is less than 30, there is no effect on lowering the thermal expansion, and if it exceeds 30, gelation occurs during the reaction.
【００１０】[0010]
実施例１〜３、比較例１〜２ エポキシ樹脂（油化シェル製「エピコート１００１」，
エポキシ当量：５００）、ジシアンジアミド（ＤＩＣ
Ｙ）、２−エチル４−メチルイミダゾール（２Ｅ４Ｍ
Ｚ）、および（化３）に示すオルガノポリシロキサン
（チッソ製「ＦＭ−３３５２」，分子量：５０００）を
表１に示す割合で配合し、メチルエチルケトンとメチル
グリコールで溶解させ固形分６０重量％のワニスを調合
した。上記ワニスをガラス織布（旭シュエーベル製，厚
み：０．１８mm）に含浸乾燥し、樹脂分４０重量％のプ
リプレグを得た。このプリプレグを４枚重ね、その両側
に１８μ厚銅箔を配置し、温度１７０℃、圧力４０kg／
cm2で９０分間加熱加圧成形して、厚さ０．８mmの両面
銅張り積層板を製造した。実施例１〜３、比較例１〜２
で製造した銅張り積層板の特性を表１に併せて示す。Examples 1-3, Comparative Examples 1-2 Epoxy resin ("Epicoat 1001" manufactured by Yuka Shell,
Epoxy equivalent: 500), dicyandiamide (DIC)
Y), 2-ethyl 4-methylimidazole (2E4M
Z), and an organopolysiloxane (“FM-3352” manufactured by Chisso, molecular weight: 5000) shown in Chemical Formula 3 in a ratio shown in Table 1, and dissolved in methyl ethyl ketone and methyl glycol to obtain a varnish having a solid content of 60% by weight. Was prepared. The varnish was impregnated and dried in a glass woven fabric (made by Asahi Schwebel, thickness: 0.18 mm) to obtain a prepreg having a resin content of 40% by weight. Four prepregs were stacked, and 18 μm thick copper foils were arranged on both sides of the prepreg.
cm 2 at heated press molding 90 minutes to produce a double-sided copper-clad laminate having a thickness of 0.8 mm. Examples 1-3, Comparative Examples 1-2
Table 1 also shows the characteristics of the copper-clad laminate manufactured in the above.
【００１１】[0011]
【化３】 Embedded image
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【００１４】[0014]
【００１５】[0015]
【００１６】[0016]
【００１７】[0017]
【００１８】実施例５〜７、比較例４ エポキシ樹脂（油化シェル製「エピコート１００１」，
エポキシ当量：５００）、および（化３）に示したオル
ガノポリシロキサン（チッソ製「ＦＭ−３３５２」，分
子量：５０００）を表３に示す割合で配合し、溶剤なし
で、１５０℃−１０時間反応させ、その反応物にジシア
ンジアミド（ＤＩＣＹ）、２−エチル４−メチルイミダ
ゾール（２Ｅ４ＭＺ）を加え、メチルエチルケトンとメ
チルグリコールで溶解させ固形分６０重量％のワニスを
調合した。上記ワニスをガラス織布（旭シュエーベル
製，厚み：０．１８mm）に含浸乾燥し、樹脂分４０重量
％のプリプレグを得た。このプリプレグを４枚重ね、そ
の両側に１８μ厚銅箔を配置し、温度１７０℃、圧力４
０kg／cm2で９０分間加熱加圧成形して、厚さ０．８mm
の両面銅張り積層板を製造した。Examples 5 to 7, Comparative Example 4 Epoxy resin ("Epicoat 1001" manufactured by Yuka Shell,
Epoxy equivalent: 500) and the organopolysiloxane (Chemical formula 3 "FM-3352", molecular weight: 5000) were blended in the proportions shown in Table 3 and reacted at 150 DEG C. for 10 hours without solvent. Then, dicyandiamide (DICY) and 2-ethyl 4-methylimidazole (2E4MZ) were added to the reaction product, and the mixture was dissolved with methyl ethyl ketone and methyl glycol to prepare a varnish having a solid content of 60% by weight. The varnish was impregnated and dried in a glass woven fabric (made by Asahi Schwebel, thickness: 0.18 mm) to obtain a prepreg having a resin content of 40% by weight. Four prepregs were stacked, and 18 μm thick copper foils were placed on both sides of the prepreg.
Heat and pressure molded at 0 kg / cm 2 for 90 minutes, 0.8mm thick
Was produced.
【００１９】実施例８ 実施例６における反応物をｎ−ヘプタンでよく洗浄して
から、それにジシアンジアミド（ＤＩＣＹ）、２−エチ
ル４−メチルイミダゾール（２Ｅ４ＭＺ）をくわえ、メ
チルエチルケトンとメチルグリコールで溶解させ固形分
６０重量％のワニスを調合した。上記ワニスを使用し、
以下、実施例６と同様に厚さ０．８mmの両面銅張り積層
板を製造した。実施例５〜８、比較例４で製造した銅張
り積層板の特性を表３に併せて示す。Example 8 The reaction product in Example 6 was thoroughly washed with n-heptane, and then dicyandiamide (DICY) and 2-ethyl-4-methylimidazole (2E4MZ) were added thereto. A 60% by weight varnish was prepared. Using the above varnish,
Thereafter, a double-sided copper-clad laminate having a thickness of 0.8 mm was produced in the same manner as in Example 6. Table 3 also shows the characteristics of the copper-clad laminates manufactured in Examples 5 to 8 and Comparative Example 4.
【００２０】[0020]
【表３】 [Table 3]
【００２１】実施例８では、反応物を洗浄してから用い
ているので、同じ配合の実施例６より銅箔の引き剥がし
強さが大きくなっている。また、オルガノポリシロキサ
ンの種類および配合量が実施例６と同じである実施例２
においては、２６０℃半田耐熱性は１０秒であった。In Example 8, since the reactant was used after being washed, the peel strength of the copper foil was higher than that of Example 6 having the same composition. Example 2 in which the kind and amount of the organopolysiloxane were the same as in Example 6
, The solder heat resistance at 260 ° C. was 10 seconds.
【００２２】[0022]
【００２３】[0023]
【００２４】[0024]
【００２５】[0025]
【発明の効果】上述のように、本発明に係る金属箔張り
積層板の製造法によれば、エポキシ樹脂にオルガノポリ
シロキサンを配合して熱膨張率を小さくしたものにおい
て、オルガノポリシロキサンの積層板表面へのブリード
を抑制して、金属箔の引き剥がし強さを十分に確保する
ことができる。本発明に係る方法により製造した金属箔
張り積層板は、プリント配線板として熱膨張率が小さ
く、実装部品の接続信頼性が高いものである。オルガノ
ポリシロキサンの１分子中に２個以上有する反応性の官
能基としてアミノ基を選択したときは、ブリードの抑制
効果が一層顕著で金属箔の引き剥がし強度も大きい。そ
して、積層板の熱膨張率も一層小さくなる。エポキシ樹
脂とオルガノポリシロキサンを予備反応させて用いた場
合は、耐熱性が高くなるのでさらに効果的である。As described above, according to the method for manufacturing a metal foil-clad laminate according to the present invention, the epoxy resin is mixed with an organopolysiloxane to reduce the coefficient of thermal expansion. Bleed to the plate surface can be suppressed, and the peel strength of the metal foil can be sufficiently ensured. The metal foil-clad laminate manufactured by the method according to the present invention has a low coefficient of thermal expansion as a printed wiring board, and has high connection reliability of mounted components. When an amino group is selected as a reactive functional group having two or more in one molecule of the organopolysiloxane, the effect of suppressing bleed is more remarkable and the peeling strength of the metal foil is large. Then, the coefficient of thermal expansion of the laminated plate is further reduced. When an epoxy resin and an organopolysiloxane are preliminarily reacted and used, heat resistance is increased, which is more effective.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０８Ｊ 5/24 ＣＦＣ Ｃ０８Ｊ 5/24 ＣＦＣ Ｈ０５Ｋ 1/03 ６１０ Ｈ０５Ｋ 1/03 ６１０Ｌ 3/00 3/00 Ｒ // Ｂ２９Ｋ 105:06 Ｂ２９Ｌ 31:34 (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 15/08 B29C 43/18 C08J 5/24 CFC H05K 1/03 610 ────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 7 Identification code FI C08J 5/24 CFC C08J 5/24 CFC H05K 1/03 610 H05K 1/03 610L 3/00 3/00 R // B29K 105: 06 B29L 31:34 (58) Field surveyed (Int. Cl. 7 , DB name) B32B 15/08 B29C 43/18 C08J 5/24 CFC H05K 1/03 610
Claims (5)
属箔と共に加熱加圧成形する積層板の製造において、 前期エポキシ樹脂には、エポキシ基、アミノ基、カルボ
キシル基のいずれかを１分子中に２個以上有するオルガ
ノポリシロキサンを、エポキシ樹脂とその硬化剤を合わ
せた固形重量１００に対し０．１〜３０配合することを
特徴とする金属箔張り積層板の製造法。1. A preparation of laminates of epoxy resin impregnated sheet-like substrate is heated pressure molding with a metal foil, the previous period epoxy resin, an epoxy group, an amino group, carboxy
A metal foil-clad laminate comprising an organopolysiloxane having at least two xyl groups in one molecule in an amount of 0.1 to 30 based on a total solid weight of 100 of an epoxy resin and a curing agent thereof. Manufacturing method.
ガノポリシロキサンを、エポキシ樹脂とその硬化剤を合
わせた固形重量１００に対し０．１〜３０配合すること
を特徴とする請求項１記載の金属箔張り積層板の製造
法。2. An organopolysiloxane having two or more amino groups in one molecule is compounded in an amount of 0.1 to 30 based on a total solid weight of 100 of the epoxy resin and its curing agent. The method for producing a metal foil-clad laminate according to the above.
属箔と共に加熱加圧成形する積層板の製造において、 エポキシ樹脂として、エポキシ基、アミノ基、カルボキ
シル基のいずれかを１分子中に２個以上有するオルガノ
ポリシロキサンとエポキシ樹脂とを予備反応させたもの
を使用し、前期予備反応させるオルガノポリシロキサン
の量は、オルガノポリシロキサンと反応させるエポキシ
樹脂と予備反応物に配合する硬化剤を合わせた固形重量
１００に対し０．１〜３０重量部であることを特徴とす
る金属箔張り積層板の製造法。3. A preparation of laminates of epoxy resin impregnated sheet-like substrate is heated pressure molding with a metal foil, epoxy resin, epoxy group, amino group, carboxy
An organopolysiloxane having two or more sil groups in one molecule is preliminarily reacted with an epoxy resin. The amount of the organopolysiloxane to be preliminarily reacted is determined by the amount of the epoxy resin to be reacted with the organopolysiloxane. Characterized in that the amount is 0.1 to 30 parts by weight based on the total solid weight of 100 and the curing agent to be added to the preliminary reaction product.
ガノポリシロキサンを予備反応させる請求項３記載の金
属箔張り積層板の製造法。4. The method for producing a metal foil-clad laminate according to claim 3, wherein an organopolysiloxane having two or more amino groups in one molecule is preliminarily reacted.
を予備反応させたものを溶剤で洗浄してから用いる請求
項３または４記載の金属箔張り積層板の製造法。5. The method for producing a metal-foil-clad laminate according to claim 3, wherein the product obtained by pre-reacting the organopolysiloxane and the epoxy resin is washed with a solvent before use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06108825A JP3089947B2 (en) | 1993-10-08 | 1994-05-24 | Manufacturing method of metal foil clad laminate |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25202093 | 1993-10-08 | ||
| JP5-252020 | 1993-10-08 | ||
| JP06108825A JP3089947B2 (en) | 1993-10-08 | 1994-05-24 | Manufacturing method of metal foil clad laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07148885A JPH07148885A (en) | 1995-06-13 |
| JP3089947B2 true JP3089947B2 (en) | 2000-09-18 |
Family
ID=26448632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06108825A Expired - Fee Related JP3089947B2 (en) | 1993-10-08 | 1994-05-24 | Manufacturing method of metal foil clad laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3089947B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10358060A1 (en) * | 2003-12-11 | 2005-07-14 | Wacker-Chemie Gmbh | Process for the preparation of highly viscous organopolysiloxanes |
| US9079376B2 (en) | 2011-01-18 | 2015-07-14 | Hitachi Chemical Company, Ltd. | Prepreg, laminate obtained with the same and printed-wiring board |
| EP2666806A1 (en) * | 2011-01-18 | 2013-11-27 | Hitachi Chemical Co., Ltd. | Prepreg, and laminate board and printed wiring board using same |
-
1994
- 1994-05-24 JP JP06108825A patent/JP3089947B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07148885A (en) | 1995-06-13 |
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