JPS58187346A - Manufacture of laminated board - Google Patents

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 本発明は、積層板あるいは銅張り積層板の製造法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing laminates or copper-clad laminates.

従来、フェノール樹脂積層板あるいは銅張り積層板の製
造に際しては、レゾール型フェノール樹脂をメタノール
、アセトン、トルエン、メチルエチルケトンなどの有機
溶剤に希釈したフェスを、リンター紙、クラフト紙など
の積層品用基材に含浸した後熱風循還乾燥炉中で前記有
機溶剤を揮散、乾燥させていた。このため、多量の有機
溶剤を必要とじ、有機溶剤の揮散、乾燥のためのエネル
ギーコストおよび廃ガス処理コストを要していた。また
、溶剤は可燃性のため危険な作業環境にあった。Conventionally, when manufacturing phenolic resin laminates or copper-clad laminates, a fest made by diluting resol-type phenolic resin with an organic solvent such as methanol, acetone, toluene, or methyl ethyl ketone is used as a base material for laminates such as linter paper or kraft paper. After impregnation, the organic solvent was volatilized and dried in a hot air circulation drying oven. Therefore, a large amount of organic solvent is required, and energy costs for volatilization and drying of the organic solvent and waste gas processing costs are required. Additionally, the solvent was flammable, creating a dangerous work environment.

本発明は、上記の従来の欠点を除去し、溶剤の使用と乾
燥工程を削減することによって、製造−■−程を効率化
した積層板あるいは銅張り積層板の製造方法を提供する
ことを目的とする。An object of the present invention is to provide a method for manufacturing a laminate or a copper-clad laminate that eliminates the above-mentioned conventional drawbacks and streamlines the manufacturing process by reducing the use of solvents and drying steps. shall be.

上記目的を達成するために本発明は、フェノニル樹脂初
期縮合物を含浸したセルローズ系紙基材に乾性油変性ノ
ボラック型フェノール樹脂とへキサメチレンテトラミン
からなる樹脂組成物を加熱溶融状態で塗付し、この基材
の複数枚を重ね合せて加熱加圧成形することを特徴とす
るものである。。In order to achieve the above object, the present invention applies a resin composition consisting of a drying oil-modified novolac type phenol resin and hexamethylenetetramine in a heated molten state to a cellulose paper base material impregnated with a phenonyl resin initial condensate. , is characterized in that a plurality of sheets of this base material are superimposed and molded under heat and pressure. .

本発明で用いるフェノール樹脂初期縮合物は、フェノー
ル類とホルムアルデヒド類を苛性ソーダ、苛性カリ、水
酸化バリウムなどの金属アルカリ、トリメチルアミン、
トリエチルアミン、ツメチルアミン、ジエチルアミンな
どのアミン化合物に代表される塩基性触媒下で反応させ
て得た１〜２核体の初期縮合物である。この初期縮合物
をリンター紙、またはクラフト紙などのセルローズ系紙
基材に含浸させると親水性があるため基材内部まで浸透
する。The phenolic resin initial condensate used in the present invention can be prepared by combining phenols and formaldehyde with caustic soda, caustic potash, metal alkalis such as barium hydroxide, trimethylamine, etc.
It is an initial condensation product of mono- or dinuclear bodies obtained by reaction under a basic catalyst represented by an amine compound such as triethylamine, trimethylamine, or diethylamine. When this initial condensate is impregnated into a cellulose paper base material such as linter paper or kraft paper, it penetrates into the interior of the base material due to its hydrophilic properties.

本発明に用いる乾性油変性ノボラック型フェノール樹脂
は、フェノール類と乾性油を酸性触媒存在下で反応させ
て得られる乾性油−フエノール類付加物にホルムアルデ
ヒド類を反応させるか、あるいはフェノール類とホルム
アルデヒド類を酸性触媒存在下で反応させて得られるノ
ボラック型うエノール樹脂に乾性油を反応させて得る。The drying oil-modified novolac type phenolic resin used in the present invention can be obtained by reacting formaldehyde with a drying oil-phenol adduct obtained by reacting phenols and drying oil in the presence of an acidic catalyst, or by reacting formaldehyde with a drying oil-phenol adduct obtained by reacting phenols and drying oil in the presence of an acidic catalyst. It is obtained by reacting a novolac-type enol resin obtained by reacting the following in the presence of an acidic catalyst with a drying oil.

乾性油変性ノボラック型フェノール樹脂の軟化点は、こ
れを基材に加熱溶融状態で塗付する工程に於いてゲル化
を防ぐため、１００℃以下が望ましい。The softening point of the dry oil-modified novolac type phenolic resin is desirably 100° C. or lower in order to prevent gelation during the process of applying it to a substrate in a heated molten state.

本発明に於いては、乾性油変性ノボラック型フェノール
樹脂に硬化剤としてヘキサメチレンテトラミンを添加す
るが、添加量は乾性油変性ノボラック型フェノール樹脂
１００重量部に対し３〜１５重量部が適当である。基材
１こ塗付するに際し、乾性油変性ノボラック型フェノー
ル樹脂−へキサメチレンテトラミン混合組成物の加熱溶
融温度は１１０　”Ｃ以下が望ましい。In the present invention, hexamethylenetetramine is added as a curing agent to the drying oil-modified novolac type phenolic resin, and the appropriate amount of addition is 3 to 15 parts by weight per 100 parts by weight of the drying oil-modified novolak type phenolic resin. . When coating one substrate, the heating and melting temperature of the drying oil-modified novolac type phenol resin-hexamethylenetetramine mixed composition is preferably 110''C or less.

実施例 フェノ　ル６８０ｇ、桐油３５０ｇにパラトルエンスル
フォン酸０．５ｊｌを加え８０〜８５℃にて１２０分間
反応させた後、８５４バラフォルムアルデヒド１９５ｇ
を加え７０〜７５℃にて１′３０分間反応させた。減圧
脱水後、軟化点６５°Ｃの桐油変性ノボラック型フェノ
ール樹脂を得た。得られた桐油変性ノボラック型フェノ
ール樹脂を８５°Ｃに加熱溶融し、ヘキサメチレノテト
ラミンを桐油変性ノボラック型フヱノール樹脂１００重
量部に対し１０重量部添加して撹拌混合した後、これを
、予めフェノール樹８ｍ初期砺合物を１０ｆｌ量憾含浸
乾燥したクラフト紙に塗付した。得られた塗工紙の樹脂
付着量は５２重量係であった。Example 0.5 jl of para-toluene sulfonic acid was added to 680 g of phenol and 350 g of tung oil, and the mixture was reacted at 80 to 85°C for 120 minutes, followed by 195 g of 854 rose formaldehyde.
was added and reacted at 70 to 75°C for 1'30 minutes. After dehydration under reduced pressure, a tung oil-modified novolac type phenol resin with a softening point of 65°C was obtained. The obtained tung oil-modified novolak phenol resin was heated and melted at 85°C, 10 parts by weight of hexamethylenenotetramine was added to 100 parts by weight of the tung oil-modified novolak phenol resin, and the mixture was stirred and mixed. A 10 fl volume of the initial 8m wood composite was applied to kraft paper which had been impregnated and dried. The resin adhesion amount of the obtained coated paper was 52% by weight.

ｌ・１塗Ｔ紙８枚とその片側表面薔こ３５μ厚銅箔を重
ね合わせた構成物を王力１ｔ　ｏ　Ｋｇ／ｃｄ。A composition consisting of 8 sheets of l.1 coated T paper and a 35μ thick copper foil layered on one side has a weight of 1 ton Kg/cd.

温度１７０℃で５５分間成形し銅張り積層板を得た 比較例 フェノール５ｓ０１桐油３５０ｇ１こバラトルエンスル
フォン酸ｏ、ｓｙ、メタノール５０ｇを加え８０〜８５
’Ｃにて１２０分間反応させた１１．２５％アンモニア
水２０９．８５繋パラフオルムアルデヒド２５０＃を加
え８０〜８５°Ｃにて２７０分間反応させた。次いで、
減圧脱水した後トルエンで希釈し樹脂濃度５０重量％の
桐油変性フェノール樹脂ワニスを得た。予めフェノール
樹脂初期縮合物を１０ｉ１ｉ量チ含浸乾燥したクラフト
紙に前記桐油変性フェノール樹脂ワニスを含浸乾燥して
樹脂付着量５１重量慢の塗工紙を得た。A comparative example in which a copper-clad laminate was obtained by molding at a temperature of 170°C for 55 minutes.
209.85 # of 11.25% ammonia water and 250 # of paraformaldehyde, which had been reacted for 120 minutes at 80-85°C, were added and reacted for 270 minutes at 80-85°C. Then,
After dehydration under reduced pressure, the mixture was diluted with toluene to obtain a tung oil-modified phenolic resin varnish with a resin concentration of 50% by weight. A kraft paper which had been previously impregnated and dried with a phenolic resin initial condensate in an amount of 10×10 was impregnated with the tung oil-modified phenolic resin varnish and dried to obtain a coated paper with a resin adhesion amount of 51 g.

上記塗工紙８枚とその片側表面に３５μ厚銅箔を重ね合
せた構成物をＩＦ力１１０ＫＰ／ｃｓ１．温度１７０℃
で５５分間成形し銅張り積層板を得た。A composition consisting of eight sheets of the above coated paper and a 35μ thick copper foil laminated on one side of the paper was coated with an IF force of 110KP/cs1. Temperature 170℃
The molding process was performed for 55 minutes to obtain a copper-clad laminate.

実施例および比較例の銅張り積層板の性能を＠１表に示
す。The performance of the copper-clad laminates of Examples and Comparative Examples is shown in Table 1.

第　　１　　表 第１表から明らかなように、本発明による銅張り積層板
の性能は、従来製造法の銅張り積層板に比べて加熱収縮
率は小さく、曲げ強さ、絶縁抵抗、吸水量、打抜加工性
は同等である。Table 1 As is clear from Table 1, the performance of the copper-clad laminate according to the present invention is that the heat shrinkage rate is lower than that of the copper-clad laminate manufactured using conventional methods, and the performance of the copper-clad laminate according to the present invention is lower in terms of bending strength, insulation resistance, water absorption, and The punching workability is the same.

本発明によれば、乾性油変性フェノール樹脂の塗工工程
では溶剤を使用せず、加熱溶融状態で塗付を行なうので
乾燥工程が不用となる。また、これに伴ってエネルギー
コストおよび廃ガス処理コストを削減てきる。更に従来
のレゾール型樹脂と異なりノボラック型樹脂を使用する
ため、硬化収縮および硬化過程での揮発分発生が少な（
、従って、加熱による寸法変化および反り、ねじれの少
ない積層板が得られる。According to the present invention, no solvent is used in the coating process of the drying oil-modified phenolic resin, and the coating is carried out in a heated molten state, thereby eliminating the need for a drying process. Additionally, energy costs and waste gas treatment costs can be reduced accordingly. Furthermore, unlike conventional resol-type resins, novolac-type resins are used, so there is less curing shrinkage and less volatile matter generation during the curing process (
Therefore, a laminate with less dimensional change, warping, and twisting due to heating can be obtained.

特許出願人 新神戸電機株式会社 代表取締役　石　垣　武三部 ２１９−patent applicant Shin-Kobe Electric Co., Ltd. Representative Director Takesanbe Ishigaki 219-

Claims (1)

【特許請求の範囲】 フェノール樹脂初期縮合物を含浸した七ｌレローズ系紙
基材に、乾性油変性ノボラック型フェノール樹ｉ旨とへ
キサメチレンテトラミンからな　　′る樹脂組成物を加
熱溶融状態で塗付し、この基宸 材の複数１数を重ね合せて加熱加圧成形することを特徴
とする積層板あるいは銅張り積層板の製造法。[Scope of Claims] A resin composition consisting of a drying oil-modified novolac type phenol resin and hexamethylenetetramine is applied in a heated molten state to a 7L rerose paper base material impregnated with a phenolic resin initial condensate. A method for producing a laminate or a copper-clad laminate, characterized in that a plurality of these basic materials are superimposed and molded under heat and pressure.