JP3983578B2 - Thermosetting resin slurry, method for producing prepreg and laminate - Google Patents

Description

【００３６】
４．測定方法
（１）樹脂組成物または樹脂スラリー中の樹脂組成物の平均粒径：粒度分布計（ＨＯＲＩＢＡ ＬＡ−９１０）により測定した。
（２）プリプレグ
▲１▼ 含浸性：プリプレグを実体顕微鏡にて観察し、ガラス繊維間のボイドの有無を確認した。ボイドが実質的に観察されなかったものを「良好」とした。
（３）積層板
▲１▼ エッチング外観：銅張積層板の銅箔をエッチングして、目視により硬化剤等の析出の有無を観察し、樹脂組成物の均一分散性を評価した。硬化剤等の析出や色調ムラ等がみられないものを「良好」とした。
▲２▼ 成形性：エッチング外観の評価用試料を用い、目視により確認した。かすれ等がないものを「良好」とした。
▲３▼ 銅箔引き剥し強さ：ＪＩＳ Ｃ ６４８１により測定した。
▲４▼ 半田耐熱性：５０×５０ｍｍの積層板を、２時間煮沸した後、２６０℃の半田浴に１分間フロートさせ、ふくれ等の有無を確認した。処理後に変化がみられなかったものを「変化なし」とした。
▲５▼ 絶縁抵抗：ＪＩＳ Ｃ ６４８１により測定した。
（４）その他
樹脂混合物中の水分量及び樹脂スラリー中の樹脂組成物含有量は、各々の試料を１５０℃の乾燥器中で３時間加熱処理し水分を除去して、処理前後の試料の重量を測定し算出した。
【００３７】
実施例１〜３はいずれも、微粒子化した樹脂組成物をノズル噴霧装置から噴霧し、これにノズル霧化装置により微粒子化された水を接触させて得られる樹脂混合物を使用した樹脂スラリーであり、また、実施例４は樹脂組成物を衝撃式粉砕装置により微粒子化しながら流動させ、これにノズル霧化装置により微粒子化された水を接触させて得られる樹脂混合物を使用した樹脂スラリーである。これらはいずれも高濃度でありながらハンドリング性に優れたものであった。そして、これらの樹脂スラリーを用いて製造したプリプレグ及び積層板は、比較例４で示した従来の有機溶剤ワニスを用いて製造したものと同等の性能が得られた。
一方、比較例１は実施例１〜３で用いた粒径の小さい樹脂組成物を用いて、従来の方法で樹脂スラリー化することを試みたが、ハンドリング可能な樹脂スラリーにすることができなかった。比較例２は、これより大きな粒径の樹脂混合物を用いたが、プリプレグにボイドが確認され、均一分散性の不足によると思われる色調ムラと、半田耐熱性処理時のミーズリングが発生した。また、比較例３は粉体塗工法で製造したものであるが、比較例２と同様の結果になった。
【００３８】
【発明の効果】
本発明は、微粒子化した固形の熱硬化性樹脂組成物をノズル噴霧装置から噴霧し、これにノズル霧化装置により微粒子化された水を接触させて得られる樹脂混合物を用いることを特徴とする熱硬化性樹脂スラリーの製造方法であり、有機溶剤を用いることなく、ハンドリング性に優れた樹脂スラリーを製造することができる。この樹脂スラリーを用いたプリプレグ及び積層板は、従来の有機溶剤を使用した樹脂ワニスを用いて製造したものと同等の特性を有するものである。従って本発明の製造方法は、省資源化、省エネルギー化、及び低コスト化を図ることができ、さらには作業環境の改善や大気汚染の低減にも寄与することができるものである。
【図面の簡単な説明】
【図１】 本発明の製造方法を実施した樹脂混合物製造装置の一例の側断面図
【図２】 本発明の製造方法を実施した樹脂混合物製造装置の一例の側断面図
【符号の説明】
１ 樹脂組成物
４ ロータリーバルブ
５ ノズル噴霧装置
８ 水
９ 液送ポンプ
１０ ノズル霧化装置
１３ 樹脂混合物製造装置本体
１４ 樹脂組成物に与えられた旋回流
１６ サイクロン
１９ 樹脂組成物
２３ 衝撃式粉砕装置[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a thermosetting resin slurry, and a method for producing a prepreg and a laminated board using the slurry.
[0002]
[Prior art]
There is a strong demand for miniaturization and high functionality for printed circuit boards, but price competition is fierce. In particular, multilayer boards used for printed circuit boards, glass cloth base epoxy resin laminates, or glass nonwoven fabrics are used as intermediate layers. As for the laminated board which used the material and the glass woven fabric as the surface layer base material, reduction of a price has become a big subject in all. Conventionally, a large amount of an organic solvent has been used for a resin varnish in a prepreg manufacturing process used for these. This is because the resin varnish is easy to prepare, and the application and impregnation of the resin to the substrate is uniform and easy. The organic solvent is removed by evaporation in the drying step after coating, but most of the organic solvent has been processed by a combustion device or the like, or has been released into the atmosphere as it is. For this reason, it has been pointed out that it contributes to global warming and air pollution. On the other hand, various attempts have been made to reduce the amount of organic solvent used, but this reduction was difficult due to manufacturing problems such as resin coating and impregnation on the substrate.
[0003]
In order to produce a prepreg without using an organic solvent, a method (hot melt method) in which a low melting point resin or a liquid resin is heated, melted and mixed, and then uniformly applied to the substrate (hot melt method) has been performed. However, the uniformity may be insufficient, and continuous production is likely to cause resin consolidation to equipment due to a decrease in control temperature during continuous production and gelation of thermosetting resin components due to heating. There were many problems in doing.
In addition, a method of directly applying a powdery resin has been proposed, but when a powdery resin having a particle size of several tens to several hundreds of μm is used, it is difficult to uniformly mix and apply the materials, and the resin It may be partially cured or the impregnation of the substrate may be insufficient. On the other hand, when a powdery resin with a smaller particle size is used, the bulk density decreases and handling becomes difficult, and the finely divided material causes secondary agglomeration and the uniform dispersibility decreases. None of these methods have been put into practical use.
[0004]
Apart from this, various investigations have also been made on aqueous resin varnishes. For example, when a low molecular weight liquid resin is emulsified and dispersed to form an O / W (oil-in-water) emulsion, or a water-soluble resin such as a water-based paint is used, Although the impregnating property can be almost the same as when using an organic solvent, it is difficult to satisfy the electrical and mechanical properties required for a laminate, and these raw materials are extremely limited. In other words, it was necessary to select from the above range, and the cost was usually higher than when an organic solvent was used.
Further, there is a method of emulsifying by using water having a low affinity for the resin and dispersing finely pulverized powder resin or the like in the resin. However, since the bulk density of a solid material generally decreases as the particle size is reduced, the apparent volume increases significantly due to the formation of fine particles. When using such a powder resin material, it is necessary to increase the ratio of water in order to prevent a decrease in handling properties due to thickening action, and the resin component is sufficiently retained on the prepreg substrate in the subsequent prepreg coating process. In some cases, it is difficult to perform the drying process, and the energy cost is increased in the drying process.
On the other hand, there is a method of blending a dispersant such as a surfactant having a lipophilic group and a hydrophilic group in order to ensure the affinity between water and the resin composition and suppress the thickening action. If these components remain in the laminate, depending on the type of dispersant used, the electrical characteristics, particularly the reliability such as migration, are reduced, and the required properties of the laminate that require high performance are satisfied. I couldn't do it.
[0005]
In view of the above problems, the present invention has been newly proposed as a method for overcoming the drawbacks, in addition to the advantages of various methods that have been made so far, in order to realize the elimination of organic solvents during prepreg production. Is.
That is, as a result of research on obtaining a prepreg made of a resin that does not use an organic solvent, which has been difficult to produce in the past, and a laminate using the prepreg, a heat obtained by uniformly dispersing a fine-particle thermosetting resin composition in water. Knowledge that by producing a curable resin slurry and using this to produce a prepreg, the dispersibility of raw material components and the impregnation of the base material can be equivalent to those using conventional organic solvents. Got. And according to this method, since the resin component used for the conventional resin varnish can be used as it is, the characteristic requested | required of a laminated board can be ensured.
[0006]
[Problems to be solved by the invention]
The present invention uses a method for producing a thermosetting resin slurry that can disperse a powder resin composition in water with high concentration and high accuracy without using a dispersant such as a surfactant, and this slurry. A method for producing a prepreg and a laminate is provided.
[0007]
[Means for Solving the Problems]
Such an object is achieved by the following present inventions (1) to (7).
(1) A method for producing a thermosetting resin slurry in which a solid thermosetting resin composition containing a thermosetting resin as an essential component is dispersed in water, wherein the thermosetting resin composition is made into fine particles. A method for producing a thermosetting resin slurry, characterized in that a resin mixture obtained by spraying from a nozzle spraying device and contacting water atomized by a nozzle atomizing device is used.
(2) The method for producing a thermosetting resin slurry according to the above (1), wherein the finely divided thermosetting resin composition is sprayed from a nozzle spraying device and is given a swirling flow. .
(3) A method for producing a thermosetting resin slurry in which a solid thermosetting resin composition containing a thermosetting resin as an essential component is dispersed in water, wherein the thermosetting resin composition is impact-pulverized. A method for producing a thermosetting resin slurry, characterized by using a resin mixture obtained by causing fluidization while making fine particles by an apparatus and bringing the water into contact with water atomized by a nozzle atomizer.
(4) The method for producing a thermosetting resin slurry according to (3), wherein the impact pulverizer is a jet mill.
(5) The production of the thermosetting resin slurry according to any one of (1) to (4), wherein the thermosetting resin composition in the thermosetting resin slurry has an average particle size of 0.1 to 10 μm. Method.
(6) The thermosetting resin slurry obtained by the production method according to any one of (1) to (5) is held on a sheet-like fiber base material, and this is heated and dried. A method for manufacturing a prepreg.
(7) Lamination characterized in that one or more prepregs obtained by the method for producing prepreg described in (6) above are overlaid, or further, metal foil is overlaid on one or both sides of the prepreg, followed by heat and pressure molding. A manufacturing method of a board.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Below, the manufacturing method of the thermosetting resin slurry of this invention, the prepreg using this, and the manufacturing method of a laminated board are demonstrated.
The method for producing a thermosetting resin slurry of the present invention is obtained by spraying a finely divided solid thermosetting resin composition from a nozzle spraying device and bringing it into contact with water atomized by a nozzle atomizing device. It is characterized by using a resin mixture.
In addition, the slurry production method of the present invention is a resin obtained by causing a solid thermosetting resin composition to flow while being atomized by an impact pulverizer, and contacting water that has been atomized by a nozzle atomizer. It is characterized by using a mixture.
And the manufacturing method of the prepreg of this invention makes the said thermosetting resin slurry hold | maintain on a sheet-like fiber base material, and heat-drys this, It is characterized by the above-mentioned.
Furthermore, the method for producing a laminated board of the present invention is characterized in that one or more prepregs obtained by the above method are superposed, or further, metal foil is superposed on one or both sides and heat-pressed.
First, the manufacturing method of the thermosetting resin slurry of this invention is demonstrated.
[0009]
The first form of the method for producing a thermosetting resin slurry (hereinafter referred to as “resin slurry”) of the present invention is to spray a finely divided solid thermosetting resin composition from a nozzle spraying device, onto which nozzle mist is sprayed. It is characterized by using a resin mixture obtained by contacting finely divided water with a pulverizing apparatus.
The solid thermosetting resin composition (hereinafter referred to as “resin composition”) in the present invention is composed of a thermosetting resin, a curing agent, a curing accelerator, an inorganic filler, a colorant, and the like, and these are mixed. Say things. The water used as a dispersion medium is usually water alone, but in addition, it may contain a water-soluble component to be blended in the resin composition, and such a case is also included in the present invention.
In the present invention, the resin mixture refers to a resin composition in which the particle surface of the resin composition is wet with water, or a resin composition in which the particle surface of the resin composition is dispersed in water. .
The method for making the resin composition into a finely divided state is not particularly limited, and examples thereof include a method using a resin composition finely divided in advance. In this case, as the resin composition, each material may be made into fine particles to a target particle size using various known crushers, or commercially available materials processed into the target properties may be used. Any of these can be used by mixing them.
[0010]
The finely divided resin composition is sprayed using a nozzle spray device. As a result, sufficient kinetic energy can be given to the resin composition, and the secondary aggregate can be dissociated by the energy given at the time of spraying even when a material having a property that tends to be secondary agglomerated after being finely pulverized is used. And can be fed into the mixing system in the form of primary particles.
When spraying from a nozzle spray device, the resin composition may be supplied directly from a hopper or the like and sprayed, or the resin composition is supplied to a fluidized bed generator using air or the like to form a fluidized bed. The mixture can also be sprayed with air. When the cohesiveness of the resin composition is high and the supply amount is difficult to stabilize when sprayed directly, the supply amount can be stabilized by using a fluidized bed generator.
[0011]
The second embodiment of the method for producing a resin slurry of the present invention is a resin mixture obtained by allowing a resin composition to flow while being atomized by an impact pulverizer and contacting water atomized by a nozzle atomizer with this resin composition. It is characterized by using. The impact pulverizer is not particularly limited, and examples thereof include jet mills such as a swirling powder collision type jet mill and a powder collision type counter jet mill. A jet mill is a device that makes resin mixture collide with each other by a high-speed jet flow using air as a medium, and not only pulverizes a single material but also simultaneously processes multiple types of materials. Further, mixing or compounding can be performed simultaneously with the formation of fine particles, so that the mixing accuracy can be improved and the number of processes can be reduced.
[0012]
In the method for producing a resin slurry of the present invention, in any of the above forms, water is water atomized by a nozzle atomizer and is brought into contact with the resin composition to obtain a resin mixture. Although it does not specifically limit as a nozzle atomizer, A collision type nozzle atomizer etc. other than a general nozzle atomizer can also be used. Water may be supplied directly into the mixing system using such a nozzle atomizing device, or when it is desired to give a larger collision force, diffusion force, etc. to the water when contacting with the resin composition, the device It is also possible to supply the fine particles of water supplied from above on another fluid medium having a larger kinetic energy. The fluid medium is usually compressed air or the like, but is not particularly limited.
[0013]
The method of bringing the resin mixture into contact with water is not particularly limited. However, in the case of the first embodiment in the slurry production method of the present invention, the resin composition is supplied by spraying from a nozzle spray device, It is preferable to give a swirl flow. As a result, the time during which the resin composition is moving in a fine particle state can be lengthened, and the chance of contact with water supplied into the apparatus can be increased. Furthermore, since the resin composition moves while rotating by itself when it flows by the swirling flow, it becomes easy to obtain an opportunity to come into contact with water with respect to its omnidirectional surface. Can be reduced.
This method requires a space for swirling the resin composition, but the resin composition sprayed by the nozzle flows while maintaining high kinetic energy, so that reaggregation of the resin composition particles can be suppressed, It is also suitable for continuous treatment by bringing it into contact with water supplied separately and efficiently.
The contacted material may be collected by a cyclone or the like while being placed in a swirling flow, or may be separated by gravity using a specific gravity difference caused by the contact. In this way, a resin mixture can be obtained.
Further, in the case of the second form in the slurry production method of the present invention, the resin composition is made fine particles by the impact type pulverizer or combined with the fine particles to flow, and then finely divided by the nozzle atomizer. What is necessary is just to make water contact. That is, a resin mixture can be obtained by using the impact pulverizer itself as a mixture production apparatus.
[0014]
The resin slurry of the present invention is produced using the resin mixture obtained by the above method. Although it does not specifically limit as a method to manufacture a resin slurry, It is good also as a resin slurry using the said resin mixture as it is, and diluting or concentrating this.
Although it does not specifically limit as a method to dilute, For example, the method of mixing a resin mixture with water in dispersion | distribution mixing apparatuses, such as a disperser, is mentioned. Since the particle surface is sufficiently wetted with water, the resin mixture obtained by the production method of the present invention can be dispersed in water by such a simple method.
The concentration method is not particularly limited as long as it can separate the resin composition and water, but a solid-liquid separation method using a centrifugal separator is preferable in terms of productivity and cost, and in particular, a screw decanter. A centrifugal sedimentation device of the type is most preferably used. Such an apparatus can easily perform solid-liquid separation even for fine particles having a size of about several μm. In addition, concentration methods such as vacuum distillation, filtration, and electrophoresis may be used.
The resin slurry obtained by such an operation is not particularly limited, but the resin composition concentration in the resin slurry is preferably 50 to 80% by weight. Thereby, it is excellent in handling property and can be used as a resin slurry suitable for making it hold | maintain to the sheet-like fiber base material mentioned later.
[0015]
Next, the material used for the resin slurry of this invention is demonstrated.
Although it does not specifically limit as a thermosetting resin in the resin composition in a resin slurry, For example, an epoxy resin, a phenol resin, a polyester resin etc. are mentioned. Moreover, when the thermosetting resin to be used requires a hardening | curing agent and a hardening accelerator, this can be mix | blended. For example, when the thermosetting resin is an epoxy resin, an acid anhydride compound type, an amine type, particularly dicyandiamide and an aromatic amine, tetramethylenehexamine, and a novolac resin can be suitably used as a curing agent. As the agent, an imidazole compound, a tertiary amine or the like can be preferably used. In addition, an inorganic base material such as aluminum hydroxide or silica powder, a colorant, or the like may be blended as necessary.
[0016]
Although the particle size of the resin composition in the resin slurry of this invention is not specifically limited, It is preferable that an average particle diameter is 0.1-10 micrometers, More preferably, it is 1-6 micrometers. Thereby, the viscosity of the resin slurry can be made excellent in handling properties. Moreover, the uniform dispersibility of each material at the time of manufacture of a resin slurry and a prepreg, and the uniform curability of the resin component at the time of manufacture of a prepreg and a laminated board can be improved. Furthermore, the resin composition particles can easily enter between the fibers of the base material, and can be easily melted and impregnated in a heating and drying process at the time of manufacturing the prepreg described later, whereby a prepreg with good impregnation properties can be obtained. When the average particle size is less than the lower limit, handling properties may be reduced due to the thickening action of the resin slurry. When the average particle size exceeds the upper limit, uniform dispersibility and impregnation tend to be reduced.
Moreover, by setting the particle diameter of the resin composition within the above range, the resin composition particles in the resin slurry are dominated by micro-Brownian motion, and a colloidal dispersion system having a very gentle gravity sedimentation rate can be obtained. Thereby, the dispersion state of the resin slurry can be kept uniform for a long time.
[0017]
Next, the manufacturing method of the slurry of this invention is demonstrated with drawing.
FIG. 1 is an example of an apparatus to which the first embodiment of the method for producing a slurry of the present invention is applied. The resin composition is sprayed from a nozzle spraying apparatus, and a swirling flow is applied in the apparatus to cause it to flow. Water that has been atomized by a nozzle spray device is supplied and both are brought into contact with each other to produce a mixture. In FIG. 1, (a) is a resin composition supply part, (b) is a water supply part, (c) is a production part and a recovery part of a resin mixture.
In FIG. 1A, the resin composition 1 is pulverized and mixed in a separate process and stocked in a hopper 2. In order to prevent bridging inside the hopper, the stirring device 3 is used as necessary. The resin composition is sequentially and quantitatively supplied by the rotary valve 4 in accordance with the mixing ratio with water, and is supplied into the apparatus by the nozzle spray device 5. Reference numeral 6 denotes an air compressor for supplying air used for nozzle spraying.
Further, in FIG. 1B, water 8 is sequentially supplied by a liquid feed pump 9 for supplying a constant amount thereof, and is supplied into the apparatus by a nozzle atomizing device 10. Reference numeral 11 denotes an air compressor for supplying air used for nozzle spraying.
In FIG. 1 (c), the resin composition is sprayed into the apparatus 13 from the supply unit 7. The apparatus 13 has a cylindrical shape, and the resin composition is sprayed and then given a swirl flow 14 in the apparatus, and rises while swirling in the apparatus. On the other hand, water is sprayed from the supply unit 12 into the apparatus. A part of the water comes into contact with the resin composition during spraying, and also flows in the same direction as the resin composition along the swirling flow of the resin composition. The resin mixture is discharged from the upper part 15 of the apparatus by the air suction 18 and sent to the storage unit 17 through the cyclone 16. Moreover, when the specific gravity of a resin mixture is large, it can also collect | recover from the lower part of an apparatus.
[0018]
FIG. 2 is an example of an apparatus to which the second embodiment of the slurry production method of the present invention is applied. The apparatus has an impact pulverization apparatus for pulverizing the resin composition and an apparatus for supplying fine water. Then, the resin composition and water are brought into contact with each other in an impact pulverizer to produce a mixture. FIG. 2 shows an example in which a jet mill is used as an impact pulverizer.
The resin composition 19 is stocked in the hopper 20. Here, the resin composition 19 may be the same as the resin composition 1 used in the first embodiment, or a resin having a particle size larger than this. In order to prevent the occurrence of bridging inside the hopper, a stirring device 21 is used as necessary. The resin composition is sequentially and quantitatively supplied by the rotary valve 22 according to the mixing ratio with water, and is supplied to the jet mill body 23 from the position of the upper part 24 of the jet mill body. The resin composition is formed into fine particles by being repeatedly collided with each other by being given a high-speed jet flow by nozzles 25 (two are shown in the figure, but the number is not limited to this and may be larger) in the jet mill. Alternatively, it is compounded while being finely divided and sent to the upper part of the apparatus.
Water is sprayed from the supply unit 12 into the jet mill by applying the apparatus shown in FIG. Thereby, contact with the finely divided resin composition is performed. The resin mixture is discharged from the upper part of the jet mill to 26 by the air suction 29, and sent to the storage unit 28 through the cyclone 27.
[0019]
Next, the manufacturing method of the prepreg of this invention is demonstrated. The method for producing the prepreg of the present invention is obtained by holding the resin slurry obtained by the above method on a sheet-like fiber base material (hereinafter referred to as “base material”) and heating and drying it. It is.
[0020]
The base material is not particularly limited, but in addition to glass fiber base materials such as glass woven fabric and glass non-woven fabric, woven fabric and non-woven fabric made of paper, synthetic fiber, etc., woven made of metal fiber, carbon fiber, mineral fiber, etc. Examples thereof include cloth, non-woven fabric, and mats. Moreover, what mixed the raw material fiber of these base materials can also be used.
The method of holding the resin slurry on the substrate is not particularly limited, but includes a dip method, a transfer method using a kiss roll, a spraying method using a spray, a coating method using various coaters such as a knife coater and a comma coater. It can be selected appropriately.
[0021]
After the resin slurry is held on the substrate, it is dried by heating. Thereby, substantially all of the water evaporates, and the prepreg impregnated between the base fibers by melting the resin component and the like can be obtained. In addition, you may apply heat until a resin component will be in a semi-hardened state as needed.
Although it does not specifically limit as said heat-drying conditions, Usually, 100-220 degreeC, Preferably it carries out at 120-190 degreeC for 2 to 10 minutes.
The amount of the resin composition to be held in the prepreg is not particularly limited, but is usually about 40 to 60% by weight with respect to the entire prepreg weight (base material + resin composition).
[0022]
Next, the manufacturing method of the laminated board of this invention is demonstrated. The method for producing a laminate of the present invention is obtained by using one or more of the above prepregs, or by superimposing metal foils on one or both sides and heating and pressing. Although it does not specifically limit as conditions of heat-pressure shaping | molding, If an example is given, it will shape | mold in temperature 150-200 degreeC, pressure 2-6 MPa, and time 15-100 minutes.
[0023]
According to the method for producing a resin slurry of the present invention, the wettability with water is improved by bringing water into contact with the finely divided resin composition, and the dispersibility is not easily lowered due to secondary aggregation of the resin composition particles. A resin mixture can be obtained. By using this resin mixture, a resin slurry having a high concentration and excellent dispersibility, which has been difficult to produce by conventional methods, can be produced. This resin slurry is excellent in handleability and can be easily held on a sheet-like substrate. Further, by using a resin composition having a small particle size in the resin slurry, it is possible to produce a prepreg having a good impregnation property and a laminate having excellent characteristics.
By applying such a production method of the present invention, a laminate having substantially the same characteristics as those produced by a conventional method can be obtained without using an organic solvent. Thereby, resource saving, energy saving, and cost reduction are achieved, and further, it can contribute to improvement of the working environment and reduction of air pollution.
[0024]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. “Parts” and “%” described here all indicate “parts by weight” and “% by weight”.
[0025]
1. Production of resin slurry
<Example 1>
(1) Preparation of resin composition
After premixing the material having the following composition with a Henschel mixer, a resin composition having an average particle diameter of 2 μm using a powder impingement jet mill apparatus (manufactured by Hosokawa Micron Corporation, counter jet mill 200AFG, nozzle diameter 3 mm × 3) I got a thing.
(1) Epoxy resin (Japan Epoxy Resin Co., Ltd., brominated epoxy resin Ep5048, epoxy equivalent 675): 100 parts
(2) Curing agent (dicyandiamide): 2 parts
(3) Curing accelerator (2-phenyl-4-methylimidazole): 0.1 part
(2) Preparation of resin mixture
This was performed using the apparatus shown in FIG. As a nozzle spraying apparatus for supplying the prepared resin composition, Atmax Co., Ltd., BN-90S-IS was used, and the air pressure was 4.0 kg / cm. ² As 100 g / min and a swirling flow was generated in the mixing apparatus. As the nozzle atomizing device on the water supply side, magic cut e-mist (nozzle type FN-Z40) manufactured by Fuso Seiki Co., Ltd. is used, and the air pressure is 4.0 kg / cm. ² As 25 g / min. These were supplied into a cylindrical apparatus having an inner diameter of 300 mm and an inner height of 400 mm, contacted with the resin composition and water, and recovered with a cyclone to obtain a resin mixture. The moisture content of this resin mixture was 20%.
(3) Production of resin slurry
Using the above resin mixture, water was further added thereto, followed by stirring with a disperser (rotation speed: 1500 rpm, 10 minutes) to produce a resin slurry having a resin composition concentration of 50%.
[0026]
<Example 2>
(1) Preparation of resin composition
The same operation as in Example 1 was performed.
(2) Preparation of resin mixture
A resin mixture was prepared by supplying the resin composition at 50 g / min and water at 50 g / min, and the same procedure as in Example 1 was performed except that the resin mixture was recovered from the lower part of the apparatus. The moisture content of this resin mixture was 50%.
(3) Production of resin slurry
The resin mixture was used as it was to obtain a resin slurry having a resin composition concentration of 50%.
[0027]
<Example 3>
(1) Preparation of resin composition
After premixing the material having the following composition with a Henschel mixer, a resin composition having an average particle diameter of 2 μm using a powder impingement jet mill apparatus (manufactured by Hosokawa Micron Corporation, counter jet mill 200AFG, nozzle diameter 3 mm × 3) I got a thing.
(1) Epoxy resin (Japan Epoxy Resin Co., Ltd., brominated epoxy resin Ep5048, epoxy equivalent 675): 100 parts
(2) Curing accelerator (2-phenyl-4-methylimidazole): 1.5 parts
(2) Preparation of resin mixture
A resin mixture was prepared by supplying the resin composition at 40 g / min and water at 80 g / min, and the same procedure as in Example 1 was performed except that the resin mixture was recovered from the lower part of the apparatus. The water content of this resin mixture was 32%.
(3) Production of resin slurry
Using the centrifugal separator, the resin mixture was treated at 5000 rpm for 3 minutes to remove the supernatant, and a resin slurry having a resin composition concentration of 50% was produced.
[0028]
<Example 4>
(1) Preparation of resin composition
A material having the following composition was premixed with a Henschel mixer to obtain a resin composition.
(1) Epoxy resin (Japan Epoxy Resin Co., Ltd., brominated epoxy resin Ep5048, epoxy equivalent 675, average particle size 80 μm): 100 parts
(2) Curing agent (dicyandiamide, average particle size 15 μm): 2 parts
(3) Curing accelerator (2-phenyl-4-methylimidazole, average particle size 15 μm): 0.1 part
(2) Preparation of resin mixture
This was performed using the apparatus shown in FIG. As an impact pulverizer, a powder impingement type jet mill device (manufactured by Hosokawa Micron Co., Ltd., counter jet mill 200AFG, nozzle diameter 3 mm × 3), an air pressure of 600 kPa and a pressurized air amount of 1.7 m are used. ^Three / Min. The resin composition is supplied at a rate of 100 g / min, and the same nozzle atomizer as that used in Example 1 is used as the water supply side nozzle, and the air pressure is 4.0 kg / cm. ² As 25 g / min. This was recovered with a cyclone to obtain a resin mixture. The moisture content of this resin mixture was 20%.
(3) Production of resin slurry
Using the above resin mixture, water was further added thereto, followed by stirring with a disperser (rotation speed: 1500 rpm, 10 minutes) to produce a resin slurry having a resin composition concentration of 50%. The average particle size of the resin composition in the resin slurry was 5.7 μm.
[0029]
<Comparative Example 1>
100 parts of the resin composition used in Example 1 was dispersed in 100 parts of water by using a disperser (rotation number: 1500 rpm), and an attempt was made to produce a resin slurry. The resin slurry was lost and could not be handled.
[0030]
<Comparative Example 2>
100 parts of the resin composition used in Example 4 was dispersed in 100 parts of water using a disperser (rotation speed: 1500 rpm, 10 minutes) to produce a resin slurry.
[0031]
<Comparative Example 3>
The resin composition used in Example 4 was used as it was.
[0032]
<Comparative Example 4>
Epoxy resin (Japan Epoxy Resin Co., Ltd., brominated epoxy resin Ep5048, epoxy equivalent 675) 100 parts, curing agent (dicyandiamide) 2 parts, and curing accelerator (2-ethyl-4-methylimidazole) 0.1 parts Was dissolved in 100 parts of methyl cellosolve to prepare a resin varnish.
[0033]
2. Manufacture of prepreg
(1) Basis weight of 104 g / m using the resin slurry obtained in Examples 1 to 4 ² Evenly applied to both sides of the glass woven fabric with a comma coater, the resin composition weight 114 g / m ² And then dried with a hot air heater at 170 ° C. for 3 minutes to obtain a prepreg.
(2) Using the resin slurry obtained in Comparative Example 2, the basis weight is 104 g / m. ² Evenly applied to both sides of the glass woven fabric with a comma coater, the resin composition weight 114 g / m ² And then dried with a hot air heater at 170 ° C. for 3 minutes to obtain a prepreg.
(3) Using the resin composition obtained in Comparative Example 3, 104 g / m ² The weight of the resin composition is 57 g / m with a knife coater on the upper surface of the glass woven fabric. ² After coating with a hot air heater at 170 ° C. for 1 minute, the glass cloth is turned upside down and the total weight of the resin composition is 114 g / m with a knife coater on the other side. ² Then, it was uniformly coated and dried with a hot air heater at 170 ° C. for 2 minutes to obtain a prepreg.
(4) Using the resin varnish obtained in Comparative Example 4, this varnish was obtained with a basis weight of 104 g / m. ² A resin composition weight of 114 g / m ² The prepreg was obtained by heating and drying with a hot air heater at 170 ° C. for 3 minutes.
[0034]
3. Manufacture of copper clad laminate
Two prepregs obtained in the examples and comparative examples are overlapped, and an electrolytic copper foil with a thickness of 18 μm is overlapped on the front and back, and heat pressing is performed at a temperature of 165 ° C. and a pressure of 4 MPa for 90 minutes using a vacuum press apparatus. Thus, a copper-clad laminate having a thickness of 0.22 mm was produced.
[0035]
Each characteristic was evaluated about the resin slurry, the prepreg, and the laminated board which were obtained by the Example and the comparative example. The results are shown in Table 1.
[Table 1]

[0036]
4). Measuring method
(1) Average particle diameter of resin composition in resin composition or resin slurry: measured by a particle size distribution meter (HORIBA LA-910).
(2) Prepreg
(1) Impregnation: The prepreg was observed with a stereomicroscope, and the presence or absence of voids between the glass fibers was confirmed. A sample in which no void was substantially observed was defined as “good”.
(3) Laminated board
(1) Etching appearance: The copper foil of the copper clad laminate was etched, and the presence or absence of precipitation of a curing agent or the like was visually observed to evaluate the uniform dispersibility of the resin composition. A sample in which no curing agent or color tone unevenness was observed was defined as “good”.
(2) Formability: Using a sample for evaluation of etching appearance, it was confirmed visually. Those with no fading were defined as “good”.
(3) Copper foil peel strength: Measured according to JIS C 6481.
{Circle around (4)} Solder heat resistance: A 50 × 50 mm laminated board was boiled for 2 hours and then floated in a 260 ° C. solder bath for 1 minute to check for blistering. Those that did not change after the treatment were defined as “no change”.
(5) Insulation resistance: Measured according to JIS C 6481.
(4) Other
The amount of water in the resin mixture and the content of the resin composition in the resin slurry are calculated by measuring the weight of the sample before and after the treatment by heating each sample in a dryer at 150 ° C. for 3 hours to remove the water. did.
[0037]
Each of Examples 1 to 3 is a resin slurry using a resin mixture obtained by spraying a finely divided resin composition from a nozzle spraying device and bringing it into contact with water atomized by a nozzle atomizing device. Further, Example 4 is a resin slurry using a resin mixture obtained by causing a resin composition to flow while being atomized by an impact pulverizer and contacting water atomized by a nozzle atomizer. All of these were excellent in handling properties despite their high concentration. The prepreg and laminate produced using these resin slurries obtained the same performance as those produced using the conventional organic solvent varnish shown in Comparative Example 4.
On the other hand, Comparative Example 1 tried to make a resin slurry by a conventional method using the resin composition having a small particle diameter used in Examples 1 to 3, but it could not be handled as a resin slurry. It was. In Comparative Example 2, a resin mixture having a particle size larger than this was used, but voids were observed in the prepreg, and color unevenness considered to be due to lack of uniform dispersibility and mesling during solder heat resistance treatment occurred. Moreover, although the comparative example 3 was manufactured by the powder coating method, it became the same result as the comparative example 2.
[0038]
【The invention's effect】
The present invention is characterized by using a resin mixture obtained by spraying a microparticulated solid thermosetting resin composition from a nozzle spraying device and bringing it into contact with water atomized by a nozzle atomizing device. This is a method for producing a thermosetting resin slurry, and a resin slurry having excellent handling properties can be produced without using an organic solvent. The prepreg and laminate using this resin slurry have characteristics equivalent to those produced using a resin varnish using a conventional organic solvent. Therefore, the production method of the present invention can achieve resource saving, energy saving, and cost reduction, and can also contribute to improvement of the working environment and reduction of air pollution.
[Brief description of the drawings]
FIG. 1 is a side cross-sectional view of an example of a resin mixture production apparatus that implements the production method of the present invention
FIG. 2 is a side cross-sectional view of an example of a resin mixture production apparatus that implements the production method of the present invention.
[Explanation of symbols]
1 Resin composition
4 Rotary valve
5 Nozzle spray device
8 water
9 Liquid feed pump
10 Nozzle atomizer
13 Resin mixture production equipment
14 Swirl flow given to resin composition
16 Cyclone
19 Resin composition
23 Impact type crusher

Claims (7)

A method for producing a thermosetting resin slurry in which a solid thermosetting resin composition containing a thermosetting resin as an essential component is dispersed in water, wherein the finely divided thermosetting resin composition is a nozzle spray device. A method for producing a thermosetting resin slurry, characterized in that a resin mixture obtained by spraying from the above and contacting water finely divided by a nozzle atomizer is used. The method for producing a thermosetting resin slurry according to claim 1, wherein the finely divided thermosetting resin composition is sprayed from a nozzle spraying apparatus and is given a swirling flow to flow. A method for producing a thermosetting resin slurry in which a solid thermosetting resin composition containing a thermosetting resin as an essential component is dispersed in water, wherein the thermosetting resin composition is finely divided by an impact pulverizer. A method for producing a thermosetting resin slurry, characterized by using a resin mixture obtained by allowing a resin mixture obtained by allowing the water to flow while being made into contact with water atomized by a nozzle atomizer. The method for producing a thermosetting resin slurry according to claim 3, wherein the impact pulverizer is a jet mill. The method for producing a thermosetting resin slurry according to any one of claims 1 to 4, wherein the thermosetting resin composition in the thermosetting resin slurry has an average particle size of 0.1 to 10 µm. A method for producing a prepreg, wherein the thermosetting resin slurry obtained by the production method according to any one of claims 1 to 5 is held on a sheet-like fiber substrate and dried by heating. One or more prepregs obtained by the method for producing prepreg according to claim 6 are overlaid, or further, metal foil is overlaid on one or both sides of the prepreg, followed by heat and pressure molding, and a method for producing a laminated board .

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