JP2008280470A - Method for producing prepreg, method for producing composite laminated board and composite laminated board - Google Patents

Method for producing prepreg, method for producing composite laminated board and composite laminated board Download PDF

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JP2008280470A
JP2008280470A JP2007127529A JP2007127529A JP2008280470A JP 2008280470 A JP2008280470 A JP 2008280470A JP 2007127529 A JP2007127529 A JP 2007127529A JP 2007127529 A JP2007127529 A JP 2007127529A JP 2008280470 A JP2008280470 A JP 2008280470A
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resin
prepreg
weight
glass
woven fabric
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Haruyuki Hatano
晴行 秦野
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Sumitomo Bakelite Co Ltd
住友ベークライト株式会社
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Abstract

A method for producing a prepreg for a composite laminate, a method for producing a composite laminate, and a composite laminate are provided that have both low linear expansion and punchability while maintaining low cost.
A method for continuously producing a prepreg composed of a first layer and a second layer, which is used for a composite laminate, wherein a glass woven fabric is impregnated with a first resin material. A first step of heating and drying, a second step of placing a glass nonwoven fabric on the glass woven fabric, impregnating a second resin material from the upper surface of the glass nonwoven fabric, and drying by heating; Processing a laminate comprising a cloth and a glass nonwoven fabric, a third step of forming the first layer obtained in the first step and the second layer obtained in the second step; Is a method for producing a prepreg for a composite laminate.
[Selection] Figure 1

Description

  The present invention relates to a method for producing a prepreg, a method for producing a composite laminate, and a composite laminate.

  Many types of laminates are used for printed circuit boards. Among these, composite laminates with glass nonwoven fabric as the intermediate layer substrate and glass woven fabric as the surface layer substrate are the basic mechanical properties, electrical Because of its excellent characteristics and low price, it is used in a wide range of industries such as industry and consumer. In addition, many studies have been made on a method for efficiently producing a prepreg for a composite laminate using a plurality of types of substrates as described above (for example, Patent Document 1).

  Composite laminates generally tend to have a higher coefficient of linear expansion than glass woven fabric laminates. Therefore, in order to further improve the reliability of solder connections with mounted components, the composite laminates have low linear expansion. The rate is being considered.

One technique for imparting low linear expansion to a composite laminate is a technique in which an inorganic filler is added to a resin composition impregnated in a substrate (for example, Patent Document 2). In recent years, high-density mounting has progressed, and further lower linear expansion has been required. There is a technique to increase the amount of inorganic filler for low linear expansion, but it is a resin material that is applied to glass woven fabric and a resin material that is applied to glass unwoven fabric. Including, the adhesion between the surface layer and the intermediate layer is not necessarily sufficient, there is a concern of peeling between the surface layer and the intermediate layer in processing steps such as cutting of the composite laminate, stamping, There has been a demand for the development of a composite laminate having both heat stability and workability.
JP 2003-236868 A JP 2005-290029 A

  The present invention has been made in view of the above circumstances, and a method for manufacturing a prepreg for a composite laminate having both stability during heat and workability while maintaining cost reduction, and a method for producing a composite laminate And providing a composite laminate.

A method for producing a prepreg according to the present invention is a method for continuously producing a prepreg composed of a first layer and a second layer, which is used for a composite laminate, and is a first method for a glass woven fabric. A first step of impregnating and heating and drying the resin material, and placing a glass nonwoven fabric on the glass woven fabric, impregnating the second resin material from the upper surface of the glass nonwoven fabric, and heating and drying the second step A third step of processing a laminate comprising glass woven fabric and glass nonwoven fabric, forming a surface layer comprising glass woven fabric and impregnating resin, and an intermediate layer comprising glass nonwoven fabric and impregnating resin;
It is characterized by including.

  As a general method of manufacturing a prepreg, after impregnating a resin material from one side of a glass woven fabric, placing the glass nonwoven fabric on the impregnated surface and impregnating another resin material from the surface side of the glass nonwoven fabric And then drying by heating. In this manufacturing method, when the glass nonwoven fabric is placed, a part of the resin material impregnated in the glass woven fabric is sucked to the glass nonwoven fabric side. When the other resin material is impregnated in the next step, the resin material may be mixed inside the glass nonwoven fabric, resulting in a non-uniform resin material. Furthermore, in a resin system with a lot of inorganic fillers, there is a concern that the resin material becomes more uneven at the interface between the glass woven fabric and the glass nonwoven fabric, and sufficient adhesion between the layers cannot be given during processing of the laminate. .

  In contrast, in the present invention, the glass woven fabric is impregnated with the first resin material and then dried by heating. Thus, when the glass nonwoven fabric is placed on the glass woven fabric, the first resin material has a high viscosity by heat drying, and the first resin material does not easily penetrate into the glass nonwoven fabric side. Therefore, the resin material is mixed inside the glass nonwoven fabric described above, and the resin material is not non-uniform.

  The glass woven fabric may be impregnated with the first resin material from one surface side, and the glass nonwoven fabric may be placed on the surface. Thereby, the first resin material is heavily impregnated on the glass woven fabric surface side of one surface side, and the glass nonwoven fabric is placed on the surface, thereby laminating and adhering to the boundary surface with the glass nonwoven fabric. Sufficient resin material can be supplied.

  Furthermore, a fourth step of impregnating the glass woven fabric with a third resin material from the other surface side may be included. Thereby, the resin component can be supplemented to the other surface side. Therefore, for example, when a metal foil is laminated and bonded to the other surface side, it is possible to secure a sufficient resin component for bonding.

  The first resin material and the second resin material can be as follows.

  The first resin material includes an epoxy resin and a curing agent, and may further include a phenoxy resin.

  The second resin material includes an inorganic filler, an epoxy resin, and a curing agent, and may not include a phenoxy resin.

  Thereby, it can be set as the prepreg by which the resin material was hard to mix from the difference in compatibility of the 1st resin material containing a phenoxy resin, and the 2nd resin material, and the interface was formed uniformly.

  In addition, it is possible to provide a method for producing a composite laminate in which two prepregs obtained by the method for producing prepreg are overlapped and laminated so that the second layer faces each other and the first layer is on the outside. Moreover, a composite laminated board can be provided with the manufacturing method of the above-mentioned composite laminated board.

  As a result, it is possible to provide a composite laminate having both heat stability and workability while maintaining cost reduction.

  According to the present invention, it is possible to provide a method for producing a composite laminate prepreg, a method for producing a composite laminate, and a composite laminate that have both thermal stability and workability while maintaining low cost. it can.

  The prepreg manufacturing method and composite laminate of the present invention will be described below.

  The method for producing a prepreg can be divided into the following four steps.

That is,
(First step) A step of impregnating a glass woven fabric with a first resin material and drying by heating.
(Second step) A step of placing a glass nonwoven fabric on a glass woven fabric, impregnating the second resin material from the upper surface of the glass nonwoven fabric, and drying by heating.
(3rd process) The process which processes the laminated body which consists of a glass woven fabric and a glass nonwoven fabric, and forms the surface layer which consists of a glass woven fabric and an impregnation resin, and the intermediate | middle layer which consists of a glass nonwoven fabric and an impregnation resin.
(Fourth step) A step of impregnating the glass woven fabric with the third resin material from the other surface side and drying by heating.

  The method for producing a prepreg according to the present invention is a method for continuously producing a prepreg composed of a first layer and a second layer, which is used for a composite laminate. When the composite laminate is a composite laminate, the composite laminate comprises a first layer that forms a surface layer and a second layer that forms a core.

Each step will be described below.
[First step]
As shown in FIG. 1, the glass resin fabric is impregnated with the first resin material and dried by heating. When the glass nonwoven fabric is placed on the glass woven fabric by impregnating the glass woven fabric with the first resin material and then heated and dried, the first resin material has a high viscosity by heating and drying. The first resin material does not easily penetrate into the nonwoven fabric side. When the second resin material is impregnated from the upper surface of the glass nonwoven fabric, the second resin material reaches the boundary surface between the glass woven fabric and the glass nonwoven fabric, so that a uniform boundary surface can be formed.

Although it does not specifically limit as a glass woven fabric, The thing per unit area is 150-250 g / cm < 2 > is preferable. More preferably, it is 190-230 g / cm < 2 >. Thereby, the mechanical strength of the composite laminate can be ensured.

  Further, the glass woven fabric may be impregnated with the first resin material from one surface side, and the glass nonwoven fabric may be placed on the surface. Thereby, the first resin material is heavily impregnated on the glass woven fabric surface side of one surface side, and the glass nonwoven fabric is placed on the surface, thereby laminating and adhering to the boundary surface with the glass nonwoven fabric. Sufficient resin material can be supplied.

  The first resin material may contain an epoxy resin and a curing agent. Heat resistance can be imparted by including an epoxy resin.

  Here, the epoxy resin is not particularly limited, and examples thereof include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD type epoxy resin, phenol novolac type epoxy resins, cresol novolac type epoxy resins and the like. Brominated epoxy resins such as novolac epoxy resins, brominated bisphenol A epoxy resins, brominated phenol novolac epoxy resins, and heterocyclic epoxy resins such as triglycidyl isocyanate, alicyclic epoxy resins, and biphenyl types Examples thereof include an epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, and the like. These can be used alone or in combination of two or more.

  Moreover, when manufacturing what does not contain a halogen substance as a composite laminated board, the epoxy resin which does not contain a halogen atom substantially can be used as said epoxy resin. In addition, as an epoxy resin which does not contain a halogen atom substantially here, what has content of the halogen atom in resin below 1 weight% can be used, for example.

  A curing agent may be used for the first resin material. Although it does not specifically limit as a hardening | curing agent, For example, an aliphatic polyamine, an aromatic polyamine, an alicyclic acid anhydride, an aromatic acid anhydride, an isocyanate compound, a novolak-type phenol resin, an imidazole compound, a dicyandiamide etc. are mentioned. These can be used alone or in combination of two or more.

The first resin material may further contain a phenoxy resin. Thereby, plasticity can be imparted between the surface layer and the intermediate layer of the composite laminate, and the dimensional change of the intermediate layer relative to the thermal history can be absorbed, so the linear expansion on the surface layer side is reduced, Solder connection reliability with a component mounted on the surface layer can be improved. At the same time, because of the difference in compatibility between the first resin material containing the phenoxy resin and the second resin material, the resin material can not be mixed with each other, and the prepreg can be formed with a uniform interface. When it is, it can be set as the laminated board excellent in the adhesive force of a surface layer and an intermediate | middle layer interface.

  Although it does not specifically limit as phenoxy resin used here, For example, in addition to phenoxy resin which has bisphenol skeletons, such as bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, bisphenol A and F mixed type phenoxy resin, it has a naphthalene skeleton. Examples include phenoxy resins and phenoxy resins having a biphenyl skeleton.

  The molecular weight of the phenoxy resin is not particularly limited, but it is preferable to use a resin having a weight average molecular weight of 10,000 or more. More preferably, it is 30000-80000. Thereby, the said characteristic can be expressed more effectively.

  In addition to the phenoxy resin, other components can be used to improve adhesion and connection reliability. For example, polyester resin, polyurethane resin, polybutadiene, polypropylene, styrene-butadiene-styrene copolymer, polyacetal resin, polyvinyl butyral resin, polymethacrylate, polycarbonate, butyl rubber, chloroprene rubber, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-methacrylic. Acid copolymers, acrylonitrile-butadiene-styrene copolymers, acrylic copolymers, polyvinyl acetate resins, nylon, styrene-isoprene copolymers, styrene-butylene-styrene block copolymers, etc. can be used. These may be used alone or in combination of two or more.

  Moreover, when manufacturing what does not contain a halogen substance as a composite laminated board, the phenoxy resin which does not contain a halogen atom substantially can be used as said phenoxy resin. Here, as the phenoxy resin substantially not containing a halogen atom, for example, a resin having a halogen atom content of 1% by weight or less in the resin can be used.

  In the first resin material, the blending ratio (E: P) of the epoxy resin (E) and the phenoxy resin (P) is not particularly limited, but may be contained at a weight ratio of 1: 9 to 8: 2. preferable. More preferably, it is 3: 7-7: 3. Thereby, the heat resistance as a composite laminated board and the said effect can be made compatible at a high level.

  The first resin material contains the epoxy resin, the curing agent, and the phenoxy resin as the main components as the resin material, but in addition, other resin materials such as, for example, within a range not impairing the effects of the present invention, In addition to phenol resin, polyimide resin, polyamide resin, etc., compounds such as tetrabromobisphenol A that reacts with epoxy resin can be blended and used.

  The first resin material may contain an inorganic filler in addition to the resin component. Thereby, a flame retardance, low linear expansion property, tracking resistance, etc. can be provided to a composite laminated sheet.

  The inorganic filler used here is not particularly limited, and examples thereof include aluminum hydroxide, calcium carbonate, clay, talc, and silica. Among these, when aluminum hydroxide is used, in addition to the above effects, flame resistance can be imparted to the composite laminate.

  When the inorganic filler is used, the blending amount is not particularly limited, but is preferably 20 to 80 parts by weight with respect to 100 parts by weight of the total resin component.

  Although the quantity of the 1st resin material apply | coated to a glass woven fabric is not specifically limited, It is preferable that it is 20-200 weight part with respect to 100 weight part of glass woven fabric. More preferably, it is 40-150 weight part. If the amount of the first resin material is within the above lower range, the adhesion between the surface layer and the intermediate layer of the composite laminate is maintained, and the surface layer and the intermediate layer are processed in processing steps such as cutting and punching. It is possible to prevent peeling between the two.

  The method for applying the first resin material to the glass woven fabric is not particularly limited. However, the glass woven material is coated with a coater device such as a comma roll coater, knife coater, die coater, reverse coater, etc., using the first resin material as a varnish. A method of coating on the upper surface of the cloth is preferred. In particular, it is preferable to use a comma roll coater or a knife coater. Thereby, even if it uses the 1st resin material with the form of a high-viscosity varnish, uniform coating can be performed easily.

In the method for producing a prepreg of the present invention, the conditions for heating and drying the glass woven fabric coated with the first resin material after the above step are not particularly limited. For example, the conditions are 120 to 180 ° C. and 1 to 5 minutes. It can be carried out.
[Second step]
Next, a glass nonwoven fabric is placed on the glass woven fabric, impregnated with the second resin material from the upper surface of the glass nonwoven fabric, and heated and dried.

  In the first step, the first resin material is heat-dried. Therefore, when the glass nonwoven fabric is placed on the glass woven fabric, the first resin material has a high viscosity by heat drying, and the first resin material does not easily penetrate into the glass nonwoven fabric side. When the second resin material is impregnated from the upper surface of the glass nonwoven fabric, the second resin material does not penetrate into the glass woven fabric side even if it reaches the interface between the glass woven fabric and the glass nonwoven fabric. A uniform boundary surface of the resin material can be formed at the boundary surface between the woven fabric and the glass nonwoven fabric.

  Although it does not specifically limit as a glass nonwoven fabric, It is preferable to use the thing whose weight per unit area is 25-150 g / cm <2>. More preferably, it is 30-120 g / cm <2>. Thereby, the mechanical strength of the composite laminate can be ensured.

  A second resin material containing an epoxy resin and an inorganic filler is applied from above the glass nonwoven fabric in the second step.

  The second resin material used in the second step may contain an epoxy resin, a curing agent, and an inorganic filler. Thereby, low linear expansion and punchability can be imparted to the composite laminate.

  As the epoxy resin, the curing agent, and the inorganic filler used for the second resin material, those similar to the first resin material can be used. In addition to these, other resin components such as a phenol resin, a polyimide resin, an amide resin, and a compound such as tetrabromobisphenol A that reacts with an epoxy resin can be used.

  Although it does not specifically limit as a compounding quantity of the inorganic filler in 2nd resin material, 130-250 weight part with respect to a total of 100 weight part of resin components (resin, hardening | curing agent, etc.) in 2nd resin material. It is preferable to do. More preferably, it is 150-200 weight part. If the blending amount is less than the above lower limit value, the effect of improving low thermal expansion and dimensional stability may be reduced. On the other hand, when the above upper limit is exceeded, the moldability may be lowered, and the resulting thermal characteristics may be lowered. Here, the resin material refers to a material containing an inorganic filler, and the resin component refers to a resin or a curing agent excluding the inorganic filler.

  Examples of inorganic fillers include, but are not limited to, silicates such as talc, fired clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica, calcium carbonate, magnesium carbonate, Carbonates such as hydrotalcite, hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, barium metaborate, boron Examples thereof include borates such as aluminum oxide, calcium borate and sodium borate, and nitrides such as aluminum nitride, boron nitride and silicon nitride. These can be used alone or in combination. Of these, aluminum hydroxide is more preferably used. Thereby, heat resistance can further be improved, maintaining high flame resistance.

  Although the quantity of the 2nd resin material apply | coated to a glass nonwoven fabric is not specifically limited, It is preferable that it is 500-2000 weight part with respect to 100 weight part of glass nonwoven fabric. More preferably, it is 700-1500 weight part. If the amount of the second resin material is less than the above lower limit, the adhesiveness between the prepregs tends to be reduced when the composite laminate is molded, which may affect the thermal characteristics of the composite laminate. When the amount is larger than the above upper limit value, the moldability is lowered.

The method of applying the second resin material to the glass nonwoven fabric is not particularly limited, but the second resin material is a varnish, and the glass nonwoven fabric is coated using a coater device such as a comma roll coater, knife coater, die coater, reverse coater, etc. A method of coating on the upper surface is preferred. In particular, it is preferable to use a comma roll coater or a knife coater. This can be heat-dried to evaporate the solvent in the second resin material. Although this heat-drying condition is not specifically limited, For example, it can carry out at 120-180 degreeC and 1 to 10 minutes.
[Third step]
Next, the laminated body which consists of a glass woven fabric and a glass nonwoven fabric is processed, and the intermediate | middle layer which consists of a surface layer which consists of glass woven fabric and an impregnation resin, and a glass nonwoven fabric and an impregnation resin is formed.

The glass woven fabric and glass nonwoven fabric obtained in the first and second steps are used as a laminate, and a prepreg is composed of a surface layer made of glass woven fabric and impregnating resin, and an intermediate layer made of glass nonwoven fabric and impregnating resin. .
[Fourth step]
In the manufacturing method of a prepreg, you may have processes other than the above. For example, the glass resin fabric is impregnated with the third resin material from the other surface side. In the first step, for example, when the first resin material is impregnated from one side of the glass woven fabric, the resin material may not be uniformly impregnated due to the influence of the viscosity of the first resin material. In this case, the amount of the resin material on the other surface side can be compensated by impregnating the third resin material from the other surface side of the glass woven fabric in the fourth step. Therefore, for example, when a metal foil is laminated and bonded to the other surface side, it is possible to secure a sufficient resin component for bonding.

  As the third resin material, a resin composition containing an epoxy resin and a curing agent can be suitably used. In addition, other resin components such as a phenol resin and a polyimide resin, and a compound such as tetrabromobisphenol A that reacts with an epoxy resin can be used in combination.

  The third resin material can be blended with an inorganic filler in addition to these resin components. Thereby, a flame retardance, low linear expansion property, tracking resistance, etc. can be provided to a composite laminated sheet.

  The inorganic filler used here is not particularly limited, and examples thereof include aluminum hydroxide, calcium carbonate, clay, talc, and silica. Among these, when aluminum hydroxide is used, in addition to the above effects, flame resistance can be imparted to the composite laminate.

  When the inorganic filler is used, the blending amount is not particularly limited, but is preferably 20 to 80 parts by weight with respect to 100 parts by weight of the total resin component.

  As the epoxy resin and the curing agent used for the third resin material, the same resin as the first resin material can be used. Among these, since both the first resin material and the third resin material are coated and impregnated on the same glass woven fabric, it is preferable to use the same type.

  Although it does not specifically limit as a form of 3rd resin material, It is preferable to set it as the varnish containing the component demonstrated above. Thereby, the handleability at the time of apply | coating to a glass woven fabric and the impregnation property to a glass woven fabric can be made favorable.

  The amount of the third resin material applied to the glass woven fabric is not particularly limited, but is preferably 20 to 200 parts by weight with respect to 100 parts by weight of the glass woven fabric. More preferably, it is 40-150 weight part. When the amount of the third resin material is less than the lower limit, the adhesion between the copper foil and the prepreg is lowered. On the other hand, when the amount is larger than the above upper limit value, the amount of the resin is increased and the moldability and the dimensional stability are liable to be reduced.

  The method for applying the third resin material to the glass woven fabric is not particularly limited, but a method in which the third resin material is used as a varnish and coating is performed using an apparatus such as a transfer roll, a roll coater, or a knife coater is preferable. Moreover, although the conditions to heat-dry are not specifically limited, For example, it can carry out at 120-180 degreeC and 1 to 10 minutes. Thereby, while substantially evaporating and removing the solvent in the resin composition used in the first to fourth steps, the prepreg having good handleability is obtained by advancing the curing reaction of the resin material halfway. Can do.

  The obtained prepreg can be used for molding a composite laminate after being cut into a prepreg having a predetermined length by a cutter device. Moreover, you may use for shaping | molding of a continuous composite laminated board with a long thing.

Moreover, the suitable combination example of these resin materials is shown.
(1) As a first resin material, 70 parts by weight of bisphenol A type epoxy resin, 27 parts by weight of cresol novolac type epoxy resin, 3 parts by weight of dicyandiamide as a curing agent, 2-ethyl-4-methyl as a curing accelerator 0.1 parts by weight of imidazole and 50 parts by weight of aluminum hydroxide.

As the second resin material, 25 parts by weight of bisphenol A type epoxy resin, 25 parts by weight of cresol novolac type epoxy resin, 25 parts by weight of tetrabromobisphenol A, 25 parts by weight of novolac type phenol resin, 2 as a curing accelerator -0.1 parts by weight of ethyl-4-methylimidazole and 175 parts by weight of aluminum hydroxide.
(2) 50 parts by weight of bisphenol A type epoxy resin, 47 parts by weight of phenoxy resin, 3 parts by weight of dicyandiamide as a curing agent, and 2-ethyl-4-methylimidazole as a curing accelerator as the first resin material 0.1 parts by weight and 50 parts by weight of aluminum hydroxide.

    As the second resin material, 25 parts by weight of bisphenol A type epoxy resin, 25 parts by weight of cresol novolac type epoxy resin, 25 parts by weight of tetrabromobisphenol A, 25 parts by weight of novolac type phenol resin, 2 as a curing accelerator -0.1 parts by weight of ethyl-4-methylimidazole and 175 parts by weight of talc.

  Next, the manufacturing method of the composite laminated board of this invention is demonstrated.

  The method for producing a composite laminate of the present invention is characterized in that two prepregs obtained by the method for producing a prepreg of the present invention are used, the glass nonwoven fabric side is overlapped, and heat-press molding is performed.

  Although it does not specifically limit as the conditions which carry out the above-mentioned heat-press molding, For example, it can carry out at the temperature of 150-200 degreeC, the pressure of 1-4 MPa, and time 60-120 minutes.

  The composite laminate thus obtained is excellent in low linear expansion and punchability.

  Next, an example of the suitable form about the manufacturing method of the prepreg of this invention is demonstrated in detail, referring drawings.

  In FIG. 1, the glass woven fabric 1 is successively supplied from the unwinding device. Then, a predetermined amount of the first resin material 3 is applied to the upper surface side 2 of the glass woven fabric 1 by a comma coater device 4, and then dried by heating using a drying device 5. Next, the glass nonwoven fabric 7 is supplied from the unwinding device, the glass nonwoven fabric 7 is placed so as to be in contact with the surface layer, and the second resin material 9 is placed by the comma coater device 10 from the upper surface side 8 of the laminated glass nonwoven fabric 7. Apply a certain amount. After passing this through the drying device 11, a predetermined amount of the third resin material 13 is applied by the transfer roll device 14 from the lower surface side 12 of the glass woven fabric. After passing this through the drying device 15, the prepreg 17 can be obtained by cutting into a predetermined length by the cutting device 16.

Hereinafter, the present invention will be described specifically by way of examples.
1. Preparation of 1st resin material, 2nd resin material, and 3rd resin material The following raw material is mix | blended in the quantity (weight part) shown in Table 1, and resin composition (a1)-(a2) Resin compositions (b1) to (b3) and a third resin material were obtained.
(1) Bisphenol A type epoxy resin: manufactured by Dainippon Ink & Chemicals, Inc. “Epicron 850”, epoxy equivalent 190
(2) Cresol-Lunovolak type epoxy resin: manufactured by Dainippon Ink & Chemicals, Inc. “Epicron N-690-75M”, epoxy equivalent 225
(3) Phenoxy resin: manufactured by Japan Epoxy Resin Co., Ltd. “Epicoat 1256”, weight average molecular weight 50000
(4) Tetrabromobisphenol A
(5) Novolac-type phenolic resin: “PR-51470” manufactured by Sumitomo Bakelite Co., Ltd.
(6) Dicyandiamide (7) Curing accelerator: 2-ethyl-4-methylimidazole (8) Inorganic filler 1: Aluminum hydroxide “CL-310” manufactured by Sumitomo Chemical Co., Ltd.
(9) Inorganic filler 2: Talc “PKP-53” manufactured by Fuji Talc Kogyo Co., Ltd.
(10) Solvent: acetone

2. Production of prepreg and composite laminate <Example 1>
100 parts by weight of the first resin material (a1) was applied to 100 parts by weight of the glass woven fabric (Nittobo Co., Ltd., “WEA 7628”, weight per unit area: 180 g / m 2). This was heat-dried at 150 ° C. for 2 minutes.

  Next, a glass nonwoven fabric (cumulus-made “EPM-4100B”, weight per unit area of 100 g / m 2) is laminated on the side of the glass woven fabric coated with the first resin material (a1). From the opposite side to the cloth, 1000 parts by weight of the second resin material (b1) was applied to 100 parts by weight of the glass nonwoven fabric. This was heat-dried at 150 ° C. for 6 minutes.

  Next, 50 parts by weight of the third resin material was applied to 100 parts by weight of the glass woven fabric from the opposite side of the glass woven fabric. This was heat-dried at 150 ° C. for 2 minutes to obtain a prepreg.

  In addition, all application amounts of the resin composition and the resin material are solid content converted values.

The two prepregs obtained above are overlapped with the glass nonwoven fabric side inside, and further, an electrolytic copper foil with a thickness of 18 μm (Furukawa Circuit Foil, “GTSMP-18”) is overlapped on both outer surfaces, 180 ° C. A composite laminate was obtained by heating and pressing at 4 MPa for 90 minutes.
<Example 2>
The first resin material (a2) was used instead of the first resin material (a1), and the second resin material (b2) was used instead of the second resin material (b1). Except this, it carried out similarly to Example 1, and obtained the prepreg and the composite laminated sheet.
<Example 3>
Instead of the first resin material (a1), the first resin material (a2) was used. Except this, it carried out similarly to Example 1, and obtained the prepreg and the composite laminated sheet.
<Comparative Example 1>
100 parts by weight of the first resin material (a1) was applied to 100 parts by weight of the glass woven fabric (Nittobo Co., Ltd., “WEA 7628”, weight per unit area: 180 g / m 2). A glass nonwoven fabric (“EPM-4100B” manufactured by Cumulus Co., Ltd., weight per unit area: 100 g / m 2) was superposed from the upper surface side coated with the first resin material (a1) and dried by heating at 150 ° C. for 2 minutes.

Next, 1000 parts by weight of the second resin material (b1) was applied to 100 parts by weight of the glass nonwoven fabric from the opposite side of the glass nonwoven fabric. This was heat-dried at 150 ° C. for 6 minutes. Except this, it carried out similarly to Example 1, and obtained the prepreg and the composite laminated sheet.
<Comparative example 2>
100 parts by weight of the first resin material (a1) was applied to 100 parts by weight of the glass woven fabric (Nittobo Co., Ltd., “WEA 7628”, weight per unit area: 180 g / m 2). A glass nonwoven fabric (“EPM-4100B” manufactured by Cumulus Co., Ltd., weight 100 g / m 2 per unit area) is overlapped from the upper surface side coated with the first resin material (a1). After applying 1000 parts by weight of the second resin material (b3) to 100 parts by weight of the nonwoven fabric, it was dried by heating at 150 ° C. for 2 minutes.

  Except this, it carried out similarly to Example 1, and obtained the prepreg and the composite laminated sheet.

  The following evaluation was performed about the composite laminated board obtained by the Example and the comparative example. The results are shown in Table 2.

3. Evaluation method (1) Thermal expansion coefficient: The thermal expansion coefficient of the obtained composite laminate was measured by the TMA method. The measurement was performed in the plane direction of the composite laminate, in the direction (X, Y) parallel to the two fiber directions of the glass woven fabric of the surface material and the thickness direction (Z) of the composite laminate. The value read the average thermal expansion between 50 ° C. and 100 ° C. when the temperature was lowered from 250 ° C. at a rate of 10 ° C. per minute.
(2) Punching workability: The thermal expansion coefficient of the obtained composite laminate was punched with a 150 t punching press “NC1-150” manufactured by Aida Engineering Co., Ltd., and the presence or absence of peeling was visually confirmed.

○: No peeling Δ: Fine peeling ×: Peeling (3) Stability during heating: Chip resistance (3216) was mounted on the laminate, and a temperature cycle test was conducted using a thermal testing machine. The temperature condition is −40 ° C. 9 minutes ⇔ 125 ° C. 9 minutes. The evaluation method was to observe the presence or absence of cracks by observing the cross section of the solder connection portion under a microscope at the end of 500 cycles.

○: No cracks Δ: Small cracks ×: Cracks Examples 1, 2, and 3 are all prepregs and composite laminates obtained by the production method of the present invention, and workability of conventional composite laminates While maintaining the above, the thermal expansion coefficient could be reduced.

  According to the production method of the present invention, it is possible to produce a prepreg that can be applied to a composite epoxy laminate having a small thermal expansion coefficient while maintaining workability substantially, and a composite substrate epoxy laminate using the prepreg. it can. The composite laminate obtained by the production method of the present invention can be expected to be used for the same applications as the glass woven fabric base epoxy resin laminate.

It is the side view which showed an example of the form of the manufacturing method of the prepreg of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Glass woven fabric 3 1st resin material 4 Comma coater apparatus 5 Drying apparatus 7 Glass nonwoven fabric 8 Superposition roll 9 Second resin material 10 Comma coater apparatus 11 Drying apparatus 13 3rd resin material 14 Transfer roll apparatus 15 Drying apparatus 16 Cutting device 17 Prepreg

Claims (10)

  1. A method of continuously producing a prepreg composed of a first layer and a second layer, used for a composite laminate,
    A first step of impregnating a glass woven fabric with a first resin material and drying by heating;
    A second step of placing a glass nonwoven fabric on the glass woven fabric, impregnating a second resin material from the upper surface of the glass nonwoven fabric, and heating and drying;
    3rd which processes the laminated body which consists of the said glass woven fabric and the said glass nonwoven fabric, and forms the 1st layer obtained at the said 1st process, and the 2nd layer obtained at the said 2nd process And the process of
    A method for producing a prepreg for a composite laminate, comprising:
  2.   The method for producing a prepreg according to claim 1, wherein the glass woven fabric is impregnated with the first resin material from one surface side, and the glass nonwoven fabric is placed on the surface.
  3.   The manufacturing method of the prepreg of Claim 2 including the 4th process of impregnating the 3rd resin material from the other surface side with respect to the said glass woven fabric.
  4.   The prepreg manufacturing method according to claim 1, wherein the first resin material includes an epoxy resin and a curing agent.
  5.   The prepreg manufacturing method according to claim 1, wherein the first resin material further contains a phenoxy resin.
  6.   The method for producing a prepreg according to claim 1, wherein the second resin material includes an inorganic filler and an epoxy resin, and does not include a phenoxy resin.
  7.   The prepreg according to any one of claims 1 to 6, wherein a content of the phenoxy resin contained in the first resin material is 5 parts by weight or more and 50 parts by weight or less in 100 parts by weight of the first resin material. Manufacturing method.
  8.   The content of the inorganic filler contained in the second resin material is 130 parts by weight or more and 250 parts by weight or less with respect to 100 parts by weight of the second resin component. The method for producing a prepreg according to 1.
  9.   9. Two prepregs obtained by the production method according to claim 1, wherein the second layer is opposed to each other, the first layer is overlaid, and laminated and formed. A method for manufacturing a composite laminate.
  10.   A composite laminate obtained by the method for producing a composite laminate according to claim 9.
JP2007127529A 2007-05-14 2007-05-14 Method for producing prepreg, method for producing composite laminated board and composite laminated board Pending JP2008280470A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001768A (en) * 2007-06-22 2009-01-08 Meian Kokusai Gigyo Kofun Yugenkoshi Prepreg
EP2644346A3 (en) * 2012-03-27 2016-03-16 MBB Fertigungstechnik GmbH Method for producing a flat prepreg material blank
JPWO2015152331A1 (en) * 2014-04-02 2017-04-13 株式会社Ihi Prepreg sheet laminating equipment

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005290029A (en) * 2004-03-31 2005-10-20 Sumitomo Bakelite Co Ltd Manufacturing method of prepreg and composite laminated plate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005290029A (en) * 2004-03-31 2005-10-20 Sumitomo Bakelite Co Ltd Manufacturing method of prepreg and composite laminated plate

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009001768A (en) * 2007-06-22 2009-01-08 Meian Kokusai Gigyo Kofun Yugenkoshi Prepreg
EP2644346A3 (en) * 2012-03-27 2016-03-16 MBB Fertigungstechnik GmbH Method for producing a flat prepreg material blank
JPWO2015152331A1 (en) * 2014-04-02 2017-04-13 株式会社Ihi Prepreg sheet laminating equipment

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