JP2000273221A - Flame-retardant prepreg and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a prepreg and a laminate having excellent flame retardance by using a powdery epoxy resin composition and even without using a halogen-based flame-retardant. SOLUTION: This prepreg is obtained by making a powdery epoxy resin composition composed of (a) an epoxy resin, (b) a phenol resin and (c) 9, 10- dihydro-9-oxa-10-phosphophenanthrene-10-oxide as essential components exist on at least one side of a sheetlike fibrous material. Preferably the powdery epoxy resin composition is a mixture of the components which are provided with mechanical energy and subjected to a mechanochemical reaction or kneaded under heating or mixed in a molten state and pulverized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a powdered epoxy resin composition and has excellent flame retardancy without using a halogen-based flame retardant, and is particularly useful for electric equipment, electronic equipment, communication equipment, etc. The present invention relates to a prepreg and a laminated board suitable for a printed circuit board to be used in the present invention.

[0002]

2. Description of the Related Art As for printed circuit boards, demands for miniaturization and high performance are increasing, but price competition is intense. In particular, multilayer laminated boards, glass cloth base epoxy resin laminated boards, or glass used for printed circuit boards are used. The cost reduction of any laminate using nonwoven fabric as the intermediate layer base material and glass woven fabric as the surface layer base material has been a major issue. Conventionally, a large amount of a solvent has been used in a process for producing a prepreg or a laminate used for these. This is because the preparation of the resin varnish is easy, and the application and impregnation of the resin on the base material is uniform and easy. This solvent evaporates in a drying step after coating and does not exist in the product, and most of the solvent is treated by a combustion device or the like or released to the atmosphere as it is. It has been pointed out that this contributes to global warming and air pollution.
On the other hand, various measures have been taken to reduce the amount of solvent used,
This reduction was difficult due to manufacturing problems such as application and impregnation of the resin to the base material.

[0003] For the production of prepregs and laminates without using a solvent, studies have been made on a method in which a low-melting-point resin or a liquid resin is heated and mixed to make it uniform and applied to a substrate (for example, see Japanese Patent Application Laid-Open No. Hei 9 (1998)). -263647). However, with such a method, uniform mixing cannot be sufficiently performed, resin consolidation in equipment due to a decrease in heating temperature during continuous production, gelation of thermosetting resin during heating, and problems such as cleaning of equipment due to this. And continuous production was difficult. On the other hand, a method of directly applying a powdery resin has also been proposed (Japanese Patent Application Laid-Open No. 50-143870), but uniform mixing and application are difficult, and partial curing occurs or impregnation of the base material is difficult. There are problems such as insufficient, and it has not been put to practical use.

A thermosetting resin represented by an epoxy resin or the like is often provided with flame retardancy in order to ensure fire safety. Conventionally, these resins have generally used a halogen-containing compound such as a brominated epoxy resin. Although these halogen-containing compounds have high flame retardancy, aromatic bromine compounds not only separate corrosive bromine and hydrogen bromide when thermally decomposed, but also have high toxicity when decomposed in the presence of oxygen. May form bromodibenzofuran and polydibromobenzooxin. For these reasons, phosphorus compounds and nitrogen compounds have been studied as flame retardants instead of bromine-containing flame retardants.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been studied to obtain a prepreg or a laminate using a solventless resin, which has been conventionally difficult to produce.
By using a powdery epoxy resin composition containing a phenolic resin and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as essential components, impregnation and curability to a substrate can be achieved. Further, the inventors have found that the flame retardancy is equivalent to the case where a conventional solvent is used, and further advanced various studies based on this finding to complete the present invention.

[0006]

The present invention comprises (a) an epoxy resin, (b) a phenolic resin, and (c) 9,10-
A prepreg, characterized in that a powdery epoxy resin composition containing dihydro-9-oxa-10-phosphaphenanthrene-10-oxide as an essential component is present on at least one surface of a sheet-like fiber base material. Preferably, this powdered epoxy resin composition is a prepreg, which is obtained by applying a mechanical energy to a mixture of each component to cause a mechanochemical reaction, or heat-kneading or melt-mixing each component and pulverized. Further, the present invention relates to a prepreg, and more particularly, to a laminated plate obtained by laminating one or more such prepregs and heating and pressing.

The epoxy resin (a) has two or more epoxy groups in one molecule, and bisphenol A
Epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, cycloaliphatic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic epoxy resin And a phenol aralkyl type epoxy resin and a naphthalene aralkyl type epoxy resin. In particular, phenol novolak type epoxy resins and cresol novolak type epoxy resins have high heat resistance and a high benzene ring content, and thus are easily carbonized when thermally decomposed. For this reason, it is preferable because it has a feature that the flame retardancy is higher than that of the bisphenol A type epoxy resin. One or a mixture of two or more of these can also be used. The epoxy resin is preferably solid at room temperature for powdering the composition, and more preferably has a melting point in the range of 50 to 130 ° C.

The phenolic resin (b) includes phenol novolak resin, cresol novolak resin, paraxylylene modified phenol resin, metaxylylene / paraxylylene modified phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin, naphthalene aralkyl resin and the like. Can be mentioned. In particular, phenol aralkyl resins and naphthalene aralkyl resins are preferable because of their low water absorption and high flame retardancy. These phenolic resins can be used alone or as a mixture of two or more, and are solid at room temperature. Melting point is usually 50-150 ° C,
Preferably, it should be in the range of 70 to 130 ° C. (C)
The component 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is a phosphorus compound having a functional group reactive with an epoxy group or the like, and in the present invention, reacts with an epoxy resin or the like. By doing
It exhibits excellent flame retardancy without deteriorating heat resistance, electrical properties and the like.

In the present invention, an epoxy resin, a phenol resin, and 9,10-dihydro-9-oxa-10-
Although phosphaphenanthrene-10-oxide is contained as an essential component, other curing agents, curing accelerators, coupling agents, and other components may be added within a range not inconsistent with the object of the present invention. The mixing ratio of each component will be described. The phenol resin of the component (b) is preferably 20 to 60 parts by weight based on 100 parts by weight of the epoxy resin of the component (a). If the amount is less than 20 parts by weight, the curing of the resin becomes insufficient. If the amount exceeds 60 parts by weight, the heat resistance may decrease due to the effect of unreacted phenol resin, which is not preferable. The phosphorus compound of the component (c) is (a) and (b)
Is preferably 0.5 to 4 parts by weight as phosphorus with respect to 100 parts by weight in total. If the amount is less than 0.5 part by weight, the effect on flame retardancy is small, and if it exceeds 4 parts by weight, heat resistance is undesirably reduced.

When the powdered epoxy resin composition is a composition obtained by applying a mechanical energy to a mixture of each component to cause a mechanochemical reaction, each component is usually a powder.
When the amount of some components is small (for example, 20% by weight or less with respect to the resin), some or all of the components may be in a liquid state, provided that the mixture with the resin or the like can be pulverized after applying mechanical energy. Can be used.

In each of the above components, the particle size of the powder is usually 1000 μm or less, preferably 0.1 to
500 μm, more preferably 0.1 to 200 μm
It is. This is because, if it exceeds 1000 μm, the surface area with respect to the particle weight becomes small, the points of contact of each component such as epoxy resin become small, and uniform dispersion becomes difficult. Or a uniform reaction may not be performed.

The modification by a mechanochemical reaction is "a modification of a solid by a solid, which utilizes the surface activity of particles by grinding, grinding, friction, and contact, and surface home appliances. The activity itself is a crystal form. In some cases, the dissolution or thermal decomposition rate is modified by increasing the transition energy or strain energy, or mechanical strength or magnetic properties are obtained. In other cases, surface activity is used for reaction or adhesion with other substances. Uses mechanical impact energy to perform not only physical modification but also chemical modification such as adhesion by electric charge or magnetism by friction, contact, embedding of modifier in nuclear material, formation of film by melting, etc. ("Overview of Practical Surface Modification Technologies" edited by the Material Technology Research Association, Industrial Technology Service Center, published March 25, 1993, p786)
Things. The present invention utilizes chemical modification by a mechanochemical reaction, but also includes a case where a solid and a liquid are chemically modified by mechanical energy.

[0013] Powder processing methods for applying mechanical energy for the mechanochemical reaction include Raikai machines, Henschel mixers, planetary mixers, ball mills,
Mixing or kneading with a medium stirring mill, a jet mill, an ang mill, a multi-stage mill-type kneading extruder or the like is available. Among them, Ongmill (Mechanofusion system manufactured by Hosokawa Micron Co., Ltd.), multi-stage mill-type kneading extruder (KC Co., Ltd.)
K: Mechanochemical dispersion method, etc.) or jet mill (manufactured by Nara Machinery Co., Ltd .: Hybridizer method, etc.) is preferred. Mixing or kneading is preferred. A kneading extruder (manufactured by KCK Corporation: mechanochemical dispersion method) is preferable.

In order to carry out the mechanochemical reaction, the softening point of the thermosetting resin is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher. This is because heat of about 20 to 50 ° C. is generated due to friction, pulverization, and fusion between the powders or between the powder and the processing apparatus during the above-mentioned processing, so that this influence is minimized. On the other hand, even if the softening point is too high, an effective mechanochemical reaction is difficult to be performed, and it is difficult to impregnate the base material of the resin composition in a later step. Softening points are preferred. Each component such as a powdery thermosetting resin and a curing agent is preferably mixed as uniformly as possible with a Henschel mixer or the like after pulverizing to the above particle size in advance before powder treatment for mechanochemical reaction. .

The particle size of the mechanochemically reacted powdery epoxy resin composition is usually 1000 μm or less, preferably 0.1 to 500 μm, and more preferably 0.1 to 200 μm. Such a particle size is to improve the fluidity of the powder composition at the time of spraying or application, and to improve the flow and surface smoothness at the time of heating and melting, to improve the resin impregnation property of the base material, It is suitable for stabilizing the distribution of the resin composition.

In the case where the powdery epoxy resin composition is a powdery material obtained by kneading or melt-mixing the components and finely pulverizing, the epoxy resin, the phenolic resin, and 9,10-dihydro-9-oxa-10- Phosphaphenanthrene
The 10-oxide is heat-kneaded or melt-mixed with a heating roll or the like, together with other optional additives, and then finely pulverized by a pulverizer. Normally, solid components are used, but components other than the epoxy resin, phenolic resin, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide may be used in liquid form.

The apparatus for heating kneading or melt mixing includes a heating roll, a single-screw or twin-screw extruder, a heating kneader such as a co-kneader, a stirring vessel equipped with a heating device such as a Henschel mixer, a reaction apparatus, and the like. Practically, a heating roll, a single screw or twin screw extruder, and a Henschel mixer are preferable. The pulverizer may be any pulverizer that can finely pulverize the resin composition that has been heated and kneaded or melt-mixed, and examples thereof include a hammer mill, an atomizer, and a jet mill.

The particle size of the finely pulverized thermosetting resin composition is usually 1000 μm or less, preferably 0.1 μm or less.
1 to 500 μm, and more preferably 0.1 to 200 μm.
μm. Such a particle size is to improve the fluidity of the powder composition at the time of spraying or application, and to improve the flow and surface smoothness at the time of heating and melting, to improve the resin impregnation property of the base material, It is suitable for stabilizing the distribution of the resin composition.

The thermosetting resin composition used in the present invention may be added, if necessary, before a mechanochemical reaction occurs.
Alternatively, before heat kneading or melt mixing, an inorganic filler can be added in advance. When an inorganic filler is added, characteristics such as tracking resistance, heat resistance, and a decrease in coefficient of thermal expansion can be imparted. Such inorganic fillers include aluminum hydroxide, magnesium hydroxide, calcium carbonate, talc, wollastonite, alumina, silica, unfired clay, fired clay, barium sulfate and the like. These particle sizes are the same as above. Further, a coupling agent such as epoxysilane or aminosilane may be added in order to improve the adhesion to the glass cloth.

The powdery epoxy resin composition obtained as described above preferably contains a fine powder additive in order to improve the flow characteristics. By blending the fine powder additive, when the powder composition is applied and impregnated on a substrate, the powder composition can be uniformly dispersed or applied, and the powder composition can be uniformly dispersed on the substrate. Distribution and smoothness of the powder composition applied surface can be obtained. This enables uniform application to the base material. As the fine powder additive, an inorganic fine powder is desirable, but an organic fine powder can also be used. The fine powder additive has an average particle size of 0.0
The thickness is from 1 to 1 μm, preferably from 0.01 to 1 μm.
One having a thickness of 0.1 μm (specific surface area: about 50 to 500 m 2 / g) is used. When the average particle size exceeds 1 μm, the specific surface area is reduced, the number of particles per unit weight is reduced, and the difference in particle size from the powdered thermosetting resin as the main component is reduced, thereby improving the fluidity. There is a possibility that a sufficient bearing effect cannot be obtained. The bearing effect in powder means that fine particles are present at the point of contact between particles having relatively large particle diameters, thereby making the movement of large particle diameters more free and improving the flowability of the powder composition as a whole. It is to let.

The compounding amount of the fine powder additive is preferably 0.1 to 5% by weight based on the whole powder composition, and 0.2 to 2.0% by weight.
% Is more preferred. In the range of 0.1 to 5% by weight, the fluidity of the powder composition can be improved without significantly lowering the properties of the laminate, and the effect is in the range of 0.2 to 2.0% by weight. Best demonstrated. As a treatment method for improving the fluidity of the powder composition containing the fine powder additive, any method may be used as long as it can uniformly mix and disperse the fine powder additive. For example, mixing with a Henschel mixer, a Raikai machine, a planetary mixer, a tumbler, a ball mill or the like can be mentioned.

The powder composition is made to exist on at least the surface of the substrate by spraying or coating. The amount of the powder composition varies depending on the fiber material, properties, and weight (per unit area) of the substrate, but is usually about 40 to 60% of the weight of the substrate. The method of causing the powder composition to be present on the substrate includes a method of sprinkling from the upper surface of the substrate, an electrostatic coating method, a fluid immersion method, a spraying method with a spray, a knife coater, a coating method using various coaters such as a comma coater, and the like. There is no particular limitation. As the base material, in addition to glass fiber base materials such as glass cloth and glass nonwoven fabric, woven and nonwoven fabrics made of paper, synthetic fibers, and the like, woven fabrics, nonwoven fabrics, mats made of metal fibers, carbon fibers, mineral fibers, and the like The raw material fibers of these substrates may be used alone or as a mixture.

When the powder composition is made to exist on the base material, the powder composition may be made to exist only on one side of the base material. However, it is preferable to use the base material in order to balance the front and back from the viewpoint of preventing warpage and the like. It is preferred that the powder composition is present on both sides of the substrate. In this case, first, the powder composition is made to exist on one surface (upper surface) of the substrate by spraying or coating, and then heated to sufficiently adhere the powder composition to the substrate. If the powder composition is also present on the opposite side, the substrate is inverted and the powder composition is similarly present on the top surface of the substrate, and then heated to sufficiently adhere the powder composition to the substrate. Heating, when the powder composition is present on the upper surface of the substrate, only the lower surface, or when heating from both surfaces and the lower surface is performed at a higher temperature,
It is preferable because the impregnation of the molten resin is performed well.
Although the heating temperature depends on the softening point of the powder composition, the surface (upper surface) on which the powder composition exists is usually 80 when heated.
To 150 ° C, preferably 100 to 140 ° C. On the opposite surface (lower surface), the temperature is usually 90 to 170 ° C.
And preferably 110 to 150 ° C.

The resin-impregnated base material may be heated so that the resin composition is more sufficiently impregnated and, if necessary, the resin is in a semi-cured state. This heating temperature is usually 100 to 20
The temperature is 0 ° C., preferably 120 to 190 ° C., but may be different depending on the fluidity and curability of the resin composition.

When the thickness of the substrate is as thin as 100 μm or less (100 g / m 2 or less for a glass substrate), or when the powder composition is easily and uniformly melted, a method in which the powder composition is present only on one side may be used. . Again, in this case,
Thereafter, a step of heating and / or heating is provided.

The prepreg obtained as described above is
One or more of the sheets are laminated with a metal foil such as a copper foil as necessary, and heated and pressed by a usual method to form a laminate or a metal foil-clad laminate. The prepreg and the laminate of the present invention can be easily manufactured using the powdered resin composition without substantially changing the performance of the prepreg or the laminate from the conventional one, and can save resources, save energy and save air by using no solvent. Contamination can be reduced, and further cost reduction can be achieved.

[0027]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 (KCK, coater method) Powdered epoxy resin having an average particle size of 150 μm (cresol novolac epoxy resin N-69 manufactured by Dainippon Ink and Chemicals, Inc.)
5, epoxy equivalent 213) 100 parts by weight, average particle size 1
34.5 parts by weight of a powdery phenol novolak resin of 00 μm (PR-51470 manufactured by Sumitomo Durez Co., Ltd.), powdered 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having an average particle diameter of 15 μm 30
Parts by weight, and powdery 2-phenyl- having an average particle size of 10 μm.
0.5 parts by weight of 4-methylimidazole is preliminarily mixed, and then a multi-stage mill-type kneading extruder (Mechanochemical dispersion system KCK-80X manufactured by KCK)
Using 2-V (6)) at 200 rpm for 1 minute, a powder composition was obtained.

Next, 100 g / m ^{2 of the} powder composition was added.
Was uniformly coated on the upper surface of the glass cloth with a knife coater so that the resin weight became 50 g / m ² . Then, from the lower surface side, a panel heater of
Warmed for minutes. Then turn the glass cloth upside down,
Resin weight 50g / m with knife coater on the other side
^The mixture was uniformly applied so as to be ² and heated with a hot air heater at 170 ° C. for 1 minute to obtain a prepreg. This prepreg is 2
A copper foil having a thickness of 18 μm is further laminated on the upper and lower sides, and a temperature of 165 ° C., a pressure of 40 kg / cm ² and a pressure of 9 kg are applied.
It was heated and pressed for 0 minutes to produce a copper-clad laminate having a thickness of 0.22 mm.

Example 2 (KCK, Aerosil, Thick Cloth, Coater Method) Fine powdered silica having an average particle size of 0.05 μm (Aerosil manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts by weight of the powdery resin composition obtained in Example 1. # 200) 1 part by weight was added, and the mixture was mixed with a Henschel mixer at 500 rpm for 5 minutes. The obtained powder composition was coated on one side of a glass cloth of 210 g / m ^{2 with} a knife coater so that the resin weight was 85 g / m ^2.
Was applied uniformly. After that, 12
It was heated for about 1 minute by a hot air heater at 0 ° C. Next, the glass cloth was turned upside down, and the other surface was uniformly coated with a knife coater so that the resin weight became 85 g / m ^2, and heated with a hot air heater at 170 ° C. for 1 minute to obtain a prepreg. Using this one prepreg, a copper-clad laminate having a thickness of 0.22 mm was produced in the same manner as in Example 1.

Example 3 (Hosokawa micron, sprinkling method) Powdered epoxy resin having an average particle size of 150 μm (cresol novolak epoxy resin N-69 manufactured by Dainippon Ink and Chemicals, Inc.)
5, epoxy equivalent 213) 100 parts by weight, average particle size 1
56 parts by weight of a 50 μm powdery phenol aralkyl resin (Milex hydroxyl equivalent 170, manufactured by Mitsui Chemicals, Inc.), powdered 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 30 having an average particle diameter of 15 μm
Parts by weight, and powdery 2-phenyl- having an average particle size of 10 μm.
0.5 parts by weight of 4-methylimidazole was premixed, and then treated with a mechanofusion machine (AM-15F, manufactured by Hosokawa Micron Corporation) at 2,000 rpm for 5 minutes to obtain a powder composition.

Next, 100 g / m ^{2 of the} powder composition was used.
Was passed through a 60-mesh sieve on one side of the glass cloth, and uniformly spread so that the resin weight became 50 g / m ² .
Then, the glass cloth was heated for 30 seconds from both sides of the glass cloth with a hot air heater at 170 ° C., then the glass cloth was turned upside down, and the other side was passed through a 60-mesh sieve so that the resin weight became 50 g / m ^2. Sprinkle at 170 ° C
And heated for 3 minutes with a hot air heater to obtain a prepreg. Using this prepreg, a thickness of 0.2
A 2 mm copper-clad laminate was produced.

Example 4 (Hosokawa Micron, Aerosil, Sprinkling Method) 1 part by weight of fine powder silica (Aerosil # 200 manufactured by Nippon Aerosil) having an average particle size of 0.05 μm was added to 100 parts by weight of the powder composition obtained in Example 3. And the mixture was mixed with a Henschel mixer at 500 rpm for 5 minutes.
Using the obtained powdery composition, a prepreg was obtained in the same manner as in Example 3, and then the prepreg was used to obtain a prepreg having a thickness of 0.1 mm.
A 22 mm copper-clad laminate was produced.

Example 5 (Roll, coater method) Powdered epoxy resin (cresol novolac type epoxy resin N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 21)
3) 100 parts by weight, 34.5 parts by weight of powdery phenol novolak resin (PR-51470, manufactured by Sumitomo Durez Co., Ltd.), powdery 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 30 Parts by weight, and powdery 2-phenyl-4-methylimidazole 0.5
Parts by weight and then using two rolls having a diameter of 12 inches, a high-speed rotation speed of 20 rpm, a high-speed roll temperature of 60 ° C, a low-speed roll temperature of 30 ° C, and a rotation ratio of 1.5: 1.
, And then taken out in the form of a sheet, cooled with cold air, and then pulverized with a fine pulverizer to obtain a powdery resin composition.
Using this powder composition, a prepreg was obtained in the same manner as in Example 1, and using this prepreg, a copper-clad laminate having a thickness of 0.22 mm was manufactured in the same manner as in Example 1.

Example 6 (Roll, Aerosil, Coater Method) Fine powdered silica having an average particle diameter of 0.05 μm (Aerosil # 200 manufactured by Nippon Aerosil) was added to 100 parts by weight of the powdery resin composition obtained in Example 5. The mixture was added at a ratio of 1 part by weight, and mixed with a Henschel mixer at 500 rpm for 5 minutes. Using this powdery composition, a prepreg was obtained in the same manner as in Example 5, and then the prepreg was used to obtain a prepreg having a thickness of 0.1 mm.
A 22 mm copper-clad laminate was produced.

Comparative Example 1 (powder, no mechanochemical treatment) Powdered epoxy resin having an average particle size of 150 μm (cresol novolac epoxy resin N-69 manufactured by Dainippon Ink and Chemicals, Inc.)
5, epoxy equivalent 213) 100 parts by weight, average particle size 1
34.5 parts by weight of a powdery phenol novolak resin of 00 μm (PR-51470 manufactured by Sumitomo Durez Co., Ltd.), powdered 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having an average particle diameter of 15 μm 30
Parts by weight, and powdery 2-phenyl- having an average particle size of 10 μm.
0.5 parts by weight of 4-methylimidazole was stirred and mixed for 1 minute at a rotation speed of 70 rpm using an anchor-type stirrer. A prepreg was obtained from this powder composition in the same manner as in Example 1. The prepreg overlay two further superimposed copper foil having a thickness of 18μm on the upper and lower, temperature 165 ° C., and heated pressing at a pressure 40 kg / cm ² 90 min, copper-clad laminate having a thickness of 0.22mm A plate was made.

[Comparative Example 2] (Conventional impregnation method) Epoxy resin (cresol novolak type epoxy resin N-695, epoxy equivalent 213 manufactured by Dainippon Ink and Chemicals, Inc.) 1
00 parts by weight, phenol novolak resin (Sumitomo Durez)
34.5 parts by weight, 9,10-
30 parts by weight of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 2-phenyl-4-
A mixture of methyl imidazole at a ratio of 0.5 part by weight was dissolved in 100 parts by weight of methylcellosolve. 100 g of this varnish was adjusted to 100 g / m ² in resin solids.
/ M2 of glass cloth soaked and impregnated at 170 ° C
And heated for 3 minutes with a hot air heater to obtain a prepreg. Two prepregs are stacked, and a thickness of 1
8μm copper foil is superimposed, temperature 165 ℃, pressure 60k
g / cm ² for 90 minutes under heat and pressure.
mm copper-clad laminate was prepared.

In the above Examples and Comparative Examples, the impregnation property, moldability, tensile strength, copper foil peeling strength, solder heat resistance, insulation resistance and flame resistance of the copper-clad laminate were measured. The results are shown in Tables 1 and 2.

[0039]

[Table 1]

[0040]

[Table 2]

(Measurement method) Impregnation: The cross section of the laminate was observed with a microscope to confirm the presence or absence of voids between glass fibers. 2. Formability: The copper foil of the copper-clad laminate was etched, the presence or absence of the precipitation of a curing agent or the like was visually observed, and the dispersibility of the resin composition was evaluated. 3. Tensile strength: Etching copper foil of copper clad laminate,
After cutting to 10 × 100 mm, the tensile strength was measured with Tensilon. 4. Copper foil peel strength: Measured according to JIS C6481. 5. Solder heat resistance: A laminate of 50 × 50 mm is subjected to 260 ° C.
Was floated in a solder bath for 3 minutes, and the presence or absence of blisters was measured. 6. Insulation resistance: Measured according to JIS C6481. 7. Flame resistance: Evaluated by the vertical method according to UL-94 standard.

As for the manufacturing cost, since the method of the embodiment does not use a solvent, the laminated plate obtained in the embodiment is reduced in cost by about 30 to 40% as compared with that obtained in the comparative example 2. Was completed.

[0043]

The prepreg and laminate of the present invention can be obtained by using a powdered epoxy resin composition having good impregnating properties and good moldability without using an organic solvent. In addition, air pollution is reduced, and resource saving and energy saving are achieved. Furthermore, a laminated board having good quality such as flame retardancy, electric characteristics, heat resistance and the like can be stably obtained without using a halogen-based flame retardant.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/49 C08K 5/49 C08L 63/00 C08L 63/00 CB F term (Reference) 4F072 AA07 AB09 AB28 AB29 AD13 AD23 AE07 AF06 AG03 AK02 AK06 AL13 4F100 AB17 AB33 AG00 AH10A AH10B AK33A AK33B AK53A AK53B BA03 BA05 BA07 BA10A BA10B BA13 DE01A DE01J DG01 DG11C DH01C EH46 GB43 JG00 JJ03 A0300 AJ18 DC41 DD07 FB07 HA12 HA13 JA08

Claims (4)

[Claims] 1. An epoxy resin, (b) a phenolic resin, and (c) 9,10-dihydro-9-oxa-1.
A prepreg, characterized in that a powdery epoxy resin composition containing 0-phosphaphenanthrene-10-oxide as an essential component is present on at least one surface of a sheet-like fiber base material. 2. The prepreg according to claim 1, wherein the powdery epoxy resin composition is obtained by applying a mechanical energy to a mixture of each component to cause a mechanochemical reaction. 3. The prepreg according to claim 1, wherein the powdery epoxy resin composition is obtained by kneading or melt-mixing each component and finely pulverizing the components. 4. A laminated plate, wherein one or more prepregs according to claim 1, 2, 3 or 4 are laminated and heated and pressed.