JP2000345006A - Flame retarded prepreg and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a prepreg and a laminate thereof which do not require an org. solvent and have good heat resistance and flame retardance. SOLUTION: This prepreg is prepd. by including, on at least one of the surfaces of a fiber sheet substrate, (a) an epoxy resin, (b) an epoxy resin curing agent and (c) an epoxy resin powdery compsn. comprising a coated-type phosphorus compd. surface-treated with a coupling agent. This prepreg is used for preparing a laminate or a copper-clad laminate. Each of the components in the epoxy resin powdery compsn. substantially has a form of powder. It is preferable that the compsn. is obtd. by subjecting them to a mechanochemical reaction by supplying a mechanical energy or it is obtd. as a powder by subjecting them to kneading with heating or melt mixing followed by pulverizing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent flame retardancy without using a halogen-based flame retardant, and is particularly suitable for printed circuit boards used in electric equipment, electronic equipment, communication equipment and the like. The present invention relates to a prepreg and a laminate.

[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 the use of solvents, 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 (see, for example, JP-A-Hei. 9-263647). 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 (for example, JP-A-50-143870). However, uniform mixing and application are difficult, and partial curing occurs, There are problems such as insufficient impregnation, 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, nitrogen compounds and inorganic flame retardants have been studied as flame retardants instead of bromine-containing flame retardants.

[0005] For example, by adding a powdery phosphorus compound whose surface is coated with a thermosetting resin or the like as a flame retardant, characteristics such as water resistance are improved, but the compatibility between the coating resin and the epoxy resin is improved. Due to the low temperature, sufficient adhesion at the interface cannot be obtained, and a decrease in heat resistance and the like is generally observed. Further, in the method of applying the resin composition containing the coating type phosphorus compound as it is in a powder state, it may be difficult to apply the resin composition uniformly due to the fluidity and cohesiveness of the powder. Generally, the smaller the particle size of the powder particles, the stronger the tendency, and if the average particle size is 25 μm or less, uniform coating cannot be performed.

[0006]

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 a coated phosphorus compound surface-treated with a coupling agent as an essential component, applicability to a substrate, impregnation,
The inventors have found that the curability, heat resistance, and flame retardancy are equivalent to those obtained when a conventional solvent is used, and further advanced various studies based on this finding to complete the present invention.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a powdery epoxy resin comprising, as essential components, (a) an epoxy resin, (b) an epoxy resin curing agent, and (c) a coated phosphorus compound surface-treated with a coupling agent. A resin composition is a prepreg characterized by being present on at least one side of a sheet-like fiber base material, preferably this powdered epoxy resin composition, each component is substantially powdery, these A prepreg that is a mechanochemical reaction given mechanical energy to the prepreg, or a prepreg that is a finely pulverized powdery material by heating and kneading or melting and mixing each component,
Further, the present invention relates to a laminate characterized in that one or a plurality of such prepregs are stacked and heated and pressed.

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 the like. 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 which is solid at room temperature is preferable for powdering the composition, and has a melting point of 50 to 13.
Those in the range of 0 ° C. are more preferred.

Examples of the epoxy resin curing agent (b) include a phenol resin and a compound having an amino group. Examples of the phenol resin include a phenol novolak resin, a cresol novolak resin, a para-xylylene-modified phenol resin, a meta-xylylene / para-xylylene-modified phenol resin, a terpene-modified phenol resin, a dicyclopentadiene-modified phenol resin, a phenol aralkyl resin, and a naphthalene aralkyl resin. Aralkyl resins and naphthalene aralkyl resins are preferred 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. The melting point may be usually in the range of 50 to 130 ° C. Epoxy resin curing agents having an amino group can be expected as a nitrogen source as a flame retardant aid, ethylenediamine, trimethylenediamine, tetramethylenediamine, linear aliphatic diamines such as hexamethylenediamine, metaphenylenediamine, paraphenylenediamine, Paraxylenediamine, diaminodiphenylmethane, diaminodiphenylpropane, diaminodiphenylether, diaminodiphenylsulfone, diaminodicyclohexane, bis (4-aminophenyl) phenylmethane, 1,5-diaminonaphthalene, meta-xylylenediamine, para-xylylenenaphthalene, 1 1,1-bis (4-aminophenyl)
Examples thereof include cyclohexane and dicyandiamide, but are not particularly limited thereto. Particularly preferred are diaminodiphenylmethane and dicyandiamide in terms of heat resistance, curability and the like. Some of these can be used in combination.

The coated phosphorus compound (c) surface-treated with a coupling agent will be described. The coating type phosphorus compound is a phosphorus compound whose surface is coated with a thermosetting resin or a thermoplastic resin, and the like. As the phosphorus compound, a polyphosphate having a high melting point, particularly, as a polyphosphate, ammonium polyphosphate or polyphosphoric acid Phosphorus compounds containing both phosphorus and nitrogen in the molecule, such as polyphosphates such as amides and melamine phosphate are preferably used. In addition to this, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tree 2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate,
Phosphate esters such as xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6-dimethylphenyl) phosphate, resorcin diphenyl phosphate, and condensates thereof can also be used.

Among the phosphorus compounds, those obtained by coating the surface of a powdery phosphorus compound with a resin film are extremely stable and excellent in chemical resistance and water resistance. In addition, since the surface of a low-melting-point material or a water-soluble phosphorus compound is coated with a thermosetting resin or a thermoplastic resin, etc., the characteristics of the laminate are not deteriorated, and therefore, it can be sufficiently practically used. .

A method of coupling the coated phosphorus compound will be described. It can be obtained by adding 0.01 to 5 parts by weight of a coupling agent, directly or diluted with an organic solvent or water, to 100 parts by weight of the coated phosphorus compound and stirring and mixing with a Henschel mixer or the like. In this case, stirring may be performed by applying heat as needed. It can also be added to a mixture of a coating type phosphorus compound with another component such as a resin.

The coupling agent used for the surface treatment of the coated phosphorus compound is preferably an amino-based or epoxy-based silane compound, but other coupling agents such as other silane coupling agents and titanium-based coupling agents are preferred. Can also be used.

By subjecting the coated phosphorus compound to a surface treatment with a coupling agent, the flowability of the powdery resin composition is improved, and uniform application to a substrate is made possible. This is probably because the surface of the coated phosphorus compound is modified by the coupling agent, and the self-aggregation property is significantly reduced. The decrease in cohesiveness is also an improvement in dispersibility, and the uniform dispersion of the coated phosphorus compound also exerts an effect of improving flame resistance. Furthermore, since the adhesion between the copper foil or the resin and the inorganic filler is improved by the coupling agent treatment, properties such as heat resistance and low moisture absorption can be imparted. The average particle diameter of the coated phosphorus compound is preferably 200 μm or less, more preferably 100 μm or less, and particularly preferably 50 μm or less, in order to effectively exert the fluidity improving effect by the treatment with the coupling agent.

In the present invention, a coated phosphorus compound surface-treated with an epoxy resin, a phenol resin and a coupling agent is contained as an essential component, but other curing agents and curing agents may be used within a range not inconsistent with the object of the present invention. Accelerators and other components may be added.

The mixing ratio of each component will be described.
The phenol resin of the component (b) is 20 to 60 parts by weight based on 100 parts by weight of the epoxy resin of the component (a). 20
If the amount is less than 10 parts by weight, the curing of the resin becomes insufficient, and
Exceeding 0 parts by weight is not preferred because heat resistance may decrease due to unreacted phenol resin. (C)
The coated phosphorus compound surface-treated with the component coupling agent is 0.5 to 4 parts by weight of phosphorus based on a total of 100 parts by weight of (a) and (b). 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.

In the case of a powdery epoxy resin composition in which each component is substantially in the form of powder and is subjected to mechanochemical reaction by applying mechanical energy thereto, a small amount of component (for example, 20% by weight based on the whole product
Part or all of the following may be liquid, and can be used if it can be pulverized after applying mechanical energy to a mixture with a resin or the like.

The particle size of these powders is usually 100
0 μm or less, preferably 0.1 to 500 μm, more preferably 0.1 to 200 μm. 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 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.

Powder processing methods for applying mechanical energy for the mechanochemical reaction include Raikai machines, Henschel mixers, planetary mixers, ball mills,
Mixing or kneading by a medium stirring mill, a jet mill, an ong mill, a multi-stage mill-type kneading extruder, or the like is available. Among them, Ongmill (Mechanofusion method manufactured by Hosokawa Micron Corporation), multi-stage mill-type kneading extruder (Made by KCK: Mechanochemical dispersion method, etc.), Jet mill (Nara Machinery Co., Ltd .: Hybrid) Tizer method, etc.),
Mixing or kneading with a medium agitating mill (Mitsui Mining Co., Ltd. dry continuous fine pulverizer dynamic mill) is preferable. In particular, in order to efficiently carry out the mechanochemical reaction, a multi-stage mill-type kneading extruder (manufactured by KCK Corporation: Mechanochemical dispersion method) is preferable.

In order to carry out a 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, so that the temperature is 150 ° C or less, particularly 130 ° C or less. 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 powdery epoxy resin composition subjected to the mechanochemical reaction is generally 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.

When the powdered epoxy resin composition is a finely pulverized powder obtained by heating and kneading or melting and mixing each component, a coated phosphorus compound surface-treated with an epoxy resin, a phenolic resin, a coupling agent, etc. Heat-kneading or melt-mixing is carried out by a heating roll or the like together with additives added as necessary, and then finely pulverized by a pulverizer. Usually, solid components are used, but liquid epoxy resins and phenol resins can also be used.

The apparatus for heat 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 reactor, 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.

Before the mechanochemical reaction occurs, the thermosetting resin composition used in the present invention may optionally contain
Alternatively, before heat kneading or melt mixing, an inorganic filler can be added in advance. Add the inorganic filler,
Properties such as flame retardancy, 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. Also, to improve the adhesion with glass cloth, epoxy silane,
A coupling agent such as aminosilane may be added.

It is preferable to add a fine powder additive to the powdery epoxy resin composition obtained as described above 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 present 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 on only one side of the base material. 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. The heating temperature depends on the softening point of the powder composition, but is usually from 80 to 150 ° C, preferably from 100 to 140 ° C, on the surface (upper surface) where the powder composition exists. On the opposite surface (lower surface), the temperature is usually 90 to 170 ° C., preferably 1 to 170 ° C.
10-150 ° C. It is not necessary to heat from the surface (upper surface) where the powder composition is present. Even when heating, it is preferable to heat the opposite surface (lower surface) to a higher temperature.

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 base material is as thin as 100 μm or less (100 g / m ² or less for a glass base material), or when the powder composition is easily and uniformly melted, a method in which the powder composition is present only on one side is used. Good. 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.

[0034]

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 (Coupling treatment: dry method) Modified melamine-coated ammonium polyphosphate having an average particle diameter of 10 μm (Terage C-60 manufactured by Chisso Corporation) 10
One part by weight of 3-glycidoxypropyltrimethoxysilane was added as a silane coupling agent to 0 part by weight to obtain a coated ammonium polyphosphate treated with a coupling agent. Powdered epoxy resin having an average particle size of 150 μm (cresol novolak epoxy resin N-695, epoxy equivalent 213, manufactured by Dainippon Ink and Chemicals, Inc.) 100
34.5 parts by weight of a powdery phenol novolak resin having an average particle diameter of 100 μm, 11 parts by weight of a coated ammonium polyphosphate treated with the coupling agent, and powdery 2-phenyl-4-methylimidazole having an average particle diameter of 10 μm 0.5 parts by weight were preliminarily mixed, and then processed at a rotation speed of 200 rpm for 1 minute using a multi-stage mill-type kneading extruder (Mechano-chemical dispersion system KCK-80X2-V (6) manufactured by KCK). A mechanochemical reaction was performed to obtain a powdery resin composition having an average particle size of 150 μm.

Further, 1 part by weight of fine powder silica (Aerosil # 200 manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 0.05 μm was added thereto, and the rotation speed was 500 using a Henschel mixer.
The mixture was mixed at 5 rpm for 5 minutes. 100 parts of this powder composition
The resin was uniformly coated on the upper surface of a g / m ² glass cloth with a knife coater so that the resin weight became 60 g / m ² . Then, a panel heater of 150 ° C from the lower side
Warmed for minutes. Then turn the glass cloth upside down,
Resin weight 60g / 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 (Coupling treatment: integral blending method) Powdered epoxy resin having an average particle size of 150 μm (cresol novolak epoxy resin N-695, epoxy equivalent 213, manufactured by Dainippon Ink and Chemicals, Inc.) 100 parts by weight, powdered phenol novolak resin 3 having an average particle diameter of 100 μm 3
1 part by weight of 3-glycidoxypropyltrimethoxysilane was directly added to a mixture of 4.5 parts by weight and 11 parts by weight of a modified melamine-coated ammonium polyphosphate having an average particle diameter of 10 μm (Terage C-60 manufactured by Chisso Corporation). Add and premix. Next, the same treatment as in Example 1 was performed and a mechanochemical reaction was performed to obtain a powdery resin composition having an average particle size of 150 μm. Further, 1 part by weight of fine powder silica (Aerosil # 200 manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 0.05 μm was added thereto, and the rotation speed was 500 rpm with a Henschel mixer.
The mixture was mixed for 5 minutes. 210 g /
resin weight with a knife coater on one surface of the glass cloth m ² was uniformly applied so as to 90 g / m ^2. Thereafter, the mixture was heated from the lower surface side by a hot air heater at 120 ° C. for about 1 minute. Then, the glass cloth was turned upside down, and the other surface was uniformly coated with a knife coater so that the resin weight became 90 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 (Coupling treatment: dry method) Modified melamine-coated ammonium polyphosphate having an average particle diameter of 10 μm (Terage C-60 manufactured by Chisso Corporation) 10
One part by weight of 3-glycidoxypropyltrimethoxysilane was added as a silane coupling agent to 0 part by weight to obtain a coated ammonium polyphosphate treated with a coupling agent. Powdered epoxy resin (Dainippon Ink Chemical Industry
Cresol novolak epoxy resin N-69
5, epoxy equivalent 213) 100 parts by weight, powdered phenol novolak resin 34.5 parts by weight, coupling-coated polyphosphoramide 18 parts by weight and powdered 2-
Premix 0.5 part by weight of phenyl-4-methylimidazole, then use two rolls 12 inches in diameter,
After processing 30 times at 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, take out the sheet, cool it with cold air, and then use a fine pulverizer. By pulverizing, a powdery resin composition having an average particle size of 150 μm was obtained. 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 4 (Coupling treatment: wet method) Modified melamine-coated ammonium polyphosphate having an average particle size of 10 μm (Terage C-60 manufactured by Chisso Corporation) 100
A part by weight was dispersed in an aqueous solution obtained by dissolving 2.5 parts by weight of 3-glycidoxypropyltrimethoxysilane in water, stirred and sedimented to obtain a coated ammonium polyphosphate treated with a coupling agent. Powdered epoxy resin (cresol novolak type epoxy resin N-695, epoxy equivalent 213, manufactured by Dainippon Ink and Chemicals, Inc.) 10
0 parts by weight, 34.5 parts by weight of a powdery phenol novolak resin, the coupling-treated coated polyphosphoramide 1
1 part by weight and 0.5 parts by weight of powdery 2-phenyl-4-methylimidazole are preliminarily mixed, then roll-kneaded and pulverized in the same manner as in Example 3 to obtain a powdery resin composition having an average particle diameter of 150 μm. Was. Further, finely divided silica having an average particle size of 0.05 μm (Aerosil # 200 manufactured by Nippon Aerosil Co., Ltd.)
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 1, and then a copper-clad laminate having a thickness of 0.22 mm was produced using the prepreg.

Comparative Example 1 (No Coupling Treatment) 100 parts by weight of a powdery epoxy resin having an average particle size of 150 μm (cresol novolak type epoxy resin N-695, epoxy equivalent 213, manufactured by Dainippon Ink and Chemicals, Inc.) Powdered phenol novolak resin 3 having an average particle diameter of 100 μm 3
4.5 parts by weight, 11 parts by weight of powdery coated ammonium polyphosphate having an average particle diameter of 10 μm, and 0.5 parts by weight of powdery 2-phenyl-4-methylimidazole having an average particle diameter of 10 μm are preliminarily mixed. Using a stone mill-type kneading extruder (Mechanochemical Dispersion System KCK-80X2-V (6) manufactured by KCK Co., Ltd.), the number of rotations was 2
The mixture was treated at 00 rpm for 1 minute and subjected to a mechanochemical reaction to obtain a powdery resin composition having an average particle size of 150 μm. Using this powdery resin composition, a prepreg was obtained in the same manner as in Example 1. Two prepregs were laminated, and a copper foil having a thickness of 18 μm was laminated on top and bottom of the prepreg.
It was heated and pressed at a pressure of 40 kg / cm ² for 90 minutes to produce a copper-clad laminate having a thickness of 0.22 mm.

Comparative Example 2 (Conventional impregnation method) Epoxy resin (cresol novolak type epoxy resin N-695, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 2)
13) 100 parts by weight, phenol novolak resin
A mixture of 5 parts by weight, 11 parts by weight of powdery coated ammonium polyphosphate having an average particle diameter of 10 μm, and 0.5 parts by weight of 2-phenyl-4-methylimidazole was dissolved in 100 parts by weight of methylcellosolve. . This varnish was added to 100 g / m ² so that the solid content of the varnish became 100 g / m ^2.
After impregnating by impregnating a glass cloth of m ² , it was heated with a hot air heater at 170 ° C. for 3 minutes to obtain a prepreg. Two prepregs are stacked, and a thickness of 18
Laminate copper foil of μm, temperature 165 ℃, pressure 60kg
/ Cm ² for 90 minutes under heat and pressure, thickness 0.22m
m of the copper-clad laminate was produced.

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

[0043]

[Table 1]

[0044]

[Table 2]

(Measurement method) Coating property: At the time of coating, it was confirmed whether or not the coating was uniform on the appearance. 2. Impregnation: The cross section of the laminate was observed with a microscope to confirm the presence or absence of voids between glass fibers. 3. 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. 4. Tensile strength: Etching copper foil of copper clad laminate,
After cutting to 10 × 100 mm, the tensile strength was measured with Tensilon. 5. Copper foil peel strength: Measured according to JIS C6481. 6. 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. 7. Insulation resistance: Measured according to JIS C6481. 8. Flame resistance: Evaluated by the vertical method according to UL-94 standard.

Regarding the manufacturing cost, the method of the embodiment does not use a solvent, and thus the obtained laminate is the same as that of the comparative example 2.
The cost could be reduced by about 30 to 40% as compared with the one obtained in the above.

[0047]

According to the present invention, the prepreg and the laminate of the present invention do not use an organic solvent, and contain an epoxy resin, an epoxy resin curing agent,
And a powdered epoxy resin composition containing a coated phosphorus compound surface-treated with a coupling agent, so that resource saving, energy saving and reduction of air pollution can be achieved, thereby saving resources and energy. This is also excellent in terms of cost reduction. Further, 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. Furthermore, by using a coated phosphorus compound surface-treated with a coupling agent, more uniform powder application becomes possible, and quality such as heat resistance, flame retardancy, and adhesion to a copper foil can be improved. .

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F070 AA46 AB01 AB10 AC20 AC55 AD06 AE07 AE08 DA46 DA47 4F072 AA04 AA07 AD23 AD33 AD53 AE01 AE07 AF06 AF19 AG03 AH05 AK05 AL13 4J002 CC04X CC05X CC07X CD02W CD03W CD05W06 CD06W CD03W CD05W06 EN076 EN126 ER026 EW047 EW157 FB097 FB137 FB167 FB267 FD010 FD136 FD137 FD14X FD146 GF00 GQ00 HA09 4J036 AA01 CC02 DA01 FA04 FA12 JA08 JA11 KA05

Claims (4)

[Claims] 1. A powdery epoxy resin composition containing (a) an epoxy resin, (b) an epoxy resin curing agent, and (c) a coated phosphorus compound surface-treated with a coupling agent, is coated on a sheet-like fiber base. A prepreg characterized by being present on at least one side of a material. 2. The prepreg according to claim 1, wherein each of the components of the powdery epoxy resin composition is substantially in the form of a powder and is subjected to a mechanochemical reaction by applying mechanical energy thereto. 3. The prepreg according to claim 1, wherein the powdery epoxy resin composition is a powdery material 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, or 3 are laminated and heated and pressed.