JP6839811B2 - Resin composition, prepreg, metal-clad laminate, printed wiring board, and metal foil with resin - Google Patents

Description

The present invention relates to a resin composition, a prepreg, a metal-clad laminate, a printed wiring board, and a metal foil with a resin. More specifically, the present invention relates to a resin composition containing an epoxy resin and a curing agent, and a prepreg, a metal-clad laminate, a printed wiring board, and a metal foil with a resin obtained by using the resin composition. ..

Conventionally, printed wiring boards used in electronic devices have been improved in heat resistance by improving the glass transition temperature (Tg) and the like, and have been made flame-retardant. In recent years, especially in the field of small electronic devices such as mobile devices, the coefficient of thermal expansion of printed wiring boards has been further reduced and the coefficient of thermal expansion (CTE) has been lowered as the devices have become smaller, thinner, and more multifunctional. The market demand for the coefficient of expansion) is increasing. Generally, an epoxy resin composition is used as an insulating material for a printed wiring board. In this epoxy resin composition, a phenol-based curing agent, a diamine-based curing agent, a cyanate-based curing agent, and an acid anhydride are used as curing agents for the epoxy resin. Physical curing agents and the like are used. Among these various curing agents, an acid anhydride-based curing agent is known to be effective in reducing the dielectric constant. As the acid anhydride-based curing agent conventionally used, a polyfunctional acid anhydride-based compound having a plurality of cyclic structures of acid anhydride groups in one molecule, a styrene-maleic acid copolymer (SMA), or the like is used. Has been done. For example, Patent Document 1 describes that a copolymer (SMA) containing styrene and maleic anhydride as essential components is used as an acid anhydride-based curing agent.

Japanese Unexamined Patent Publication No. 9-194610

However, when the above-mentioned polyfunctional acid anhydride-based compound is used as a curing agent for an epoxy resin, it cannot sufficiently meet the market demand level in order to reduce the dielectric constant, and the adhesive strength such as peel strength is not sufficient. It was a little inferior. Further, SMA is more effective than polyfunctional acid anhydride-based compounds in achieving a lower dielectric constant, but has a problem of lower peel strength.

The present invention has been made in view of the above points, and is a resin composition, a prepreg, a metal-clad laminate, and a printed wiring board that can realize a high glass transition temperature, reduce the dielectric constant, and increase the peel strength. It is an object of the present invention to provide a plate and a metal foil with a resin.

The resin composition according to one embodiment of the present invention is a reaction product of (A) an epoxy resin, (B) a bifunctional polyphenylene ether compound and a monofunctional acid anhydride, and is a preliminary reaction capable of reacting with an epoxy group. It contains a compound and (C) a curing agent for epoxy resin. When the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass, the content of the component (B) is 5 to 60 parts by mass.

In the above resin composition, preferably, the component (B) is the acid anhydride group of the monofunctional acid anhydride when the amount of the hydroxyl group of the bifunctional polyphenylene ether compound is 1 equivalent. The amount is 1.5 equivalents or less.

In the above resin composition, preferably, when the amount of the epoxy group of the component (A) is 1 equivalent, the amount of the functional group that reacts with the epoxy group in the component (B) and the above ( The total amount of the epoxy group reacting with the functional group in the component C) is 0.8 to 1.2 equivalent.

The resin composition preferably further contains a phosphorus-containing flame retardant, and the total mass of the component (A), the component (B), and the component (C) is 100 parts by mass. In addition, the phosphorus content is 1 part by mass or more.

The resin composition preferably further contains an inorganic filler, and the total mass of the component (A), the component (B), and the component (C) is 100 parts by mass. , The content of the inorganic filler is 5 to 50 parts by mass.

In the above resin composition, preferably, the inorganic filler contains an inorganic filler treated with a surface treatment agent.

In the above resin composition, preferably, the inorganic filler treated with the surface treatment agent contains the surface treatment agent when the content of the inorganic filler is 100 parts by mass. The amount is 1 to 10 parts by mass.

The prepreg according to the embodiment of the present invention has the above-mentioned resin composition and a base material impregnated with the above-mentioned resin composition.

The metal-clad laminate according to the embodiment of the present invention has an insulating layer containing a cured product of the above resin composition and a metal layer in contact with the insulating layer.

The printed wiring board according to the embodiment of the present invention has an insulating layer containing a cured product of the above resin composition and wiring provided on the surface of the insulating layer.

The metal leaf with resin according to one embodiment of the present invention has an insulating layer containing a semi-cured product of the above resin composition and a metal leaf in contact with the insulating layer.

According to the present invention, by using a prereactant in which a bifunctional polyphenylene ether compound and a monofunctional acid anhydride are reacted in advance, volatilization of the monofunctional acid anhydride is suppressed, and the monofunctional acid anhydride is used as an epoxy resin. It can be incorporated into the curing reaction system. Then, by curing the epoxy resin with the prereactant and the curing agent for the epoxy resin, it is possible to realize a high glass transition temperature, reduce the dielectric constant, and improve the peel strength.

FIG. 1 is a cross-sectional view of a prepreg according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of a metal-clad laminate according to an embodiment of the present invention. FIG. 3 is a cross-sectional view of a printed wiring board according to an embodiment of the present invention. FIG. 4 is a cross-sectional view of a metal leaf with a resin according to an embodiment of the present invention.

The resin composition according to one embodiment of the present invention is a reaction product of (A) an epoxy resin, (B) a bifunctional polyphenylene ether compound and a monofunctional acid anhydride, and is a preliminary reaction capable of reacting with an epoxy group. It contains a compound and (C) a curing agent for epoxy resin. When the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass, the content of the component (B) is 5 to 60 parts by mass.

Conventionally, when an acid anhydride compound is used as it is as a curing agent for an epoxy resin in a printed wiring board using an epoxy resin, it cannot sufficiently meet the market demand level in order to reduce the dielectric constant. It was also difficult to improve the glass transition temperature. Therefore, as a result of repeated diligent studies, first, monofunctional acid anhydride was focused on as a curing agent capable of reducing the dielectric constant. Then, it was found that when an acid anhydride is used as a curing agent for the epoxy resin, a high glass transition temperature can be realized and a low dielectric constant can be achieved. On the other hand, monofunctional acid anhydrides are volatile due to their relatively small molecular weight. It was also found that due to its volatility, a part of the acid anhydride was volatilized and disappeared in the process of impregnating the base material with the resin composition and drying it to produce a prepreg. If a part of the acid anhydride is volatilized, the component ratio of the resin composition may change significantly before and after the production of the prepreg. Further, when a part of the acid anhydride disappears, it becomes difficult for the curing to proceed, and there is a possibility that sufficient curing property cannot be obtained. There is concern that the characteristics of the printed wiring board may be adversely affected by the change in the component ratio due to the volatilization of the curing agent and the decrease in the progress of curing. Therefore, further studies were carried out, and the resin composition according to the embodiment of the present invention was completed.

Hereinafter, the resin composition according to one embodiment will be further described.

Component (A): Epoxy resin The component (A) is an epoxy resin. The epoxy resin contains an epoxy group. The epoxy resin is preferably bifunctional or higher. A bifunctional or higher functional epoxy resin has high reactivity. In addition, bifunctional or higher means having two or more epoxy groups in one molecule. There is no particular upper limit on the number of epoxy groups in one molecule of the epoxy resin, but the number of epoxy groups may be, for example, 5 or less.

Examples of the epoxy resin include dicyclopentadiene type epoxy resin, phosphorus-containing epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and bisphenol A. Examples thereof include novolak type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, polyfunctional phenol diglycidyl ether compound, and polyfunctional alcohol diglycidyl ether compound. Only one type of epoxy resin may be used, or two or more types may be used in combination.

The epoxy resin may contain a phosphorus-containing epoxy resin. When a phosphorus-containing epoxy resin is used, the phosphorus content in the resin composition can be increased, thereby improving the flame retardancy.

Component (B): Prereactant Component (B) is a reactant of a bifunctional polyphenylene ether compound and a monofunctional acid anhydride. This reactant is defined as a pre-reactant. This reactant is capable of reacting with epoxy groups. That is, the component (B) is a component generated by the reaction in advance of the reaction of the resin composition. Since the component (B) can react with the epoxy group, it can react with the epoxy resin of the component (A). The component (B) is a curing component. The component (B) has a functional group that reacts with an epoxy group.

The bifunctional polyphenylene ether compound is a polyphenylene ether compound (PPE compound) having two hydroxyl groups (OH) in one molecule. The polyphenylene ether compound may be either a bifunctional polyphenylene ether or a modified bifunctional polyphenylene ether. The bifunctional polyphenylene ether compound may be a polyphenylene ether resin (PPE resin). Bifunctional in a bifunctional polyphenylene ether compound means that ideally two hydroxyl groups are present in one molecule. However, since the raw materials may vary, for example, the number of hydroxyl groups per molecule may be in the range of 1.8 to 2.2.

The bifunctional polyphenylene ether compound may have, for example, a structure in which two polyphenylene ether structures are bonded to one core structure. A hydroxyl group is arranged at the end of the polyphenylene ether structure. The bifunctional polyphenylene ether compound may be called a bifunctional polyphenylene ether oligomer. An example of the structural formula of the bifunctional polyphenylene ether compound is shown below. In the following formula, Y is the core structure. In the following structural formula, there is no modification to the benzene ring. The bifunctional polyphenylene ether compound may be modified by appropriate chemical modification based on the structure of the following formula. The modification can be carried out, for example, by introducing a functional group into the benzene ring.

In the above equation, n and m represent integers of 0 or more.

A monofunctional acid anhydride is an acid anhydride having one acid anhydride group (-COOCO-) in one molecule. The acid anhydride group has a structure in which two carboxylic acids in the molecule are dehydrated and condensed. The monofunctional acid anhydride forms an acid anhydride group in the molecule and has a cyclic structure.

Examples of the monofunctional acid anhydride include acid anhydrides such as dicarboxylic acid compounds. More specifically, as monofunctional acid anhydrides, for example, maleic anhydride, phthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylbicyclo [2.2.1] heptan-2, Examples thereof include 3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride and the like. Further, examples of the monofunctional acid anhydride include acid anhydrides such as tricarboxylic acid compounds. More specific examples of such monofunctional acid anhydrides include trimellitic acid anhydrides and the like. Among these, alicyclic acid anhydride is preferable. Specific examples of the alicyclic acid anhydride include 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, and bicyclo [2.2]. .1] Heptane-2,3-dicarboxylic acid anhydride, 1,2,3,6-tetrahydrophthalic anhydride and the like can be mentioned. These alicyclic acid anhydrides are suitable for reducing the dielectric constant. Only one type of monofunctional acid anhydride may be used, or two or more types may be used in combination. For example, a plurality of different types of alicyclic acid anhydrides may be used.

In this embodiment, the monofunctional acid anhydride is pre-reacted. Therefore, the volatility of the monofunctional acid anhydride is effectively suppressed even when the boiling point is 150 ° C. or lower and further 130 ° C. or lower. This is because the monofunctional acid anhydride is incorporated into the bifunctional polyphenylene ether compound by a chemical bond, so that it no longer has a structure of the monofunctional acid anhydride and does not volatilize even when heated. Therefore, the pre-reaction is particularly effective when using monofunctional acid anhydrides with lower boiling points. Further, since the monofunctional acid anhydride has a relatively small molecular weight as compared with a normal curing agent for epoxy resin, it is effective in suppressing an increase in varnish viscosity. From this point of view, for example, a monofunctional acid anhydride having a molecular weight of 400 or less is suitable. When such a monofunctional acid anhydride is used, the dielectric constant (relative permittivity (Dk)) of the cured product can be lowered and the peel strength can be increased as compared with the case where the polyfunctional acid anhydride is used. Can be done. When a plurality of monofunctional acid anhydrides are used, the weight average molecular weight of the mixed acid anhydrides is preferably 400 or less, and all of the plurality of monofunctional acid anhydrides have a molecular weight of 400 or less. Is more preferable. The molecular weight of the monofunctional acid anhydride is more preferably 300 or less.

In the preliminary reaction, the hydroxyl group at the end of the bifunctional polyphenylene ether compound can attack the acid anhydride group to open the ring of the acid anhydride group and form an ester bond. Preliminary reactions can produce ester compounds derived from bifunctional polyphenylene ether compounds and monofunctional acid anhydrides. The component (B), that is, the prereactant, contains an ester compound of a bifunctional polyphenylene ether compound and a monofunctional acid anhydride. In the preliminary reaction, the ring-opening reaction of the acid anhydride produces a carboxy group. The carboxy group becomes a functional group that reacts with the epoxy resin in the component (B). The reaction of the bifunctional polyphenylene ether compound with the monofunctional acid anhydride ideally produces a product in which the monofunctional acid anhydride is ring-opened and bonded to both ends of the bifunctional polyphenylene ether compound. In this case, the prereactant may have two carboxy groups in one molecule.

The component (B) can be obtained as a prereactant by mixing the above bifunctional polyphenylene ether compound and a monofunctional acid anhydride and heating them to react with each other.

As for the component (B), the amount of the acid anhydride group of the monofunctional acid anhydride is preferably 1.5 equivalents or less when the amount of the hydroxyl group of the bifunctional polyphenylene ether compound is 1 equivalent. Thereby, a resin composition having excellent performance and a cured product thereof can be obtained. In particular, the adverse effect of curing due to the residual monofunctional acid anhydride can be reduced. In the equivalent ratio, at the time of the preliminary reaction, a bifunctional polyphenylene ether compound having 1 equivalent of a hydroxyl group and a monofunctional acid anhydride having 1.5 equivalents of an acid anhydride group are mixed and reacted. This equivalent is a relative value relative to the reactive functional group. The amount of the acid anhydride group of the monofunctional acid anhydride with respect to the amount of the hydroxyl group of the bifunctional polyphenylene ether compound is preferably 0.8 equivalent or more and 1.2 equivalent or less. As a result, it becomes easy to obtain a preliminary reaction product having good curability. The equivalent of the hydroxyl group of the bifunctional polyphenylene ether compound can be defined as the phenol equivalent.

The component (B) is a reactant obtained by a preliminary reaction, and strictly speaking, in addition to the reactant of the bifunctional polyphenylene ether compound and the monofunctional acid anhydride, the simple reaction did not occur. It may contain functional acid anhydrides and unreacted bifunctional polyphenylene ether compounds. It may be said that the component (B) contains a pure reaction product (that is, a reaction product in which a bifunctional polyphenylene ether compound and a monofunctional acid anhydride are all reacted in an ideal amount) and other components. Then, such a component (B) can be mixed with the component (A) and other components including the component (C) to form a resin composition. As for the component (B), the amount of the monofunctional acid anhydride in the component (B) (that is, the amount of the monofunctional acid anhydride remaining after the reaction) should be as small as possible. In the component (B), the amount of the monofunctional acid anhydride remaining without the reaction is 20 equivalents or less with respect to 100 equivalents of the portion derived from the monofunctional acid anhydride in the pure reaction product produced by the reaction. Is preferable, and 10 equivalents or less is preferable.

(C) Hardener for Epoxy Resin The component (C) is a hardener for epoxy resin. The epoxy resin curing agent can react with the epoxy group and can cure the epoxy resin. The component (C) has a functional group that reacts with an epoxy group.

As the curing agent for epoxy resin, a group of polyfunctional acid anhydride, styrene anhydride maleic acid resin (SMA), amine-based curing agent, thiol-based curing agent, cyanate-based curing agent, active ester-based curing agent, and phenol-based curing agent. It is preferable to use at least one selected from the above. Of these, the polyfunctional acid anhydride is an acid anhydride having two or more acid anhydride groups as functional groups in one molecule. The polyfunctional acid anhydride may contain an alicyclic polyfunctional acid anhydride. The polyfunctional acid anhydride can supplement the action of the acid anhydride of the component (B). Specific examples of the polyfunctional acid anhydride include ethylene glycol bisanhydrotrimeritate. The styrene maleic anhydride resin (SMA) is a copolymer of styrene and maleic anhydride, and the ratio of styrene to maleic anhydride is not particularly limited. For example, the equivalent ratio of styrene: maleic anhydride may be in the range of 1: 1 to 8: 1. Further, specific examples of the amine-based curing agent include dicyandiamide and the like. Specific examples of the thiol-based curing agent include pentaerythritol tetrakis (3-mercaptobutyrate) and the like. Further, specific examples of the cyanate-based curing agent include bisphenol A type cyanate resin and the like. Further, specific examples of the phenolic curing agent include novolak type phenolic resin and the like. Only one type of curing agent for epoxy resin may be used, or two or more types may be used in combination.

The composition for an epoxy resin may or may not contain a monofunctional acid anhydride, but it is preferable that the composition does not contain a monofunctional acid anhydride. Since the monofunctional acid anhydride is a component that easily volatilizes, if the monofunctional acid anhydride is present in the resin composition as it is, it may adversely affect the curing. The resin composition of the present embodiment has an advantage that the monofunctional acid anhydride is contained in the component (B). It is preferable that all of the monofunctional acid anhydrides used in the resin composition are used as the component (B).

The functional group that reacts with the epoxy group in the epoxy resin curing agent can be an appropriate functional group that the above-mentioned epoxy resin curing agent has. Examples of the functional group include, but are not limited to, an acid anhydride group, an amino group, a thiol group, a cyanate group, and a phenol group.

Here, both the component (B) and the component (C) are capable of reacting with the epoxy resin and function as a so-called curing agent. Therefore, it can be said that both the component (B) and the component (C) are curing components (components that cure the epoxy resin). For convenience, the component (B) may be referred to as a first curing agent, and the component (C) may be referred to as a second curing agent. As described above, when the component (B) and the component (C) are contained as the curing component, it is finally possible to obtain the same effect as when the monofunctional acid anhydride is used as the curing agent, and the cured product can be obtained. The characteristics of can be improved. If the component (C) alone, that is, if the curing component does not contain a prereactant, it is difficult to use the monofunctional acid anhydride, so that it is difficult to obtain the advantageous effect of the monofunctional acid anhydride. Further, if the component (B) alone, that is, if all of the curing components are prereactants, there is a possibility that sufficient curability cannot be obtained. In this way, the component (B) and the component (C) complement each other in curability, and by making the best use of their respective characteristics, excellent curability can be exhibited.

The resin composition preferably has a content of the component (B) of 5 to 60 parts by mass when the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass. .. Thereby, a resin composition having excellent performance and a cured product thereof can be obtained. In particular, a uniform resin composition can be easily obtained, alkali resistance is improved, and the dielectric property can be reduced, so that a cured product having excellent dielectric properties can be obtained. If the content of the component (B) exceeds 60 parts by mass, the resin composition may be easily phase-separated. On the other hand, if the content of the component (B) is less than 5 parts by mass, the alkali resistance of the resin composition may decrease, and the relative permittivity (Dk) may increase, resulting in deterioration of the dielectric properties. .. The content of the component (B) is more preferably 10 to 50 parts by mass, further preferably 15 to 40 parts by mass. The content of the component (B) can be considered as the total amount of the bifunctional polyphenylene ether compound and the monofunctional acid anhydride. Strictly speaking, the pre-reaction can cause dehydration condensation, which can result in less weight than a simple total amount, but because the amount is small, the total amount can be approximated to the amount of pre-reactant.

Further, when the amount of the epoxy group of the component (A) is 1 equivalent, the resin composition reacts with the amount of the functional group that reacts with the epoxy group in the component (B) and the epoxy group in the component (C). The total with the amount of functional groups is preferably 0.8 to 1.2 equivalents. Thereby, a resin composition having excellent performance and a cured product thereof can be obtained. In particular, it is possible to obtain a cured product having excellent flame retardancy, a high glass transition temperature, a large peel strength, and improved alkali resistance. The total amount of the reactive groups of the component (B) and the component (C) is more preferably 0.9 to 1.1 equivalents.

The resin composition may further contain a flame retardant, a curing accelerator, and the like.

As the flame retardant, a halogen-based flame retardant or a non-halogen flame retardant can be used. As the non-halogen flame retardant, for example, a phosphorus-containing flame retardant can be used. When a phosphorus-containing flame retardant is used, the phosphorus content in the total amount of the organic component and the phosphorus-containing flame retardant of the resin composition is optimized in order to obtain good flame retardancy. When the resin composition contains a phosphorus-containing flame retardant, the phosphorus content is 1 part by mass or more when the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass. Is preferable. Thereby, a cured product having excellent flame retardancy can be obtained. The phosphorus content is more preferably 1.5 parts by mass or more. The upper limit of the phosphorus content is not particularly limited, but the phosphorus content may be 5 parts by mass or less, and further may be 3 parts by mass or less in relation to other components. This is because if a phosphorus-containing flame retardant having a content exceeding a necessary and sufficient content for imparting flame retardancy is used, the electrical characteristics, heat resistance, and the like may be deteriorated.

Further, it is preferable that at least a part of the phosphorus-containing flame retardant has a functional group that reacts with an acid anhydride group or a carboxy group (-COOH). Specifically, the phosphorus-containing flame retardant is preferably a reactive phosphorus-containing flame retardant having a functional group that reacts with an acid anhydride group or a carboxy group (-COOH). The acid anhydride group in this case is, for example, the acid anhydride group contained in the unreacted monofunctional acid anhydride, and the carboxy group is, for example, when the bifunctional polyphenylene ether compound reacts with the monofunctional acid anhydride. It is a carboxy group formed by opening the ring of an acid anhydride group of a monofunctional acid anhydride. Specific examples of the functional group of the reactive phosphorus-containing flame retardant include a hydroxy group and an amino group. Since the monofunctional acid anhydride contains a large amount of oxygen atoms, it tends to reduce the flame retardancy of the cured product. However, when the monofunctional acid anhydride is reacted with the above-mentioned reactive phosphorus-containing flame retardant, Since the phosphorus atom can be present near the oxygen atom, the flame retardancy can be improved.

Further, a molten phosphorus-containing flame retardant and a dispersed phosphorus-containing flame retardant that do not react with the monofunctional acid anhydride, or a phosphorus-free flame retardant may be used as long as the effect of the resin composition is not impaired. The melt-type phosphorus-containing flame retardant dissolves in the resin composition to form a uniform system, and specific examples thereof include phosphazene and the like. The dispersed phosphorus-containing flame retardant is a dispersion system that is dispersed without being dissolved in the resin composition, and specific examples thereof include aluminum phosphinate, which is a metal phosphate.

The flame retardant may contain a flame retardant other than the phosphorus-containing flame retardant. Only one type of flame retardant may be used, or two or more types may be used in combination.

The curing accelerator is not particularly limited as long as it can accelerate the reaction between the epoxy resin and the curing agent, but an imidazole-based compound can be used. Examples of the imidazole-based compound include 2-ethyl-4-methylimidazole (2E4MZ). The content of the curing accelerator is not particularly limited as long as the effect of the resin composition is not impaired. For example, when the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass, the content of the curing accelerator may be 0.01 to 1 part by mass.

The resin composition may further contain an inorganic filler or the like. As the inorganic filler, for example, silica such as spherical silica or crushed silica, metal hydroxide such as aluminum hydroxide or magnesium hydroxide, or the like can be used. The content of such an inorganic filler can be appropriately determined in consideration of the balance between low dielectric constant and low CTE, and is not particularly limited. When the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass, the content of the inorganic filler is preferably 5 to 50 parts by mass. When the content of the inorganic filler is 5 parts by mass or more, high CTE can be suppressed. When the content of the inorganic filler is 50 parts by mass or less, it is possible to suppress a decrease in the fluidity of the resin composition. The content of this inorganic filler is more preferably 10 to 45 parts by mass.

The inorganic filler preferably contains an inorganic filler that has been treated with a surface treatment agent. When the inorganic filler is surface-treated, the inorganic filler and the organic component can be firmly bonded to each other, and the characteristics of the cured product can be improved. The surface treatment agent may contain an organic functional group. The inorganic filler treated with such a surface treatment agent can be called an inorganic filler having an organic functional group.

The inorganic filler preferably contains an inorganic filler that has been surface-treated with a silane coupling agent in advance. Such an inorganic filler can be called a silane coupling inorganic filler. When it has an organic functional group, it can be called an inorganic filler with an organic functional group. The silane coupling agent serves as a surface treatment agent.

Examples of the silane coupling agent include epoxysilane, isocyanatesilane, aminosilane, vinylsilane, methacrylsilane, acrylicsilane, ureidosilane, mercaptosilane, sulfidesilane, and styrylsilane. Only one type of silane coupling agent may be used, or two or more types may be used in combination. Generally, the amount of polar groups generated by the reaction between the epoxy resin and the acid anhydride-based curing agent is small, but even if the amount of polar groups produced is small as described above, the inorganic filler is surface-treated as described above. With the silane coupling agent, the inorganic filler and the organic component can be firmly bonded to each other, and the alkali resistance of the cured product of the resin composition can be improved.

Examples of the inorganic filler treated with the silane coupling agent include epoxysilane-treated crushed silica, epoxysilane-treated spherical silica, and isocyanatesilane-treated spherical silica.

Examples of the surface treatment method for the inorganic filler include a direct treatment method and an integral blending method. The direct treatment method is a method in which the inorganic filler is directly treated with a silane coupling agent in advance, and the inorganic filler after the surface treatment is blended with the base varnish described later. The integral blending method is a method of adding a silane coupling agent to a base varnish containing an inorganic filler. Compared with the integral blend method, the direct treatment method is preferable because it can efficiently bind the inorganic filler and the organic component and further improve the alkali resistance of the cured product of the resin composition.

The inorganic filler treated with the surface treatment agent preferably has a surface treatment agent content of 1 to 10 parts by mass when the content of the inorganic filler is 100 parts by mass. Thereby, the alkali resistance and heat resistance of the cured product can be improved. In particular, when the inorganic filler is surface-treated with a silane coupling agent by the integral blend method, the content of the silane coupling agent is 1 to 10 parts by mass when the content of the inorganic filler is 100 parts by mass. It is preferable to have. When the content of the silane coupling agent is 1 part by mass or more, the alkali resistance of the cured product of the resin composition can be further improved. When the content of the silane coupling agent is 10 parts by mass or less, the decrease in heat resistance can be suppressed. The content of this silane coupling agent is more preferably 1.5 to 8 parts by mass.

In the resin composition, the silane coupling agent and the inorganic filler may be separately blended. The resin composition may contain a silane coupling agent. At this time, as described above, it is preferable that the silane coupling agent functions as a surface treatment agent to couple the inorganic filler by the integral blend method, but the silane coupling agent couples the inorganic filler. You don't have to. Even when the silane coupling agent is contained in the resin composition as it is without coupling with the inorganic filler, the bond between the inorganic filler and the organic component can be strengthened. It is considered that this is because the same action as coupling (that is, surface treatment) can occur during the preparation and reaction of the resin composition. The quantitative relationship between the inorganic filler and the silane coupling agent is the same as described above. However, it is preferable that the inorganic filler is surface-treated with a silane cup agent in advance.

The resin composition can be prepared as a resin varnish as follows.

First, a preliminary reaction product, which is the component (B), is prepared. The step of preparing the pre-reactant is defined as the pre-reactant step. Specifically, at least a bifunctional polyphenylene ether compound and a monofunctional acid anhydride are mixed and dissolved in a solvent to prepare a mixture. The mixture may be varnished. At this time, the mixture may contain an organic component such as a curing accelerator or a non-reactive flame retardant that does not directly affect the preliminary reaction. However, other organic components having reactivity with the bifunctional polyphenylene ether compound and the monofunctional acid anhydride (for example, a curing agent for epoxy resin and a reactive flame retardant) are not added to this mixture, and a preliminary reaction is carried out. It is preferable to mix after. More preferably, a mixture is prepared in which only the bifunctional polyphenylene ether compound and the monofunctional acid anhydride are mixed in a solvent. The amount of solvent in the mixture can be adjusted so that the solid content (non-solvent component) concentration is 60 to 80% by mass. Then, the preliminary reaction is allowed to proceed by heating the mixture at, for example, 60 to 130 ° C. for 1 to 10 hours, preferably 75 to 110 ° C. for 3 to 10 hours while stirring with a stirrer such as a disper. As a result, a prereactant obtained by reacting the bifunctional polyphenylene ether compound with the monofunctional acid anhydride is formed in the varnish (mixture).

As the solvent used for preparing the mixture (varnish) in the preliminary reaction, a solvent having no reactivity with the bifunctional polyphenylene ether compound or the monofunctional acid anhydride can be used. Examples of the solvent include ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone (MEK), and aromatic hydrocarbons such as benzene and toluene. On the other hand, a solvent having a hydroxyl group, such as an alcohol solvent, has reactivity with an acid anhydride, and therefore its use is preferably avoided.

In the pre-reaction step, it is preferable to experimentally grasp the correlation between the heating temperature and reaction time, which are the pre-reaction conditions, and the ring-opening rate of the monofunctional acid anhydride by sampling or the like. Thereby, by adjusting the above-mentioned preliminary reaction conditions, the ring-opening rate of the monofunctional acid anhydride in the product of the preliminary reaction can be adjusted. From the ring-opening rate, the amount of monofunctional acid anhydride remaining in the component (B) can be determined. The heating temperature and reaction time conditions thus obtained can be applied to actual production. The above heating temperature and heating time are examples, and are appropriately adjusted.

In the pre-reaction, the monofunctional acid anhydride is ring-opened by reaction with a bifunctional polyphenylene ether compound. The progress of the reaction of the monofunctional acid anhydride can be confirmed by the ring-opening rate of the monofunctional acid anhydride. In the preliminary reaction product, the ring-opening rate of the monofunctional acid anhydride is preferably 80% or more (upper limit is 100%). As a result, the residual amount of the monofunctional acid anhydride in the preliminary reaction product is reduced, and the adverse effect of the monofunctional acid anhydride can be reduced. When the ring opening rate of the monofunctional acid anhydride is less than 80%, a large amount of unreacted monofunctional acid anhydride remains, and the monofunctional acid anhydride easily volatilizes and disappears during the production of the prepreg. As a result, it is considered that the curing component is insufficient and the cross-linking density of the cured product of the resin composition is lowered, the glass transition temperature (Tg) of the cured product is lowered, the heat resistance is deteriorated, and the peel strength is lowered. It may decrease.

The ring-opening rate of the monofunctional acid anhydride can be calculated, for example, by comparing the infrared absorption spectra of the mixture before and after the reaction. The mixture may have peaks due to cyclic acid anhydride groups near ^{1800 to 1900 cm -1} before and after the reaction (preliminary reaction). Also, the mixture may have a peak due to the benzene ring near ^{1450 to 1580 cm -1} , which is not involved in the reaction. Then, the peak caused by the benzene ring is used as an internal standard, and the amount (however, relative value) of the peak caused by the acid anhydride group is determined before and after the reaction. The amount of peaks is determined by the area ratio using the internal standard. Specifically, the area of the peak caused by the acid anhydride group before the reaction (A ₁ ), the area of the peak caused by the acid anhydride group after the reaction (A ₂ ), and the area of the peak caused by the benzene ring before the reaction (A 1). B ₁ ) and the area of the peak due to the benzene ring after the reaction (B ₂ ) are used. Then, the area ratio (A ₁ / B ₁ ) becomes the amount of the acid anhydride group before the reaction, and the area ratio (A ₂ / B ₂ ) becomes the amount of the acid anhydride group after the reaction. Substitute these into the following equation.

Ring-opening rate (%) = {1- (A ₂ / B ₂ ) / (A ₁ / B ₁ )} × 100
Thereby, the ring-opening rate of the monofunctional acid anhydride can be obtained.

Since the ring-opening rate of the monofunctional acid anhydride changes depending on the heating temperature and the heating time at the time of preparing the varnish, the heating conditions can be appropriately adjusted so that the ring-opening rate is 80% or more. The conditions for this preliminary reaction can be appropriately set by sampling the reactants over time while performing the preliminary reaction and confirming the ring-opening rate.

As a result, a preliminary reaction product of the component (B) is obtained. The prereactant does not have to be purified, and it is preferable to proceed to the next step (base varnish preparation step) as it is. As a result, manufacturing efficiency is improved. The pre-reaction step is continuously shifted to the base varnish preparation step.

In the base varnish preparation step, the component (B) produced by the preliminary reaction is mixed with the component (A), the component (C), and other components (excluding the inorganic component) as necessary, and further necessary. The base varnish can be prepared by adding and mixing the solvent according to the above. The base varnish is a varnish containing an organic component excluding inorganic components such as an inorganic filler. Further solvents may be added in the base varnish preparation step. The viscosity can be adjusted as appropriate by adding a solvent.

When preparing a resin composition that does not contain an inorganic component such as an inorganic filler, the base varnish becomes a resin varnish (resin composition) as it is. Then, this resin varnish can be used for manufacturing a prepreg or the like.

On the other hand, when preparing a resin composition containing an inorganic component, the inorganic component is added to the above base varnish. At this time, it is preferable that the base varnish to which the inorganic component is added is stirred and mixed at 20 to 40 ° C. for 1 to 3 hours to make it uniform. This step is defined as an inorganic component blending step. The inorganic component is, for example, an inorganic filler. In the inorganic component blending step, a direct treatment method can be applied to blend the surface-treated inorganic filler into the base varnish. Alternatively, the inorganic filler and the surface treatment agent may be separately directly blended into the base varnish, and the surface treatment of the inorganic filler may be performed by the integral blending method. The surface treatment in this case can be performed through stirring and mixing of the resin varnish. Alternatively, the inorganic filler and the surface treatment agent may be simply blended separately without considering the surface treatment.

From the above, a resin composition can be obtained. In the above production method, the resin composition is obtained as a resin varnish. Then, the prepreg, the metal-clad laminate, the printed wiring board, and the metal foil with resin are manufactured by using the resin composition.

FIG. 1 is a cross-sectional view of the prepreg 1 according to the present embodiment. The prepreg 1 has an uncured resin composition 2 and a base material 3 impregnated with the resin composition 2. As the resin composition 2, the resin composition 2 described above is used.

In the present embodiment, the resin varnish of the resin composition 2 obtained as described above is impregnated into the base material 3 such as glass cloth. Then, the base material 3 impregnated with the resin varnish is dried by heating at 110 ° C. or higher and 140 ° C. or lower. The prepreg 1 can be produced by removing the solvent in the resin varnish by this drying and semi-curing the resin composition 2. At this time, since the monofunctional acid anhydride is basically a preliminary reaction product, volatilization of the monofunctional acid anhydride is unlikely to occur during heating and drying. Most of the portion derived from the monofunctional acid anhydride remains in the semi-cured resin composition 2 in the prepreg 1.

The above heat drying may be carried out by appropriately adjusting the conditions so that the gel time of the prepreg 1 becomes a desired time, and for example, the gel time is preferably 60 seconds or more and 240 seconds or less. The gel time of the prepreg 1 is the time from immediately after the semi-cured resin composition 2 collected from the prepreg 1 is placed on a plate heated to 170 ° C. until the resin composition 2 gels. The amount of resin in the prepreg 1 is preferably 30 parts by mass or more and 80 parts by mass or less (30% by mass or more and 80% by mass or less) in the resin composition 2 with respect to 100 parts by mass of the prepreg 1. The amount of resin in the prepreg 1 is the content of the resin composition 2 in the prepreg 1.

FIG. 2 is a cross-sectional view of the metal-clad laminate 11 according to the present embodiment. The metal-clad laminate 11 has an insulating layer 12 containing a cured product of the resin composition 2 and a metal layer 13 in contact with the insulating layer 12.

In the present embodiment, the metal-clad laminate 11 can be manufactured by laminating the metal layer 13 on the prepreg 1 manufactured as described above and heat-pressing molding. As the prepreg 1, for example, a laminated body in which a plurality of prepregs 1 are stacked is used. The metal layer 13 is bonded to the surfaces located at both ends of the laminated body of the prepreg 1 in the laminating direction by using, for example, copper foil. In the metal-clad laminate 11, the cured product of the prepreg 1 constitutes the insulating layer 12. The prepreg 1 and the metal layer 13 are heated and pressurized under the conditions of, for example, 140 ° C. or higher, 200 ° C. or lower, 0.5 MPa or higher, 5.0 MPa or lower, 40 minutes or longer, 240 minutes or lower. Since the cured resin layer constituting the insulating layer 12 is composed of the cured product of the resin composition 2, the glass transition temperature can be increased to improve the heat resistance. Further, since the preliminary reaction product and the curing agent for epoxy resin are used in combination as a curing component, the dielectric constant of the insulating layer 12 can be lowered.

Further, the metal-clad laminate 11 according to the present embodiment can be manufactured without using the prepreg 1. For example, the varnish-like resin composition 2 is directly applied to the surface of the metal layer 13, and the metal layer 13 and the resin composition 2 are heated and pressurized to obtain the varnish-like resin composition 2 and the insulating layer 12 from the varnish-like resin composition 2. Is obtained. The heating and pressurizing conditions are the same as the method for producing the insulating layer 12 from the prepreg 1. The metal-clad laminate 11 is manufactured by the above method.

FIG. 3 is a cross-sectional view of the printed wiring board 21 according to the present embodiment. The printed wiring board 21 has an insulating layer 12 containing a cured product of the resin composition 2 and wiring 14 provided on the surface of the insulating layer 12.

The printed wiring board 21 can be manufactured by forming the wiring 14 having a desired pattern on the metal-clad laminate 11. As an example, the printed wiring board 21 uses an insulating layer 12 made of a cured product of the prepreg 1. For example, the printed wiring board 21 can be manufactured by forming the wiring 14 having a desired pattern on the surface of the metal-clad laminate 11 using the subtractive method.

Further, when this printed wiring board 21 is used as a core material (inner layer material), a multilayer printed wiring board can be manufactured. When manufacturing a multi-layer printed wiring board, the wiring (inner layer pattern) of the core material is roughened by black oxidation treatment or the like. After that, the metal layer 13 is laminated on the surface of the core material with the prepreg 1 interposed therebetween. The core material on which the metal layers 13 are stacked is heated and pressed to form a laminated structure. Also at this time, for example, heating and pressurization are performed under the conditions of 140 ° C. or higher, 200 ° C. or lower, 0.5 MPa or higher, 5.0 MPa or lower, 40 minutes or longer, 240 minutes or lower. Next, drilling and desmearing are performed. After that, a wiring (outer layer pattern) is formed from the metal layer 13 by using the subtractive method, and a through hole is formed by plating the inner wall of the hole. Through the above process, a multilayer printed wiring board is manufactured. The number of layers of the multilayer printed wiring board is not particularly limited.

In the printed wiring board 21, the dielectric constant of the insulating layer 12 is lowered. Therefore, when transmitting a signal through the wiring 14, the signal speed can be increased and a large amount of information can be processed at high speed.

FIG. 4 is a cross-sectional view of the metal leaf 31 with resin according to the present embodiment. The resin-attached metal foil 31 has an insulating layer 32 containing a semi-cured product of the resin composition 2 and a metal foil 33 in contact with the insulating layer 32.

By manufacturing the printed wiring board 21 using the metal foil 31 with resin, the printed wiring board 21 is provided in which the loss during signal transmission is further reduced while maintaining the adhesion between the wiring 14 and the insulating layer 12. be able to.

The metal leaf 31 with a resin is produced, for example, by applying the varnish-like resin composition 2 on the metal leaf 33 and heating the metal leaf 33. The varnish-like thermosetting resin composition 2 is applied onto the metal leaf 33, for example, by using a bar coater. The applied resin composition 2 is heated under the conditions of, for example, 80 ° C. or higher, 180 ° C. or lower, 1 minute or longer, and 10 minutes or lower. The heated resin composition 2 is formed on the surface (which serves as the contact surface) of the metal foil 33 as the uncured insulating layer 32.

Further, as a method of manufacturing the printed wiring board 21, in addition to the method of manufacturing by using the metal-clad laminate 11, a method of manufacturing by using the metal foil 31 with resin can be mentioned. As a method of manufacturing the printed wiring board 21 using the metal foil 31 with resin, a method of using the metal foil 31 with resin by laminating it on a resin substrate on which wiring is formed, or a method of superimposing a plurality of metal foils 31 with resin. The method to be used can be mentioned. At this time, the uncured insulating layer 32 is cured by heating. Then, by removing a part of the layer made of the metal foil 33, the wiring is formed from the layer of the metal foil 33.

Hereinafter, the present invention will be specifically described with reference to Examples.

Details of the raw materials of the resin compositions shown in Tables 1 to 3 below are described below.

[material]
[Epoxy resin: component (A)]
"HP-7200HHH" manufactured by DIC Corporation, which is a dicyclopentadiene type epoxy resin (epoxy equivalent: 280 to 290 g / eq, softening point: 100 to 105 ° C.)
-"FX-289-P" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., which is a phosphorus-containing epoxy resin (epoxy equivalent: 390 g / eq, phosphorus content: 3.5 wt%)
[Preliminary reactant: component (B)]
-"PPE resin MX90" manufactured by SABIC, which is a bifunctional polyphenylene ether compound (bifunctional PPE compound) (Mn: 1600 g / mol)
"Ricacid MH-700" (4-methylhexahydrophthalic anhydride / hexahydrophthalic anhydride = 70/30) (liquid alicyclic acid anhydride, acid anhydride) manufactured by Shin Nihon Rika Co., Ltd., which is a monofunctional acid anhydride. Equivalent: 161 to 166 g / eq, neutralization value: 675 to 695 KOH mg / g, freezing point: 20 ° C.)
[Curing agent: component (C)]
-"Ricacid TMEG-S" (ethylene glycol bisanhydrotrimeritate) manufactured by New Japan Chemical Co., Ltd., which is a polyfunctional acid anhydride (acid anhydride equivalent: 204 g / eq, softening point: 64-76 ° C)
"B-4500" manufactured by DIC Corporation, which is an alicyclic polyfunctional acid anhydride (powdered acid anhydride, acid anhydride group equivalent: 132 g / eq)
"SMA EF-30" manufactured by CRAY VALLY, which is a polyfunctional acid anhydride and a styrene maleic anhydride copolymer (styrene: maleic anhydride = 3: 1 styrene / maleic anhydride copolymer, styrene) Maleic anhydride resin, neutralizing value: 280 KOHmg / g, weight average molecular weight: 9500)
-Amine-based curing agent "DICY" manufactured by Nippon Carbide Industries Co., Ltd. (dicyandiamide)
-"Carens MT PE1" manufactured by Showa Denko KK, a thiol-based curing agent (tetrafunctional thiol, pentaerythritol tetrakis (3-mercaptobutyrate), molecular weight: 544.8)
-LONZA's "BADBy" (bisphenol A type cyanate ester), which is a cyanate-based curing agent.
"EXB-9485" manufactured by DIC Corporation, which is an active ester-based curing agent (ester group equivalent 204 g / eq, softening point 90 ° C.)
"TD-2090" manufactured by DIC Corporation, which is a phenolic curing agent (phenolite TD-2090, hydroxyl group equivalent 105 g / eq, softening point 117-123 ° C)
[Flame retardants]
-"SPB-100" manufactured by Otsuka Chemical Co., Ltd., which is a molten phosphorus-containing flame retardant (phosphazene, phosphorus content: 13 wt%)
-"OP-935" manufactured by Clariant Japan Co., Ltd., which is a dispersive phosphorus-containing flame retardant (aluminum phosphide, phosphorus content: 23 wt%)
"HPC-9100" manufactured by DIC Corporation, which is a reactive phosphorus-containing flame retardant (phosphorus content: 10 to 11 wt%, softening point: 133 to 147 ° C.)
-Reactive phosphorus-containing flame retardant "Emerald 2000" manufactured by Chemtura Japan Co., Ltd. (phosphorus content: 9.8 wt%)
[Curing accelerator]
-2-Ethyl-4-methylimidazole (2E4MZ), which is an imidazole-based curing accelerator
[Inorganic filler]
・ "Megasil 525" manufactured by Sibelco Japan Co., Ltd., which is melt-crushed silica.
"Megasil 525 RCS" manufactured by Sibelco Japan Co., Ltd., which is crushed silica treated with epoxy silane (crushed silica surface-treated with epoxy silane in advance, D100: <11 μm)
-Epoxysilane treated spherical silica "2500-SEJ" manufactured by Admatex Co., Ltd. (spherical silica surface-treated with epoxysilane in advance)
-Isocyanate silane treated spherical silica "2500-GNO" manufactured by Admatex Co., Ltd. (spherical silica surface-treated with isocyanate silane in advance)
-Aluminum hydroxide "CL-303M" manufactured by Sumitomo Chemical Co., Ltd.
[Silane coupling agent]
-Aminosilane "KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd. (3-aminopropyltrimethoxysilane)
-Mercaptosilane "KBM-802" manufactured by Shin-Etsu Chemical Co., Ltd. (3-mercaptopropylmethyldimethoxysilane)
-Epoxysilane "KBM-402" manufactured by Shin-Etsu Chemical Co., Ltd. (3-glycidoxypropylmethyldimethoxysilane)
-Isocyanatesilane "KBE-9007" manufactured by Shin-Etsu Chemical Co., Ltd. (3-isocyanatepropyltriethoxysilane)
Although not shown in Tables 1 to 3, MEK (methyl ethyl ketone) or toluene was used as a solvent for forming the resin varnish.

[Resin composition]
In the examples, the bifunctional polyphenylene ether compound and the monofunctional acid anhydride, which are the raw materials of the component (B), are blended in the blending ratios (parts by mass) shown in Tables 1 to 3 below, and this is used as a solvent (toluene). ) Was diluted so that the solid content (non-solvent component) concentration was 60 to 80% by mass. This was heated at 75 to 110 ° C. for 3 to 10 hours while stirring and mixing with a disper to obtain a preliminary reaction product as the component (B). The temperature and time conditions in the pre-reaction were adjusted so that the ring-opening rate of the monofunctional acid anhydride was as high as possible (at least 80% or more). The method of calculating the ring-opening rate is as described above.

Subsequently, in the compounding ratio (parts by mass) shown in Tables 1 to 3 below, the pre-reactant which is the component (B), the epoxy resin which is the component (A), and the curing agent which is the component (C) are added. A curing accelerator and a flame retardant are blended, diluted with a solvent (MEK or toluene) so that the solid content (non-solvent component) concentration is 60 to 80% by mass, and this is stirred and mixed with a varnish to make it uniform. The base varnish was prepared by dilution.

As for Comparative Examples, with respect to Comparative Examples 1, 2 and 7 having a preliminary reaction, a base varnish was prepared through the preliminary reaction in the same manner as in the above Examples. With respect to Comparative Examples 3 to 6 having no pre-reaction, the components in the component (B) were added without reacting (pre-reaction), and the base varnish was prepared in the same manner as above except for the above.

Next, other components (inorganic filler and silane coupling agent) were added to the base varnish at the blending ratios (parts by weight) shown in Tables 1 to 3 below, and this was mixed with a disper at room temperature for 2 hours. Stirred and mixed to homogenize. As a result, a resin composition obtained as a resin varnish was obtained.

[Remarks: Explanation of equivalent ratio]
The equivalent ratios listed in the “Remarks” column of Tables 1 to 3 will be supplementarily described. The equivalent ratio is determined based on the functional group (reactive group) that reacts.

The equivalent ratio of the reactive groups of the bifunctional polyphenylene ether compound in the component (B) to the monofunctional acid anhydride "PPE reactive group: acid anhydride reactive group in (B)" can be obtained as follows. Consider Example 1 as an example of equivalent calculation. Since the bifunctional PPE compound "MX90" has a molecular weight of 1600 and two hydroxyl groups (OH) per molecule, the phenol equivalent is 1600/2 = 800. The monofunctional acid anhydride group "Ricacid MH-700" has an acid anhydride group equivalent of 163.9. Therefore, in the composition of Example 1,
For MX90, 18.14 / 800 = 0.022
For MH-700, 3.72 / 163.9 = 0.022
As shown in Table 1, the equivalent ratio is 1: 1.

Further, the equivalent ratio of the reactive group of the component (A), the reactive group of the component (B), and the reactive group of the component (C) "the epoxy equivalent of (A): the total of the reactive groups of (B) and (C)" is , It is obtained as follows. Consider Example 2 as an example of equivalent calculation. In the epoxy resin of the component (A), the epoxy equivalent is used in the calculation of the equivalent of the reactive group. The epoxy equivalent of "HP-7200HHH" is 286g and the epoxy equivalent of "FX-289-P" is 390. In the epoxy resin curing agent "B-4500" as the component (C), since it is an acid anhydride, an acid anhydride group equivalent 132 is used. Further, the reactive groups of the component (B) are both ends of the bifunctional polyphenylene ether compound when the bifunctional polyphenylene ether compound in the component (B) and the monofunctional acid anhydride are reacted at an equivalent ratio of 1: 1. It can be considered that an acid anhydride is bound to. Then, the reaction group equivalent of the component (B) is calculated as (1600 + 164 + 164) / 2 = 964. Using the above information, in the composition of Example 2, in the component (A),
About HP-7200HHH 10.18 / 286 = 0.0356
About FX-289-P 49.5 / 390 = 0.1269
In the end, in the component (A), the amount of reactive groups is 0.1625, which is the sum of these.
In addition, in the component (C),
About B-4500 18.46 / 132 = 0.1398
Then, in the component (C), this value becomes the amount of the reactive group.
In addition, in the component (B),
The weight is the sum of the two components (18.14 + 3.72) / 964 = 0.0227.
After all, in the component (B), this value becomes the amount of the reactive group.
Therefore, the equivalent ratio of reactive groups is
0.1625: (0.0227 + 0.1398) = 1: 1
As shown in Table 1, the equivalent ratio is 1: 1.

By performing the above equivalent ratio calculation, the equivalent ratios of the other examples are also calculated in the same manner. In the calculation of the equivalent ratio, the values may be appropriately approximated by a method such as rounding.

[Prepreg]
A glass cloth (“7628 type cloth” manufactured by Nitto Boseki Co., Ltd.) was prepared as a base material. This base material is impregnated with the above resin varnish (resin composition), and this is heated and dried at 110 to 140 ° C. by a non-contact type heating unit to remove the solvent in the resin varnish, and the resin composition is half. It was cured. As a result, a prepreg was produced. The resin content (content of the resin composition) of the prepreg was 45 to 55% by mass with respect to the total amount of the prepreg.

The above drying conditions were adjusted so that the gel time of the prepreg was 40 to 60 seconds. The gel time is obtained by placing a resin varnish or a resin collected from a prepreg on a heat plate at 170 ° C. and measuring the time until it gels.

[Copper-clad laminate]
Two copper foils (manufactured by Mitsui Mining & Smelting Co., Ltd., thickness 35 μm, ST foil, one side roughened surface) were prepared. In addition, eight of the above prepregs (340 mm × 510 mm) were prepared. Next, eight prepregs were stacked, copper foils were laminated on both sides of the prepreg with the roughened surface inside, and the copper foil was heated and pressed to form a laminate. The conditions for heating and pressurizing are 180 ° C., 2.94 MPa, and 60 minutes. As a result, a copper-clad laminate was obtained. The thickness of the copper-clad laminate is 3.2 mm.

[Evaluation]
[Glass-transition temperature]
The copper foil was removed from the copper-clad laminate, and the glass transition temperature of this laminate (insulator) was measured using a viscoelastic spectrometer "DMS6100" manufactured by Seiko Instruments Co., Ltd. Specifically, the measurement was performed with the bending module at a frequency of 10 Hz, and the temperature at which tan α was maximized when the temperature was raised from room temperature to 280 ° C. under the condition of a temperature rising rate of 5 ° C./min was defined as the glass transition temperature.

[Relative permittivity (Dk)]
Using an "impedance / material analyzer 4291A" manufactured by Hewlett-Packard, the relative permittivity of the copper-clad laminate at 1 GHz was measured according to IPC-TM-650 2.5.5.9.

[Peel strength]
The peeling strength of the copper foil on the surface of the copper-clad laminate was measured according to JIS C 6481. That is, the copper foil was peeled off at a speed of about 50 mm per minute, and the peeling strength (kN / m) at that time was measured as the peel strength.

[Flame retardance]
Copper-clad laminates with plate thicknesses of 0.8 mm, 1.2 mm, and 1.6 mm were manufactured in the same manner as described above by adjusting the number of prepregs. After removing the copper foil on the surface of each copper-clad laminate by etching, a flame retardancy test was conducted according to "Test for Flammability of Plastic Materials-UL 94" of Underwriters Laboratories to evaluate the flame retardancy. Those satisfying V-0 were regarded as "OK", and those not satisfying V-0 were regarded as "NG". Tables 1 to 3 below show the plate thickness and whether or not the plate thickness satisfies V-0.

[Alkali resistance]
A copper-clad laminate having a plate thickness of 0.8 mm was produced by the same method as described above. After removing the copper foil on the surface of the copper-clad laminate by etching, it was immersed in a sodium hydroxide aqueous solution (10% by mass) at 70 ° C. for 30 minutes. Then, the weight loss rate was calculated from the weight before and after immersion. The results are divided as follows.
"A": Weight loss rate is 0% by mass or more and less than 0.2% by mass;
"B": Weight loss rate is 0.2% by mass or more and less than 0.3% by mass;
"C": Weight loss rate is 0.3% by mass or more and less than 0.4% by mass;
"D": Weight loss rate is 0.4% by mass or more.

The above results are shown in Tables 1 to 3.

As a guideline for the evaluation standard, it is good that the glass transition temperature (Tg) is 150 ° C. or higher. Further, it is good that the peel strength is 0.80 kN / m or more. Further, it is good that Dk is 3.4 or less. The flame retardancy is good when it is 0.8 mm or more and OK. Alkali resistance is good when the evaluation is "A", "B" and "C".

As is clear from Tables 1 to 3, the examples have a higher glass transition temperature, a lower dielectric constant, a higher peel strength, a generally higher flame retardancy, and an excellent alkali resistance as compared with the comparative examples. Was confirmed to be obtained in a well-balanced manner at a good level.

In Comparative Examples 2 and 7, the resin varnish caused phase separation. Although the components of Comparative Example 3 are the same as those of Example 1, the performance is inferior to that of Example 1 because the preliminary reaction has not been performed. In Comparative Example 5, the copper-clad laminate could not be manufactured. It is considered that this is because the monofunctional acid anhydride has volatilized.

1 prepreg 2 resin composition 3 base material 11 metal-clad laminate 12, 32 insulation layer 13 metal layer 14 wiring 21 printed wiring board 31 metal foil with resin 33 metal foil

Claims (12)

(A) Epoxy resin and
(B) A reaction product of a bifunctional polyphenylene ether compound and a monofunctional acid anhydride, which is a preliminary reaction product capable of reacting with an epoxy group.
(C) Containing a curing agent for epoxy resin,
When the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass, the content of the component (B) is 5 to 60 parts by mass.
The monofunctional acid anhydride of the component (B) contains at least one of 4-methylhexahydrophthalic anhydride or hexahydrophthalic anhydride.
The component (C) contains a polyfunctional acid anhydride.
Resin composition. The polyfunctional acid anhydride contains an alicyclic polyfunctional acid anhydride.
The resin composition according to claim 1. The amount of the acid anhydride group of the monofunctional acid anhydride of the component (B) is 1.5 equivalents or less when the amount of the hydroxyl group of the bifunctional polyphenylene ether compound is 1 equivalent.
The resin composition according to claim 1 or 2. When the amount of the epoxy group of the component (A) is 1 equivalent, the amount of the functional group that reacts with the epoxy group in the component (B) and the amount of the functional group that reacts with the epoxy group in the component (C). Is 0.8 to 1.2 equivalents,
The resin composition according to any one of claims 1 to 3. Further containing a phosphorus-containing flame retardant,
When the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass, the phosphorus content is 1 part by mass or more.
The resin composition according to any one of claims 1 to 4. Contains more inorganic filler,
When the total mass of the component (A), the component (B) and the component (C) is 100 parts by mass, the content of the inorganic filler is 5 to 50 parts by mass.
The resin composition according to any one of claims 1 to 5. The inorganic filler comprises an inorganic filler that has been treated with a surface treatment agent.
The resin composition according to claim 6. The inorganic filler treated with the surface treatment agent has a content of 1 to 10 parts by mass of the surface treatment agent when the content of the inorganic filler is 100 parts by mass.
The resin composition according to claim 7. The resin composition according to any one of claims 1 to 8.
It has a base material impregnated with the resin composition.
Prepreg . An insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8.
It has a metal layer in contact with the insulating layer.
Metal-clad laminate . An insulating layer containing a cured product of the resin composition according to any one of claims 1 to 8.
It has wiring provided on the surface of the insulating layer.
Printed wiring board . An insulating layer containing a semi-cured product of the resin composition according to any one of claims 1 to 8.
It has a metal foil in contact with the insulating layer.
Metal leaf with resin .

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