JP6573181B2 - Metal-clad laminate and packaging substrate material - Google Patents

Description

  The present invention relates to an epoxy resin composition preferably used in the field of electronic materials (particularly electronic circuit board materials), a metal-clad laminate using the epoxy resin composition, and a substrate material for packages.

  Epoxy resin compositions are widely used as printed wiring board materials because of their excellent adhesion, electrical insulation and chemical resistance.

  However, with recent miniaturization and higher performance of memories, higher transmission speeds are required. For this reason, the printed wiring board requires not only insulation reliability but also superior dielectric characteristics. On the other hand, it has been found that it is difficult to reduce the dielectric constant only with a material having a high dielectric constant such as an epoxy resin. Therefore, it is known to combine special techniques such as modified polyphenylene ether (PPO) and hollow filler (for example, Patent Document 1 or 2). In addition, a technique of blending an epoxy resin with a radical polymerization type thermosetting resin has been reported (Patent Document 3, etc.).

On the other hand, in general, brominated flame retardants, which are considered to be unfavorable in recent years, are used for printed wiring boards as described above. Under such circumstances, cyclic phenoxyphosphazene compounds are widely used as halogen-free phosphorus-based flame retardants in the field of electronic materials. In particular, liquid phosphazene compounds can provide stable varnish even when the amount added is increased. (For example, Patent Document 4).
JP 2004-269785 A JP-A-10-298407 JP 2008-133329 A JP 2009-235123 A

  However, materials such as PPO and hollow filler described in Patent Documents 1 and 2 are materials with high hurdles in terms of handleability and cost. Furthermore, there is a possibility that quality such as the substrate Tg and flame retardancy may be deteriorated. In addition, in a material in which a radical polymerization type thermosetting resin is blended with an epoxy resin as described in Patent Document 3, the radical polymerization type thermosetting resin has a lower dielectric constant than an epoxy resin. However, there are problems from the viewpoint of flame retardancy, peel strength, and Tg reduction of the substrate.

  On the other hand, the package material is required to be halogen-free, and halogen-free flame retardants mainly composed of phosphates are mainly used. However, such flame retardants have poor solubility and are difficult to use in a large amount in a resin system. However, the use of a liquid phosphazene compound described in Patent Document 4 solves such a problem, and flame retardants. It is a technology that can achieve varnish stability while having excellent properties. However, adding a large amount of a liquid flame retardant may cause a decrease in heat resistance, substrate Tg and elastic modulus depending on the amount of the flame retardant.

  For this reason, in order to improve flame retardancy, it is necessary to make the resin itself difficult to burn. Melamine cyanurate, a material that is sometimes used as a halogen-free flame retardant, is not compatible with radical polymerization systems and causes curing inhibition and local curing acceleration. I couldn't.

  The present invention has been made in view of such circumstances, and an epoxy resin composition having all of flame retardancy, high Tg, peel strength, and low dielectric constant, and a metal-clad laminate using the epoxy resin composition Etc. to be provided.

  Thus, as a result of intensive studies, the present inventors have found that the above problems can be solved by an epoxy resin composition having the following constitution, and have further completed the present invention based on such findings.

  That is, the epoxy resin according to one aspect of the present invention includes (A) a radical polymerizable monomer, (B) a radical polymerization initiator, (C) an epoxy resin, (D) a curing agent for curing the epoxy resin, And (E) an epoxy resin composition containing a liquid phosphorus-based flame retardant, wherein the resin component of the epoxy resin composition comprises the (A) radical polymerizable monomer, the (C) epoxy resin, and the (D And (A) the radically polymerizable monomer contains a monomer having a triazine ring skeleton and having two or more (meth) acrylic radical reactive groups.

  The epoxy resin composition preferably further contains (F) an inorganic filler.

  In the epoxy resin composition, it is more preferable that the (A) radical polymerizable monomer and the (C) epoxy resin do not contain a halogen molecule.

  In the epoxy resin composition, the radical polymerizable monomer (A) is preferably ε-caprolactone-modified.

  A metal-clad laminate relating to a further aspect of the present invention is obtained by impregnating a fiber base material with the above epoxy resin composition and laminating a metal foil on the base material.

  Moreover, the board | substrate material for packages regarding the further situation of this invention is comprised by the said metal-clad laminated board, It is characterized by the above-mentioned.

  According to the present invention, there are provided an epoxy resin composition balanced in all of flame retardancy, high Tg, peel strength, and low dielectric constant, and a metal-clad laminate and a packaging substrate material using the same. be able to.

FIG. 1 is a cross-sectional view showing an example of a metal-clad laminate according to an embodiment of the present invention.

  Hereinafter, although the embodiment concerning the present invention is described concretely, the present invention is not limited to these.

  The epoxy resin composition according to this embodiment includes (A) a radical polymerizable monomer, (B) a radical polymerization initiator, (C) an epoxy resin, (D) a curing agent for curing the epoxy resin, and (E ) An epoxy resin composition containing a liquid phosphorus flame retardant, wherein the resin component of the epoxy resin composition comprises the (A) radical polymerizable monomer, the (C) epoxy resin, and the (D) curing agent. The (A) radical polymerizable monomer contains a monomer having a triazine ring skeleton and having two or more (meth) acrylic radical reactive groups.

  With such a structure, it is considered that an epoxy resin composition having both flame retardancy, high Tg, and low dielectric constant can be obtained.

  Hereinafter, each component which the epoxy resin composition of this embodiment contains is demonstrated in detail.

(A) Radical Polymerization Monomer In the present embodiment, the radical polymerizable monomer contains a monomer having a triazine ring skeleton and having two or more (meth) acrylic radical reactive groups.

  Examples of such a monomer having a triazine ring skeleton and having two or more (meth) acrylic radical reactive groups include ethoxylated isocyanuric acid triacrylate (having a triazine ring and an acrylate or methacrylate type radical reaction). Monomer having three groups), isocyanuric acid ethylene oxide-modified tri (meth) acrylate, ethoxylated isocyanuric acid di (meth) acrylate, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, and the like can be suitably used. . By including such a monomer, the reactivity is improved, and it is considered that not only the Tg can be improved but also the flame retardancy can be improved.

  In addition, with respect to the three characteristics of low Tg, low peel strength, and flame retardancy, which have been a problem when including conventional radical polymerizable monomers, monomers having a triazine ring as described above are effective. It acts and can suppress the deterioration of these characteristics.

  Furthermore, it is more preferable to use the above-mentioned monomer modified with ε-caprolactone. By doing so, liquefaction can be facilitated (liquefaction is possible at normal temperature), and varnish stability can be improved. .

  The radical polymerizable monomer of the present embodiment contains other radical polymerizable monomers in addition to the monomer having the triazine ring skeleton as described above and having two or more (meth) acrylic radical reactive groups. It is preferable. Examples of other radical polymerizable monomers include diallyl phthalate, styrene, methyl styrene, halogenated styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, divinylbenzene, Vinyl naphthalene, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dicyclopentadiene, etc. 1 type or 2 types or more of these are used. Among these, styrene-based, divinylbenzene-based, acrylic-based, methacryl-based, dicyclopentadiene-based and the like having a dielectric constant of about 2 to 3 are particularly preferably used because of their excellent low dielectric properties. As more specific examples, for example, styrene, divinylbenzene, vinylnaphthalene, dicyclopentadiene type acrylic (methacrylic) monomer and the like can be preferably cited.

  In addition, it is preferable that the radically polymerizable monomer of this embodiment does not contain triallyl isocyanurate (TAIC). This is because the reactivity (reaction speed) with the (meth) acrylic monomer is different, and it is difficult to obtain an appropriately mixed copolymer, which may cause problems such as a decrease in Tg and a decrease in heat resistance. Because.

  The compounding amount of the radically polymerizable monomer in the resin composition of the present embodiment usually has a triazine ring skeleton when the resin component obtained by summing the later-described epoxy resin and radically polymerizable monomer is 100 parts by mass, And it is preferable to set it as about 20-75 mass parts as a monomer component which has two or more (meth) acrylic-type radical reactive groups, and other monomer components.

  Since only the triazine ring skeleton monomer may not provide good dielectric properties, it is desirable to use another monomer having excellent dielectric properties for the base resin.

  If the amount of the monomer having a triazine ring skeleton and having two or more (meth) acrylic radical reactive groups is less than 5 parts by mass, sufficient flame retardancy may not be obtained. Moreover, when it exceeds 30 mass parts, there exists a possibility that a dielectric characteristic may deteriorate. On the other hand, if the other monomer component is less than 20 parts by mass, the reactivity is low and sufficient reaction heat cannot be obtained, and Tg may decrease. Moreover, when it exceeds 70 mass parts, it will become very brittle as resin and there exists a possibility that workability may fall and a flame retardance may fall.

  Furthermore, it is preferable that 50% by mass or more of the radically polymerizable monomer of the component (A) is an acrylate monomer, and it is considered that a varnish superior in rapid reactivity can be obtained thereby. In addition, it is preferable that the (A) radical polymerizable monomer does not contain a halogen molecule from the viewpoint of obtaining a halogen-free material.

(B) Radical polymerization initiator A radical polymerization initiator is mix | blended in order to start hardening reaction of a radically polymerizable monomer.

  Specific examples of the radical polymerization initiator include, for example, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as benzoyl peroxide and isobutyl peroxide, and cumene hydroperoxide. , Hydroperoxides such as t-butyl hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1- Peroxyketals such as di-t-butylperoxy-3,3,5-trimethylcyclohexanone, 2,2-di- (t-butylperoxy) -butane, t-butylperbenzoate, t-butylperoxy -2-ethylhe Organic peroxides such as alkyl peresters such as sanoate, percarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisobutyl carbonate, and inorganic oxidation such as hydrogen peroxide Things. These may be used alone or in combination of two or more.

  Although it does not restrict | limit especially as a compounding quantity of a radical polymerization initiator, About 0.2-2 mass parts with respect to 100 mass parts of radically polymerizable monomers, More preferably, it is 0.5-1.0 mass. It is preferable that it is about a part.

(C) Epoxy resin The epoxy resin used in the present embodiment is not particularly limited, and specific examples include, for example, novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, glycidyl esters, and glycidyl amines. And heterocyclic epoxy resins.

  Specific examples of the novolak type epoxy resin include naphthalene type novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, and the like. Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Specific examples of the alicyclic epoxy resin include 3,4-epoxy-6-methyl. Cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4- Specific examples of glycidyl esters include diglycidyl phthalate, diglycidyl tetrahydrophthalate, and glycidyl dimer, and specific examples of glycidyl amines include tetraglycidyl diamino. Examples include diphenylmethane, triglycidyl P-aminophenol, N, N-diglycidylaniline, and specific examples of the heterocyclic epoxy resin include 1,3-diglycidyl-5,5-dimethylhydantoin, triglycidyl isocyanurate, and the like. Is mentioned.

  Of these, dicyclopentadiene-based, naphthalene-based novolak-type epoxy resins and the like are preferably used because they are excellent in high Tg and low dielectric properties. In addition, by making the main skeleton of the epoxy resin the same as the above-mentioned radical polymerizable monomer, the compatibility is improved, the varnish stability is improved, and the Tg of the cured resin is improved by the effect of IPN (Interpenetrating Polymer Network). It is thought that the peel strength can be improved. Moreover, it is preferable that (C) epoxy resin does not contain a halogen molecule from the viewpoint of obtaining a halogen-free material.

  In general, the amount of the epoxy resin is preferably about 20 to 50 parts by mass when the resin component totaled with the above-mentioned radical polymerizable monomer is 100 parts by mass. When the epoxy resin is 40 to 50 parts by mass, the peel strength is strong, and when it is 20 to 30 parts by mass, the dielectric characteristics are improved.

  Moreover, the compounding ratio of the said epoxy resin and the said radically polymerizable monomer is 20: 80-80: 20 normally, Preferably it is 25: 75-35: 65. If the blending ratio of the epoxy resin and the radical polymerizable monomer is within the above range, the blended varnish shows stable characteristics, maintains the high Tg of epoxy and the low dielectric characteristics of the radical polymerizable monomer, and is flame retardant. An excellent cured resin can be obtained.

(D) Curing agent for epoxy resin The epoxy resin usually contains a curing agent for curing the epoxy resin.

  As a specific example of the curing agent, imidazoles are preferably used in terms of excellent reactivity with the epoxy resin. Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and the like. It is done.

  Although it does not restrict | limit especially as a compounding quantity of a hardening | curing agent, It is preferable to mix | blend in the range of 0.5-5 by an epoxy equivalent ratio with respect to the quantity of an epoxy resin.

(E) Liquid phosphorus flame retardant The epoxy resin composition of the present embodiment further contains a liquid phosphorus flame retardant.

  Although the liquid phosphorus flame retardant used in the present embodiment is not particularly limited, for example, a liquid phosphazene compound is preferably used. By doing so, when mixing a flame retardant with resin or a solvent, the solubility of a flame retardant rises and by extension, stability of the varnish of a resin composition can be acquired. Moreover, it is thought that by using an appropriate amount of the liquid phosphazene compound, it is possible to obtain a well-balanced epoxy resin composition having both flame retardancy and low dielectric constant.

  In the epoxy resin composition of the present embodiment, the content of the flame retardant (phosphazene compound) is preferably 25 to 35 parts by mass, more preferably 26 to 30 parts by mass with respect to 100 parts by mass of the resin component. If the content of the flame retardant (phosphazene compound) is 25 parts by mass or more with respect to 100 parts by mass of the resin component, sufficient flame retardancy can be ensured by blending. Moreover, it is preferable to set it as 35 mass parts or less from a viewpoint of ensuring the elasticity modulus of resin cured material.

  As a more specific example, in this embodiment, a cyclic phenoxyphosphazene compound that is liquid at room temperature represented by the following general formula (I) can be used as a flame retardant.

（式中、ｍは３〜２５の整数、Ｒはそれぞれ独立して、フェノキシ基、式（ＩＩ）：

(Wherein, m is an integer of 3 to 25, R is each independently a phenoxy group, formula (II):

で表される基、式（ＩＩＩ）：

A group represented by formula (III):

で表される基、式（ＩＶ）：

A group represented by formula (IV):

で表される基から選ばれる基であり、Ｒ基の個数の３３〜６６％が式（ＩＩ）、式（ＩＩＩ）、及び式（ＩＶ）から選ばれる何れかの基である）。

And 33 to 66% of the number of R groups is any group selected from formula (II), formula (III), and formula (IV)).

  In the cyclic phenoxyphosphazene compound represented by the general formula (I), 33 to 66% of all phenoxy groups in the cyclic phenoxyphosphazene is selected from the above formula (II), formula (III), and formula (IV). A liquid cyclic phenoxyphosphazene compound substituted with a group. Since such a liquid cyclic phosphazene compound has high compatibility with a resin component and a solvent in the varnish, it is considered that a resin composition having high varnish stability can be obtained.

  In such a liquid cyclic phenoxyphosphazene compound, 33 to 66% of all phenoxy groups of the cyclic phenoxyphosphazene compound are replaced with any group selected from formula (II), formula (III), and formula (IV). Can be obtained.

  When 33 to 66% of the R group is substituted with any group represented by the formula (II), the formula (III), or the formula (IV), it is liquid at room temperature. On the other hand, when the R group is less than 16% and exceeds 83%, the cyclic phenoxyphosphazene compound has high crystallinity and becomes a solid at room temperature. Therefore, by converting 33 to 66% of the R group of the cyclic phenoxyphosphazene compound represented by the general formula (I) to any group selected from the formula (II), the formula (III), and the formula (IV) A cyclic phenoxyphosphazene compound that is liquid at room temperature is obtained.

  In addition, the substitution ratio of the R group in the cyclic phenoxyphosphazene compound can be measured by elemental analysis.

  Such a cyclic phenoxyphosphazene compound represented by the general formula (I) is obtained by reacting a phenol compounded in a predetermined molar ratio and various substituted phenols with sodium hydroxide as shown in Scheme 1 described later. Sodium phenolate and various substituted sodium phenolates are obtained, and the obtained sodium phenolate and various substituted sodium phenolates are mixed with hexachlorocyclotriphosphazene in a solvent such as toluene at a predetermined temperature condition, for example, 80 to 120. It can be obtained by reacting in a temperature range of about 0 ° C. for a predetermined time, for example, 4 to 12 hours.

  In the general formula (I), an example of a reaction scheme when m = 3 is shown below. In addition, although the following reaction scheme showed as a typical example the case where three of R groups were substituted by any group chosen from Formula (II), Formula (III), and Formula (IV), sodium phenolate The number and type of R groups to be substituted can be adjusted by adjusting the molar ratio between and the substituted sodium phenolate.

(Scheme 1)

（スキーム１及びスキーム２中、Ｒｘは−ＯＣＨ_２ＣＨ_２ＯＣＯＣＯＣＨ_３、−ＯＣＮ、−ＣＨ_３の何れかの基）。 (Scheme 2)

(In Schemes 1 and 2, Rx is _{-OCH 2 CH 2 OCOCOCH 3, -OCN} , any of the groups -CH _3).

(F) Inorganic filler Although the resin composition of this embodiment contains the said (A)-(E) component as an essential structure, it is preferable to contain the inorganic filler other than that. The inorganic filler used in the present embodiment is not particularly limited, but is selected from the group consisting of silica compounds such as fused silica, crushed silica and spherical silica, metal hydroxides such as aluminum hydroxide, nickel, iron, cobalt and chromium. A composite metal oxide containing at least two kinds of metal elements can be used. In particular, by using fused silica as an inorganic filler, the elastic modulus of the cured resin can be improved. Furthermore, it is desirable to use spherical fused silica from the viewpoint of varnish stability. Moreover, aluminum hydroxide etc. can be used conveniently from a flame-retardant viewpoint.

  The average particle size of the fused silica is not particularly limited, but is about 0.1 to 20.0 μm, preferably about 0.5 to 5.0 μm. More preferably, if two or more types of fused silica having different average particle diameters are used, it is considered that the filling rate of the inorganic filler can be increased without excessively increasing the viscosity of the resin.

  It is preferable that an inorganic filler is contained in 10-100 mass parts with respect to 100 mass parts of resin components as mentioned above. If the content of the inorganic filler is 30 parts by mass or more with respect to 100 parts by mass of the resin component, a cured resin product having excellent elastic modulus and flame retardancy can be obtained. Stability can be secured and a cured resin product having excellent dielectric properties can be obtained.

  In a more preferred embodiment, the inorganic filler preferably contains 10 to 40 parts by mass of fused silica and 5 to 15 parts by mass of aluminum hydroxide with respect to 100 parts by mass of the resin component. This is because the three properties of the obtained resin cured product, ie, dielectric properties, flame retardancy, and elastic modulus can be secured in a well-balanced manner.

(Other additives)
In the epoxy resin composition of the present embodiment, as components other than those described above, additives such as a flame retardant aid, a flow modifier, a lubricant, a silane coupling agent, a colorant, and the like, as long as the object of the present invention is not impaired. May be added as necessary.

(Production method)
The epoxy resin composition of the present embodiment can be obtained by mixing the above components. In addition, when using liquid resin at normal temperature as a resin component, a liquid phosphazene compound can be easily dissolved in the said liquid resin component at the said normal temperature by using a liquid phosphazene compound. Moreover, when using resin solid at normal temperature as a resin component, it can be used by making it dissolve in there as a radical polymerizable monomer as mentioned above. Also in this case, if the phosphazene compound is liquid, it can be easily dissolved in a solvent.

The epoxy resin composition of the present embodiment thus obtained has a high flame retarding effect, a low dielectric constant, and excellent Tg. Therefore, the epoxy resin composition of the present invention is cured. The obtained cured product can realize a low dielectric constant of the resin solid material while maintaining high Tg, peel strength, and flame retardance, which have been difficult to achieve at the same time. Therefore, an electronic material that requires high-frequency characteristics or the like, specifically, impregnating the fiber base material with the resin composition, and at least one of the base material
It is preferably used for a metal-clad laminate obtained by laminating a metal foil on the surface, a package substrate material composed of the metal-clad laminate, and various molding materials.

(Metal-clad laminates and packaging substrate materials)
Next, a metal-clad laminate using the epoxy resin composition will be described.

  In the metal-clad laminate according to the present embodiment, a fiber base material is impregnated with the above epoxy resin composition, a metal foil is laminated on at least one surface of the base material, and heated or heated and pressed as necessary. Can be obtained.

  The fiber base material impregnated with the epoxy resin composition (varnish) is not particularly limited, whether it is a woven fabric base material or a non-woven fabric base material. However, since the difference in dielectric constant between the materials (resin and fiber) is small, low dielectric constant It is preferred to use a substrate of a rate. As a result, the frequency dependence of the dielectric constant can be reduced, which is advantageous because the difference between the relative dielectric constant at 1 GHz and the relative dielectric constant at 10 GHz is considered to be small. Specifically, a glass fiber substrate having a low dielectric constant can be mentioned.

  As such a glass fiber base material, a commercially available product can be used. For example, NE glass (manufactured by Nitto Boseki Co., Ltd.) or L glass (Asahi Kasei E-material) having a relative dielectric constant lower than that of general E glass. As a specific example, it may be mentioned.

  The thickness of the fiber base material used in the present embodiment is not particularly limited, and is, for example, about 50 to 80 μm.

  FIG. 1 is a schematic cross-sectional view showing an example of a metal-clad laminate 4 according to this embodiment. Specifically, as the metal-clad laminate 4 according to the present embodiment, for example, as shown in FIG. 1, the metal layer 1 is provided on the surface on which the resin layer 2 and the glass fiber substrate 3 are laminated. Is mentioned.

  The method for producing the copper clad laminate according to the present embodiment is not particularly limited. For example, the step of impregnating the base material with the thermosetting resin composition for copper clad laminate and the resin composition are impregnated. A step of bonding a copper foil to at least one surface of the substrate and a step of curing the resin composition.

  Specifically, for example, from the substrate roll wound with the substrate as described above, the substrate is continuously supplied to the coating step, and the varnish-like resin composition is applied to the glass substrate. Impregnation, a copper foil is bonded to the surface of the base material impregnated with resin, and the resin component is cured. Curing can be performed by heating or heating and pressing.

  In addition, since the radical polymerization type thermosetting monomer in the resin composition undergoes radical polymerization, the curability decreases due to contact with oxygen. Therefore, when copper foil is pasted on both sides, or when copper foil is pasted on only one side, it is possible to suppress contact with air by pasting a film such as a PET film on the other side. preferable.

  According to such a manufacturing method, since each said process can be performed continuously, there exists an advantage that the continuous production of a copper clad laminated board is attained.

  Further, the present embodiment includes a package substrate material composed of the metal-clad laminate.

  Various molding materials such as the metal-clad laminate or the packaging substrate material obtained in this way have high flame retardancy, low dielectric constant, peel strength and high Tg, as described above, so that electronic materials As excellent and very useful.

  As described above, the present specification discloses various modes of technology, of which the main technologies are summarized below.

  The epoxy resin according to one aspect of the present invention includes (A) a radical polymerizable monomer, (B) a radical polymerization initiator, (C) an epoxy resin, (D) a curing agent for curing the epoxy resin, and ( E) An epoxy resin composition containing a liquid phosphorus flame retardant, wherein the resin component of the epoxy resin composition is the (A) radical polymerizable monomer, the (C) epoxy resin, and the (D) curing. And (A) the radical polymerizable monomer contains a monomer having a triazine ring skeleton and having two or more (meth) acrylic radical reactive groups.

  With such a configuration, an epoxy resin composition having a high flame retarding effect, a low dielectric constant, and excellent peel strength and Tg can be obtained.

  The epoxy resin composition preferably further contains (F) an inorganic filler. Thereby, there is an advantage that necessary rigidity is obtained as a substrate characteristic and workability is improved, and an advantage that flame retardancy is improved.

  Moreover, in the said epoxy resin composition, it is preferable that the said (A) radically polymerizable monomer and the said (C) epoxy resin do not contain a halogen molecule. Thereby, an environmentally friendly halogen-free material can be provided.

  Furthermore, in the epoxy resin composition, it is preferable that the (A) radical polymerizable monomer is ε-caprolactone-modified. Thereby, liquefaction of the resin composition is facilitated, and varnish stability is considered to be further improved.

  A metal-clad laminate relating to a further aspect of the present invention is obtained by impregnating a fiber base material with the above epoxy resin composition and laminating a metal foil on the base material. With such a configuration, a metal-clad laminate having high flame retardancy, low dielectric constant, peel strength and high Tg can be obtained.

  Moreover, the board | substrate material for packages regarding the further situation of this invention is comprised by the said metal-clad laminated board, It is characterized by the above-mentioned. With such a configuration, a packaging substrate material having high flame retardancy, low dielectric constant, peel strength and high Tg can be obtained.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by the following Example.

First, the raw materials used in this example are shown together.
(A) Radical polymerizable monomer / ethoxylated isocyanuric acid triacrylate (monomer having a triazine ring and three (meth) acrylic radical reactive groups, trade name A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.)
Ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (ε-caprolactone-modified monomer having a triazine ring and three (meth) acrylic radical reactive groups, Shin-Nakamura Chemical Co., Ltd. Product name A-9300-1CL)
・ Dicyclopentadiene-based (meth) acrylate (trade name DCP, A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd.)
・ Styrene (trade name styrene monomer manufactured by NS Styrene Monomer Co., Ltd.)
・ Triallyl isocyanurate (trade name TAIC manufactured by Nippon Kasei Co., Ltd.)
(B) Radical polymerization initiator cumene hydroperoxide (CHP) (trade name Park Mill H-80, manufactured by NOF Corporation)
・ 1,1-bis (t-hexylperoxy) cyclohexane (trade name Perhexa HC, manufactured by NOF Corporation)
(C) Epoxy resin / dicyclopentadiene type novolac type epoxy resin (trade names HP-4700H, HP-4700HHH manufactured by DIC Corporation)
・ Naphthalene type novolac type epoxy resin (trade name HP-9900, HP-9500 manufactured by DIC Corporation)
(D) Epoxy resin curing agent / imidazole (trade names 2E4MZ, 2E4MZ-CN, manufactured by Shikoku Kasei Co., Ltd.)
(E) Phosphorus flame retardant / liquid phosphazene: Liquid phosphazene compound in which m = 3 or more in the general formula (I) and 33 to 66% of all phenoxy groups are substituted with the group of the formula (IV) (Brand name FP-390 manufactured by Fushimi Pharmaceutical Co., Ltd.)
Solid phosphinate (OP935 from Clariant)
(F) Inorganic filler / fused silica: Ultrafine silica filler (trade name SFP-130MC manufactured by Denki Kagaku Kogyo Co., Ltd.) Average particle size 0.5 μm
Aluminum hydroxide: (trade name CL-303, manufactured by Sumitomo Chemical Co., Ltd.) Average particle size: 4.0 μm

(Examples 1-10 and Comparative Examples 1-2)
Mixing ratio shown in Table 1 (Numerical values in the table represent parts by mass. In addition, the resin component (monomer and epoxy resin) is the compounding amount when the resin component is 100 parts by mass, and includes epoxy curing agent and radical. The blending amount of the polymerization initiator, inorganic filler and phosphorus flame retardant indicates the blending amount when the resin component is 100 parts by mass). Each material is weighed in a container, stirred with a disper, and then used with a bead mill. By uniformly mixing, a liquid epoxy resin composition (varnish) was obtained. And the obtained resin composition of each Example and a comparative example was used for the following evaluation tests.

[Varnish stability evaluation]
200 g of the obtained varnish was weighed into a glass container, and changes such as separation and gelation of the resin when left at 30 ° C. were visually observed and evaluated according to the following criteria.
A: No change was observed for more than 1 week, and it was stable.
◯: Resin gelation or separation was observed within 3 days to 1 week.
X: Gelation or separation of the resin was observed within 3 days.

[Flame retardance evaluation]
Next, on a copper foil (JTCS18 (trade name), manufactured by JX Nippon Mining & Metals Co., Ltd.), a glass cloth (L glass, manufactured by Asahi Kasei E-Materials Co., Ltd., thickness 0.075 μm) is stacked, About 100 parts by mass of glass cloth was impregnated with about 150 parts by mass of a liquid epoxy resin composition (obtained from Examples and Comparative Examples, respectively). And copper foil was further arranged on the upper surface, and it put into oven and hardened the resin component, and obtained the copper clad laminated board.

  And after peeling the copper foil of the surface of the obtained copper clad laminated board, combustibility was evaluated according to the combustibility test of UL94 (0.2t).

[Glass transition temperature (Tg)]
Tg of the copper-clad laminate obtained above was measured using a viscoelastic spectrometer “DMS100” manufactured by Seiko Instruments Inc. At this time, dynamic viscoelasticity measurement (DMA) was performed with a tension module at a frequency of 10 Hz, and the temperature at which tan δ was maximized when the temperature was raised from room temperature to 320 ° C. at a temperature increase rate of 5 ° C./min was Tg. did.

[Dielectric properties (dielectric constant (Dk) and dielectric loss tangent (Df))]
The dielectric constant and dielectric loss tangent of each evaluation board (copper-clad laminate obtained above) at 1 GHz and 10 GHz were measured by a cavity resonator perturbation method. Specifically, the dielectric constant and dielectric loss tangent of the evaluation substrate at 1 GHz were measured using a network analyzer (N5230A manufactured by Agilent Technologies).

[Peel strength]
According to JIS C 6481. Measured by autograph. Specifically, peel the minimum value of load when copper foil with a length of 100 mm and a width of 10 ± 0.1 mm is processed and peeled off continuously at a speed of about 50 mm per minute. Measured as strength. The unit is expressed in kN / m.

  The above evaluation results are shown in Table 1.

  The epoxy resin compositions obtained in Examples 1 to 10 according to the present invention all had flame retardancy at V-0 or V-1 level, and were excellent in varnish stability. In addition, the Tg of 220 ° C or higher was achieved with a curing time of about 30 minutes, and the low dielectric constant of the resin solids while maintaining the high Tg, peel strength, and flame retardance that had been difficult to achieve at the same time. It was confirmed that it can be realized.

  In particular, when ε-caprolactone-modified monomers were used as in Examples 2, 4 and 6, the varnish stability was very excellent.

  In contrast, in Comparative Example 1 in which TAIC was contained instead of containing a monomer having a triazine ring skeleton and having two or more (meth) acrylic radical reactive groups, the varnish stability was inferior. The peel strength was also low.

  Moreover, in the comparative example 2 which contained solid phosphazene instead of liquid phosphazene, it was inferior to varnish stability and peel strength was not obtained.

1 Copper foil 2 Resin layer 3 Glass cloth 4 Metal-clad laminate

Claims (5)

(A) radical polymerizable monomer, (B) radical polymerization initiator, (C) epoxy resin, (D) a curing agent for curing the epoxy resin, and (E) an epoxy containing a liquid phosphorus flame retardant A resin composition comprising:
The resin component of the epoxy resin composition is composed of the (A) radical polymerizable monomer, the (C) epoxy resin, and the (D) curing agent,
Wherein the (A) radical-polymerizable monomer having a triazine ring skeleton, and (meth) containing a monomer having two or more acrylic radical reactive group, the epoxy resin composition impregnated into the fiber base material, the base A metal-clad laminate obtained by laminating a metal foil on at least one surface of a material . The metal-clad laminate according to claim 1, wherein the epoxy resin composition further contains (F) an inorganic filler. 3. The metal-clad laminate according to claim 1, wherein in the epoxy resin composition, the (A) radical polymerizable monomer and the (C) epoxy resin do not contain a halogen molecule. The metal-clad laminate according to any one of claims 1 to 3, wherein in the epoxy resin composition, the radically polymerizable monomer (A) is ε-caprolactone-modified. The board | substrate material for packages comprised with the metal-clad laminated board in any one of Claims 1-4 .

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