JP2014148562A - Curable resin composition, film, prepreg, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition that gives a cured product having low linear expansion and excellent electric characteristics and heat resistance.SOLUTION: The curable resin composition comprises a polyfunctional epoxy compound (A), an active ester compound (B), a benzoxazine compound (C), and a filler (D), in which a ratio of phenolic hydroxyl groups in the benzoxazine compound (C) to active ester groups of the active ester compound (B) is 0.3 to 0.9 in terms of an equivalent ratio of (phenolic hydroxyl groups)/(active ester groups).

Description

  The present invention relates to a curable resin composition, a film, a prepreg, and a cured product.

  With the pursuit of downsizing, multi-functionalization, high-speed communication, etc. of electronic devices, there is a need for higher density circuit boards used in electronic devices. To meet such demands for higher density, Circuit boards are being made multilayered. In such a multilayer circuit board, for example, an electrical insulation layer is laminated on an inner layer substrate composed of an electrical insulation layer and a conductor layer formed on the surface thereof, and a conductor layer is formed on the electrical insulation layer. Further, it is formed by repeatedly stacking these electrical insulating layers and forming the conductor layer.

  As a material for constituting such an electrical insulating layer of the multilayer circuit board, a ceramic or a thermosetting resin is generally used. Among these, epoxy resins as thermosetting resins are widely used because they are excellent in terms of balance between economy and performance.

  As an epoxy resin material for constituting such an electrical insulating layer, for example, Patent Document 1 discloses an epoxy resin, an epoxy curing agent, a phenoxy resin and / or a polyvinyl acetal resin, and a resin containing a phosphorus-containing benzoxazine compound. A composition is disclosed.

International Publication No. 2009/038166

  However, when the present inventors examined, when the insulating resin layer of the printed circuit board for electronic materials was formed using the resin composition of patent document 1 mentioned above, the linear expansion coefficient (especially high temperature) of a resin layer was formed. It has become clear that there is a problem that the linear expansion coefficient on the side is large and the deformation of the laminated substrate becomes large.

  An object of the present invention is to provide a curable resin composition that gives a cured product having low linear expansion and excellent electrical characteristics and heat resistance, and a film, a prepreg, and a cured product obtained using the same. .

  As a result of diligent research to achieve the above object, the present inventors contain a polyfunctional epoxy compound, an active ester compound, a benzoxazine compound, and a filler, and the blending ratio of the benzoxazine compound to the polyfunctional epoxy compound is The present inventors have found that a resin composition controlled within a predetermined range can provide a cured product having low linear expansion and excellent electrical characteristics and heat resistance, and has completed the present invention.

That is, according to the present invention,
[1] A polyfunctional epoxy compound (A), an active ester compound (B), a benzoxazine compound (C), and a filler (D), and an active ester group of the active ester compound (B); The ratio of the benzoxazine compound (C) to the phenolic hydroxyl group is a curable resin composition having an equivalent ratio of “phenolic hydroxyl group / active ester group” of 0.3 to 0.9,
[2] The ratio of the epoxy group of the polyfunctional epoxy compound (A), the active ester group of the active ester compound (B), and the phenolic hydroxyl group of the benzoxazine compound (C) is “(active ester group) + Phenolic hydroxyl group) / epoxy group "in an equivalent ratio of 1.0 to 2.0, the curable resin composition according to [1] above,
[3] The curable resin composition according to [1] or [2], wherein a content ratio of the benzoxazine compound (C) is 38 to 85 parts by weight with respect to 100 parts by weight of the polyfunctional epoxy compound (A). ,
[4] A film comprising the resin composition according to any one of [1] to [3],
[5] A prepreg formed by impregnating a fiber base material with the curable resin composition according to any one of [1] to [3], and
[6] The resin composition according to any one of [1] to [3], the film according to [4], or the cured product obtained by curing the prepreg according to [5],
Is provided.

  According to the present invention, the curable resin composition has a low linear expansion (particularly, the linear expansion coefficient is kept low even at high temperatures), and gives a cured product excellent in electrical characteristics and heat resistance, and A film, a prepreg, and a cured product obtained using the same are provided.

  The curable resin composition of the present invention contains a polyfunctional epoxy compound (A), an active ester compound (B), a benzoxazine compound (C), and a filler (D), and the active ester compound (B ) And the phenolic hydroxyl group of the benzoxazine compound (C) is an equivalent ratio of “phenolic hydroxyl group / active ester group” of 0.3 to 0.9. .

(Polyfunctional epoxy compound (A))
The polyfunctional epoxy compound (A) used in the present invention is not particularly limited as long as it has two or more epoxy groups.

  Examples of the polyfunctional epoxy compound (A) include phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, cresol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, polyphenol type epoxy compounds, and brominated bisphenol A. Type epoxy compounds, brominated bisphenol F type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, etc. glycidyl ether type epoxy compounds, alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, isocyanurate type epoxy compounds And an epoxy compound having an alicyclic olefin structure or a fluorene structure. Among these, bisphenol A type epoxy compound, polyphenol type epoxy compound, and alicyclic type from the point that the mechanical properties of the obtained film, multilayer film, prepreg, laminate and cured product can be improved. Epoxy compounds having an olefin structure or a fluorene structure are preferred. Furthermore, the epoxy compound which has an alicyclic olefin structure from the point which makes the resin fluidity | liquidity of a resin composition favorable is especially preferable. In addition, these may be used individually by 1 type and may use 2 or more types together.

  As the bisphenol A type epoxy compound, for example, trade names “jER827, jER828, jER828EL, jER828XA, jER834” (manufactured by Mitsubishi Chemical Corporation), trade names “Epicron 840, Epicron 840-S, Epicron 850, Epicron 850-S”. , Epicron 850-LC ”(manufactured by DIC,“ Epicron ”is a registered trademark), and the like. As a polyphenol type epoxy compound, a brand name "1032H60, XY-4000" (above, Mitsubishi Chemical Corporation make) etc. are mentioned, for example. As an epoxy compound having an alicyclic olefin structure or a fluorene structure, an epoxy compound having a dicyclopentadiene skeleton [for example, trade names “Epicron HP7200L, Epicron HP7200, Epicron HP7200H, Epicron HP7200HH, Epicron HP7200HHH” (above, manufactured by DIC Corporation) ); Trade name “Tactix 558” (manufactured by Huntsman Advanced Materials); trade names “XD-1000-1L, XD-1000-2L” (manufactured by Nippon Kayaku Co., Ltd.)] and epoxy compounds having a fluorene skeleton [For example, the product names “ONCOAT EX-1010, ONCOAT EX-1011, ONCOAT EX-1012, ONCOAT EX-1020, ONCOAT EX-1030, ONCOAT EX-1040, ONCOA EX-1050, ONCOAT EX-1051 "(manufactured by Nagase ChemteX Corporation," ONCOAT "is a registered trademark); trade name" Ogsol PG-100, Ogsol EG-200, Ogsol EG-250) "(above, Osaka Gas Chemical Co., Ltd., “Ogsol” is a registered trademark)] and the like. In addition to these, liquid polyfunctional epoxy compounds [for example, trade names “Denacol EX-711, Denacol EX-721, Denacol EX-810, Denacol EX-811, Denacol EX-821, Denacol EX-830, Denacol EX-851 "(Nagase ChemteX Corporation," Denacol "is a registered trademark); trade name" Epolide GT401 "(above, Daicel Chemical Industries," Epolide "is a registered trademark)) can be used. .

(Active ester compound (B))
The active ester compound (B) used in the present invention may be any compound having an active ester group, but in the present invention, a compound having at least two active ester groups in the molecule is preferable. The active ester compound (B) acts as a curing agent for the epoxy compound (A) by the action of the active ester group.

  The active ester compound (B) is preferably an active ester compound obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound from the viewpoint of heat resistance and the like. An active ester compound obtained by reacting an acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound, and a thiol compound is more preferable, and among them, a carboxylic acid compound and a phenolic compound are preferred. An aromatic compound obtained from a reaction with an aromatic compound having a hydroxyl group and having at least two active ester groups in the molecule is particularly preferred. The active ester compound (B) may be linear or multi-branched. For example, the active ester compound (B) is derived from a compound having at least two carboxylic acids in the molecule. When the compound having at least two carboxylic acids in the molecule contains an aliphatic chain, the compatibility with the epoxy resin can be increased, and when it has an aromatic ring, the heat resistance is improved. Can be high.

  Specific examples of the carboxylic acid compound for forming the active ester compound (B) include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like. . Among these, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred, phthalic acid, isophthalic acid and terephthalic acid are more preferred, and isophthalic acid and terephthalic acid are further preferred. preferable.

  Specific examples of the thiocarboxylic acid compound for forming the active ester compound (B) include thioacetic acid and thiobenzoic acid.

  Specific examples of the phenol compound and naphthol compound for forming the active ester compound (B) include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, and methyl. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxy Benzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, phenol novolac, etc. The Among these, from the viewpoint of heat resistance and solubility, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl Diphenol and phenol novolak are preferable, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolak are more preferable, and dicyclopentadienyl diphenol and phenol novolak are more preferable.

  Specific examples of the thiol compound for forming the active ester compound (B) include benzenedithiol and triazinedithiol.

  In the present invention, as the active ester compound (B), for example, active ester compounds disclosed in JP-A Nos. 2002-12650 and 2004-277460, or commercially available products can be used. Examples of commercially available active ester compounds include trade names “EXB9451, EXB9460, EXB9460S, HPC-8000-65T” (manufactured by DIC), trade names “DC808” (manufactured by Japan Epoxy Resins), trade names, and the like. “YLH1026” (manufactured by Japan Epoxy Resin Co., Ltd.) and the like can be mentioned.

  The production method of the active ester compound (B) is not particularly limited, and can be produced by a known method. For example, by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Can be obtained.

  The compounding amount of the active ester compound (B) in the curable resin composition of the present invention is preferably 20 to 120 parts by weight, more preferably 40 to 100 parts per 100 parts by weight of the polyfunctional epoxy compound (A). Part by weight, more preferably in the range of 50 to 90 parts by weight. By making the compounding quantity of an active ester compound (B) into the said range, the electrical property as a hardened | cured material, low heat property, and a linear expansion coefficient can be improved.

(Benzoxazine compound (C))
The benzoxazine compound (C) used in the present invention is a compound having a benzoxazine ring, which is a condensed ring of oxazine and a benzene ring. Also included are polymers that have been made. The benzoxazine compound (C) usually generates a phenolic hydroxyl group by opening the oxazine ring, and acts as a curing agent for the epoxy compound (A) by the action of such a phenolic hydroxyl group. is there.

As such a benzoxazine compound (C), for example, a compound represented by the following general formula (1), the following general formula (2) or the following general formula (3), an oligomer of the compound, Examples thereof include polymers polymerized by ring-opening polymerization of an oxazine ring.

In the general formulas (1), (2), and (3), X ¹ , X ² , and X ³ are each a methylene group, ethylene group, propylene group, or phenylene group that may have a substituent. , A biphenylene group, a naphthylene group, a cyclohexylene group, a dicyclopentadienylene group or a linking group containing a sulfur atom. In the general formula (3), each R ¹ is independently a hydrogen atom, methyl group, ethyl group, propyl group, phenyl group, biphenyl group, naphthyl group, cyclohexyl group or dicyclopentadienyl group. is there.

  Moreover, as a benzoxazine compound (C), you may use a commercial item, for example, Pd type benzoxazine (Hydroxyl equivalent 217, Shikoku Kasei Kogyo Co., Ltd.), Fa type benzoxazine (Hydroxyl equivalent) 217, manufactured by Shikoku Kasei Kogyo Co., Ltd.), trade names "BS-BXZ, BF-BXZ, BA-BXZ" (above, manufactured by Konishi Chemical Co., Ltd.), trade names "MT35800, MT35900, MT36000, RD2009-008, RD2007-027" (Above, manufactured by Huntsman).

  In the curable resin composition of the present invention, the ratio of the active ester group of the active ester compound (B) to the phenolic hydroxyl group of the benzoxazine compound (C) is an equivalent ratio of “phenolic hydroxyl group / active ester group”. , 0.3 to 0.9, and preferably 0.31 to 0.8. By setting the equivalent ratio of “phenolic hydroxyl group / active ester group” within the above range, it is possible to further improve the heat resistance and the linear expansion coefficient when cured.

  The blending amount of the benzoxazine compound (C) in the curable resin composition of the present invention is preferably 38 to 85 parts by weight, more preferably 40 parts per 100 parts by weight of the polyfunctional epoxy compound (A). It is -70 weight part, More preferably, it is the range of 42-60 weight part. By making the compounding quantity of a benzoxazine compound (C) into the said range, the electrical property as a hardened | cured material, low heat property, and a linear expansion coefficient can be improved.

  In the curable resin composition of the present invention, the ratio of the epoxy group of the polyfunctional epoxy compound (A) to the active ester group of the active ester compound (B) and the phenolic hydroxyl group of the benzoxazine compound (C) is The equivalent ratio of “(active ester group + phenolic hydroxyl group) / epoxy group” is preferably in the range of 1.0 to 2.0, more preferably in the range of 1.05 to 1.8. More preferably, it is in the range of 1.1 to 1.7. By setting the equivalent ratio of “(active ester group + phenolic hydroxyl group) / epoxy group” and the equivalent ratio of “phenolic hydroxyl group / phenolic ester group” within the above range, heat resistance when cured product and line The expansion coefficient can be further improved.

(Filler (D))
The filler (D) used in the present invention is not particularly limited as long as it is generally used industrially, and any of inorganic fillers and organic fillers can be used, but inorganic fillers are preferred. Used. By mix | blending a filler (D), when it is set as hardened | cured material, the hardened | cured material obtained can be made into what has low linear expansion property.

  Specific examples of inorganic fillers include calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, hydrated alumina, magnesium hydroxide, aluminum hydroxide , Barium sulfate, silica, talc, clay and the like. Among these, those that are not decomposed or dissolved by an oxidizing compound such as an aqueous solution of permanganate used for the surface roughening treatment of the cured product are preferable, and silica is particularly preferable because fine particles are easily obtained. . The inorganic filler may be treated with a silane coupling agent or an organic acid such as stearic acid.

  Further, the filler (D) is preferably a non-conductive material that does not deteriorate the dielectric properties when the resin layer is used. In addition, the shape of the filler (D) is not particularly limited, and may be spherical, fibrous, plate-like, etc. In order to make the dispersibility and the resin fluidity of the resin composition good, A fine spherical shape is preferred.

  The average particle diameter of the filler (D) is preferably 0.05 to 1.5 μm, more preferably 0.1 to 1 μm. When the average particle diameter of the filler (D) is in the above range, the linear expansion coefficient when the resin layer is formed can be lowered while the fluidity of the curable resin composition is improved. The average particle diameter can be measured with a particle size distribution measuring device.

  The blending amount of the filler (D) is in the curable resin composition (in the curable resin composition excluding the organic solvent when an organic solvent is included), preferably 30 to 90% by weight, more preferably 40. -80% by weight, more preferably 50-70% by weight.

(Other ingredients)
Moreover, the curable resin composition of this invention may contain the hardening accelerator as needed. The curing accelerator is not particularly limited, and examples thereof include aliphatic polyamines, aromatic polyamines, secondary amines, tertiary amines, acid anhydrides, imidazole derivatives, organic acid hydrazides, dicyandiamide and derivatives thereof, urea derivatives, and the like. Among them, imidazole derivatives are particularly preferable among these.

  The imidazole derivative is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include 2-ethylimidazole, 2-ethyl-4-methylimidazole, bis-2-ethyl-4-methylimidazole, and 1-methyl. Alkyl-substituted imidazole compounds such as 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-heptadecylimidazole; 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Aryl groups and aralkyl groups such as methylimidazole, 1-benzyl-2-ethylimidazole, 1-benzyl-2-phenylimidazole, benzimidazole, 2-ethyl-4-methyl-1- (2′-cyanoethyl) imidazole, etc. ring Such as imidazole compounds substituted with a hydrocarbon group containing a granulation and the like. These can be used individually by 1 type or in combination of 2 or more types.

  The blending amount in the case of blending the curing accelerator may be appropriately selected according to the purpose of use, but is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyfunctional epoxy compound (A). Preferably it is 0.5-8 weight part, More preferably, it is 0.5-6 weight part.

  Furthermore, the curable resin composition of the present invention is for the purpose of improving the flame retardancy when used as a cured product, for example, for forming a general electric insulation film such as a halogen-based flame retardant or a phosphate ester-based flame retardant. You may mix | blend the flame retardant mix | blended with this resin composition. When the flame retardant is blended in the curable resin composition of the present invention, the blending amount is preferably 100 parts by weight or less, more preferably 60 parts by weight or less with respect to 100 parts by weight of the polyfunctional epoxy compound (A). It is.

  Further, the curable resin composition of the present invention further includes a flame retardant aid, a heat resistance stabilizer, a weather resistance stabilizer, an anti-aging agent, an ultraviolet absorber (laser processability improver), a leveling agent, if necessary. You may mix | blend arbitrary components, such as an antistatic agent, a slip agent, an antiblocking agent, an antifogging agent, a lubricant, a dye, a natural oil, a synthetic oil, a wax, an emulsion, a magnetic body, a dielectric property modifier, and a toughening agent. What is necessary is just to select suitably the mixture ratio of these arbitrary components in the range which does not impair the objective of this invention.

  The method for producing the curable resin composition of the present invention is not particularly limited, and the above components may be mixed as they are, or may be mixed in a state dissolved or dispersed in an organic solvent. Then, a composition in a state where a part of each of the above components is dissolved or dispersed in an organic solvent may be prepared, and the remaining components may be mixed with the composition.

(the film)
The film of this invention is a molded object formed by shape | molding the curable resin composition of this invention mentioned above in a sheet form or a film form.

  When the curable resin composition of the present invention is molded into a sheet shape or a film shape to obtain a molded body, the curable resin composition of the present invention is added to an organic solvent as necessary, and a support. It is preferably obtained by applying, spraying or casting to the substrate and then drying.

  Examples of the support used in this case include a resin film and a metal foil. Examples of the resin film include polyethylene terephthalate film, polypropylene film, polyethylene film, polycarbonate film, polyethylene naphthalate film, polyarylate film, and nylon film. Among these films, a polyethylene terephthalate film or a polyethylene naphthalate film is preferable from the viewpoint of heat resistance, chemical resistance, peelability, and the like. Examples of the metal foil include copper foil, aluminum foil, nickel foil, chrome foil, gold foil, and silver foil.

  The thickness of the sheet-like or film-like molded body is not particularly limited, but is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 5 to 80 μm from the viewpoint of workability and the like.

  Examples of the method for applying the curable resin composition of the present invention include dip coating, roll coating, curtain coating, die coating, slit coating, and gravure coating.

  In the present invention, it is preferable that the curable resin composition of the present invention is in an uncured or semi-cured state as a sheet-shaped or film-shaped molded body. Here, uncured means a state in which substantially all of the polyfunctional epoxy compound (A) is dissolved when the molded body is immersed in a solvent capable of dissolving the polyfunctional epoxy compound (A). The semi-cured is a state where it is cured halfway to such an extent that it can be further cured by heating. Preferably, one half of the multifunctional epoxy compound (A) is dissolved in a solvent capable of dissolving the multifunctional epoxy compound (A). Part (specifically, an amount of 7% by weight or more and an amount such that a part remains), or the volume after the molded body is immersed in a solvent for 24 hours The state which is 200% or more (swelling rate) of the volume before immersion.

  Moreover, after apply | coating the curable resin composition of this invention on a support body, you may dry as needed. The drying temperature is preferably a temperature at which the curable resin composition of the present invention is not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds too much, and the resulting molded article may not be in an uncured or semi-cured state. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  And the film of this invention obtained in this way is used in the state made to adhere on a support body, or peeling from a support body.

(Multilayer film)
A multilayer film having the above-described adhesive layer made of the curable resin composition of the present invention and the plated layer made of the resin composition for plated layer can be obtained.

  Although it does not specifically limit as a resin composition for to-be-plated layers for forming a to-be-plated layer, What contains the alicyclic olefin polymer which has a polar group, and a hardening | curing agent is mentioned.

  The alicyclic olefin polymer having a polar group is not particularly limited, and examples of the alicyclic structure include those having a cycloalkane structure or a cycloalkene structure. From the viewpoint of mechanical strength, heat resistance, and the like. Those having a cycloalkane structure are preferred. Moreover, as a polar group contained in the alicyclic olefin polymer having a polar group, the same epoxy reactive group contained in the alicyclic olefin polymer (E) described above can be used, Therefore, as the alicyclic olefin polymer having a polar group, the same alicyclic olefin polymer (E) as described above can be used.

  Further, the curing agent is not particularly limited as long as it can form a crosslinked structure in the alicyclic olefin polymer by heating, and is blended into a general resin composition for forming an electrical insulating film. A curing agent can be used. Specific examples of such curing agents include polyvalent epoxy compounds, polyvalent isocyanate compounds, polyvalent amine compounds, polyhydric hydrazide compounds, aziridine compounds, basic metal oxides, and organometallic halides.

  For example, the multilayer film is formed by the following two methods: (1) The above-described resin composition for a layer to be plated is applied, spread, or cast on a support, and is dried as necessary. , A method for further applying or casting the above-described curable resin composition of the present invention and drying it as necessary; (2) applying the above-mentioned resin composition for a layer to be plated on a support; A molded body for a layer to be plated formed by spraying or casting and drying as necessary is formed into a sheet or film, and the above-described curable resin composition of the present invention is applied onto a support. Manufactured by a method of manufacturing by spreading, casting or drying, if necessary, forming into a sheet or film, laminating a molded product for an adhesive layer, and integrating these molded products can do. Among these production methods, the production method (1) is preferred because it is an easier process and is excellent in productivity. In this case, the support and coating method used when the resin composition for a layer to be plated and the curable resin composition of the present invention are applied can be the same as those of the above-described film of the present invention.

  Moreover, in the said multilayer film, it is preferable that the to-be-plated layer and contact bonding layer which comprise the said multilayer film are a non-hardened or semi-hardened state. By making these into an uncured or semi-cured state, the adhesive layer constituting the multilayer film can be made highly adhesive.

(Prepreg)
The prepreg of the present invention is a sheet-shaped or film-shaped composite molded body formed by impregnating a fiber base material with the above-described resin composition of the present invention.

  Examples of the fiber base used in this case include organic fibers such as polyamide fiber, polyaramid fiber and polyester fiber, and inorganic fibers such as glass fiber and carbon fiber. Moreover, as a form of a fiber base material, the form of textiles, such as a plain weave or a twill, or the form of a nonwoven fabric, etc. are mentioned.

  The thickness of the sheet-like or film-like composite molded body is not particularly limited, but is usually 1 to 150 μm, preferably 2 to 100 μm, and more preferably 5 to 80 μm from the viewpoint of workability. The amount of the fiber base in the composite molded body is usually 20 to 90% by weight, preferably 30 to 85% by weight.

  The method for impregnating the fiber base material with the curable resin composition of the present invention is not particularly limited, but an organic solvent is added to the curable resin composition of the present invention to adjust the viscosity and the like. The method of immersing a fiber base material in the added curable resin composition, the method of apply | coating or spraying the curable resin composition which added the organic solvent to a fiber base material, etc. are mentioned. In the method of coating or spraying, a fiber base material is placed on a support, and a curable resin composition to which an organic solvent is added can be coated or sprayed. In addition, as a sheet-like or film-like composite molded body, the curable resin composition of the present invention is contained in an uncured or semi-cured state, similarly to the above-described sheet-shaped or film-shaped molded body. Is preferred.

  Moreover, after impregnating the fiber base material with the curable resin composition of this invention, you may dry as needed. The drying temperature is preferably a temperature at which the curable resin composition of the present invention is not cured, and is usually 20 to 300 ° C, preferably 30 to 200 ° C. If the drying temperature is too high, the curing reaction proceeds too much, and the resulting composite molded article may not be in an uncured or semi-cured state. The drying time is usually 30 seconds to 1 hour, preferably 1 minute to 30 minutes.

  And the prepreg of this invention obtained in this way can be made into hardened | cured material by heating this and making it harden | cure.

  The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, more preferably 100 to 200 ° C. The curing time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven.

(Laminate)
A laminate formed by laminating the above-described film, multilayer film, or prepreg on a substrate can be obtained. The laminate may be at least a film formed by laminating the above-described film, multilayer film, or prepreg, and an electric circuit composed of a substrate having a conductor layer on the surface and the above-described film, multilayer film, or prepreg. What laminates | stacks an insulating layer is preferable.

  A substrate having a conductor layer on the surface has a conductor layer on the surface of the electrically insulating substrate. The electrically insulating substrate contains a known electrically insulating material (for example, alicyclic olefin polymer, epoxy resin, maleimide resin, (meth) acrylic resin, diallyl phthalate resin, triazine resin, polyphenyl ether, glass, etc.). The resin composition is formed by curing. Although a conductor layer is not specifically limited, Usually, it is a layer containing the wiring formed with conductors, such as an electroconductive metal, Comprising: Various circuits may be included further. The configuration and thickness of the wiring and circuit are not particularly limited. Specific examples of the substrate having a conductor layer on the surface include a printed wiring board and a silicon wafer substrate. The thickness of the substrate having a conductor layer on the surface is usually 10 μm to 10 mm, preferably 20 μm to 5 mm, more preferably 30 μm to 2 mm.

  The substrate having a conductor layer on the surface is preferably pretreated on the surface of the conductor layer in order to improve adhesion to the electrical insulating layer. As a pretreatment method, a known technique can be used without any particular limitation. For example, if the conductor layer is made of copper, an oxidation treatment method in which a strong alkali oxidizing solution is brought into contact with the surface of the conductor layer to form a copper oxide layer on the conductor surface and roughened, After oxidation with this method, reduce with sodium borohydride, formalin, etc., deposit and roughen the plating on the conductor layer, contact the organic acid with the conductor layer to elute the copper grain boundaries and roughen And a method of forming a primer layer with a thiol compound or a silane compound on the conductor layer. Among these, from the viewpoint of easy maintenance of the shape of a fine wiring pattern, a method in which an organic acid is brought into contact with a conductor layer to elute and roughen the grain boundaries of copper, and a primer using a thiol compound or a silane compound A method of forming a layer is preferred.

  Further, for example, on the substrate having a conductor layer on the surface, the above-described film (that is, a molded product obtained by molding the curable resin composition of the present invention into a sheet or film), a laminated film (of the present invention). A composite molded product obtained by impregnating a fiber base material with a prepreg (a curable resin composition of the present invention) or a prepreg (adhesive layer comprising a curable resin composition and a layer to be plated) or a prepreg. ) Can be produced by thermocompression bonding.

  As a method of thermocompression bonding, a molded body with a support or a composite molded body is superposed so as to be in contact with the conductor layer of the substrate described above, and a pressure laminator, a press, a vacuum laminator, a vacuum press, a roll laminator or the like The method of carrying out thermocompression bonding (lamination) using is mentioned. By heating and pressurizing, bonding can be performed so that there is substantially no void at the interface between the conductor layer on the substrate surface and the molded body or composite molded body.

  The temperature of the thermocompression bonding operation is usually 30 to 250 ° C., preferably 70 to 200 ° C., the pressure applied is usually 10 kPa to 20 MPa, preferably 100 kPa to 10 MPa, and the time is usually 30 seconds to 5 seconds. Time, preferably 1 minute to 3 hours. The thermocompression bonding is preferably performed under reduced pressure in order to improve the embedding property of the wiring pattern and suppress the generation of bubbles. The pressure under reduced pressure at which thermocompression bonding is performed is usually 100 kPa to 1 Pa, preferably 40 kPa to 10 Pa.

(Cured product)
The hardened | cured material of this invention can be made into hardened | cured material by performing the process hardened | cured with respect to the location which consists of the curable resin composition in the said film, the said multilayer film, the said prepreg, and the said laminated body. Curing is usually performed by heating the entire substrate on which the film or multilayer film of the present invention is formed on the conductor layer. Curing can be performed simultaneously with the above-described thermocompression bonding operation. Alternatively, the thermocompression may be performed after the thermocompression operation is performed under conditions that do not cause curing, that is, at a relatively low temperature and in a short time.

  In addition, for the purpose of improving the flatness of the electrical insulating layer or increasing the thickness of the electrical insulating layer, two or more films, multilayer films, prepregs, etc. of the present invention are bonded and laminated on the conductor layer of the substrate. May be.

  The curing temperature is usually 30 to 400 ° C, preferably 70 to 300 ° C, more preferably 100 to 200 ° C. The curing time is 0.1 to 5 hours, preferably 0.5 to 3 hours. The heating method is not particularly limited, and may be performed using, for example, an electric oven.

(Complex)
Another conductor layer can be formed on the electrical insulating layer of the laminate to obtain a composite. As the conductor layer, metal plating or metal foil can be used. Examples of the metal plating material include gold, silver, copper, rhodium, palladium, nickel or tin, and examples of the metal foil include those used as a support for the above-mentioned film, multilayer film or prepreg. In addition, the method of using metal plating as the conductor layer is preferable from the point that fine wiring is possible. Hereinafter, the manufacturing method of the composite will be described by exemplifying a multilayer circuit board using metal plating as a conductor layer.

  First, a via hole or a through hole that penetrates the electrical insulating layer is formed in the laminate. The via hole is formed to connect the respective conductor layers constituting the multilayer circuit board when the multilayer circuit board is used. The via hole or the through hole can be formed by chemical processing such as photolithography or physical processing such as drilling, laser, or plasma etching. Among these methods, a laser method (carbon dioxide laser, excimer laser, UV-YAG laser, or the like) is preferable because a finer via hole can be formed without degrading the characteristics of the electrical insulating layer.

Next, the surface roughening process which roughens the surface of the electric insulation layer (namely, cured | curing material of this invention) of a laminated body is performed. The surface roughening treatment is performed in order to improve the adhesiveness with the conductive layer formed on the electrical insulating layer.
The surface average roughness Ra of the electrical insulating layer is preferably 0.05 μm or more and less than 0.5 μm, more preferably 0.06 μm or more and 0.3 μm or less, and the surface 10-point average roughness Rzjis is preferably 0.00. They are 3 micrometers or more and less than 6 micrometers, More preferably, they are 0.5 micrometers or more and 5 micrometers or less. In this specification, Ra is the arithmetic average roughness shown in JIS B0601-2001, and the surface ten-point average roughness Rzjis is the ten-point average roughness shown in JIS B0601-2001 appendix 1.

  Although it does not specifically limit as a surface roughening processing method, The method etc. which make an electrical insulating layer surface and an oxidizing compound contact are mentioned. Examples of the oxidizing compound include known compounds having oxidizing ability, such as inorganic oxidizing compounds and organic oxidizing compounds. In view of easy control of the surface average roughness of the electrical insulating layer, it is particularly preferable to use an inorganic oxidizing compound or an organic oxidizing compound. Examples of inorganic oxidizing compounds include permanganate, chromic anhydride, dichromate, chromate, persulfate, activated manganese dioxide, osmium tetroxide, hydrogen peroxide, periodate, and the like. . Examples of the organic oxidizing compound include dicumyl peroxide, octanoyl peroxide, m-chloroperbenzoic acid, peracetic acid, and ozone.

  There is no particular limitation on the method of roughening the surface of the electrical insulating layer using an inorganic oxidizing compound or an organic oxidizing compound. For example, there is a method in which an oxidizing compound solution prepared by dissolving the oxidizing compound in a soluble solvent is brought into contact with the surface of the electrical insulating layer. The method for bringing the oxidizing compound solution into contact with the surface of the electrical insulating layer is not particularly limited. For example, the dipping method in which the electrical insulating layer is immersed in the oxidizing compound solution, the surface tension of the oxidizing compound solution is used. Any method may be used, such as a liquid filling method in which the oxidizing compound solution is placed on the electric insulating layer, or a spray method in which the oxidizing compound solution is sprayed on the electric insulating layer. By performing the surface roughening treatment, it is possible to improve the adhesion between the electrical insulating layer and another layer such as a conductor layer.

  The temperature and time for bringing these oxidizing compound solutions into contact with the surface of the electrical insulating layer may be set arbitrarily in consideration of the concentration and type of the oxidizing compound, the contact method, etc. It is 250 degreeC, Preferably it is 20-180 degreeC, and time is 0.5 to 60 minutes normally, Preferably it is 1 to 40 minutes.

  Note that the surface of the electrical insulating layer after the surface roughening treatment is washed with water in order to remove the oxidizing compound after the surface roughening treatment. In addition, if a substance that cannot be washed with water is attached, the substance can be further washed with a dissolvable cleaning solution or brought into contact with other compounds to make it soluble in water. Wash with water. For example, when an alkaline aqueous solution such as an aqueous potassium permanganate solution or an aqueous sodium permanganate solution is brought into contact with the electrical insulating layer, a mixed solution of hydroxyamine sulfate and sulfuric acid is used to remove the generated manganese dioxide film. It can wash | clean with water, after neutralizing-reducing process with the acidic aqueous solution of this.

Next, after surface roughening treatment is performed on the electrical insulating layer of the laminate, a conductor layer is formed on the surface of the electrical insulating layer and the inner wall surfaces of the via holes and through holes.
The conductive layer is formed by electroless plating from the viewpoint that a conductive layer having excellent adhesion can be formed.

  For example, when forming a conductor layer by an electroless plating method, first, before forming a metal thin film on the surface of the electrical insulation layer, catalyst nuclei such as silver, palladium, zinc, and cobalt are formed on the electrical insulation layer. It is common to attach. The method for attaching the catalyst nucleus to the electrical insulating layer is not particularly limited. For example, a metal compound such as silver, palladium, zinc, or cobalt, or a salt or complex thereof is added to water or an organic solvent such as alcohol or chloroform to 0.001. Examples include a method of reducing a metal after dipping in a solution (which may contain an acid, an alkali, a complexing agent, a reducing agent, etc., if necessary) dissolved at a concentration of 10 to 10% by weight.

  As the electroless plating solution used in the electroless plating method, a known autocatalytic electroless plating solution may be used, and the metal species, reducing agent species, complexing agent species, hydrogen ion concentration, The dissolved oxygen concentration is not particularly limited. For example, electroless copper plating solution using ammonium hypophosphite, hypophosphorous acid, ammonium borohydride, hydrazine, formalin, etc. as a reducing agent; electroless nickel-phosphorous plating solution using sodium hypophosphite as a reducing agent Electroless nickel-boron plating solution using dimethylamine borane as a reducing agent; electroless palladium plating solution; electroless palladium-phosphorous plating solution using sodium hypophosphite as a reducing agent; electroless gold plating solution; electroless silver Plating solution: An electroless plating solution such as an electroless nickel-cobalt-phosphorous plating solution using sodium hypophosphite as a reducing agent can be used.

  After forming the metal thin film, the substrate surface can be brought into contact with a rust preventive agent to carry out a rust prevention treatment. Moreover, after forming a metal thin film, a metal thin film can also be heated in order to improve adhesiveness. The heating temperature is usually 50 to 350 ° C, preferably 80 to 250 ° C. In this case, heating may be performed under a pressurized condition. As a pressurizing method at this time, for example, a method using a physical pressurizing means such as a hot press machine or a pressurizing and heating roll machine can be cited. The applied pressure is usually 0.1 to 20 MPa, preferably 0.5 to 10 MPa. If it is this range, the high adhesiveness of a metal thin film and an electrically insulating layer is securable.

  A resist pattern for plating is formed on the metal thin film thus formed, and further, plating is grown thereon by wet plating such as electrolytic plating (thick plating), then the resist is removed, and further etched. The metal thin film is etched into a pattern to form a conductor layer. Therefore, the conductor layer formed by this method usually consists of a patterned metal thin film and plating grown thereon.

  Alternatively, when a metal foil is used instead of metal plating as the conductor layer constituting the multilayer circuit board, it can be manufactured by the following method.

  That is, first, in the same manner as described above, a laminate composed of an electrical insulating layer made of a film, a multilayer film or a prepreg and a conductor layer made of a metal foil is prepared. As such a laminated body, when laminated, the curable resin composition has a degree of curing that can maintain each required characteristic, and there is no problem when it is processed afterwards or when a multilayer circuit board is formed. In particular, it is desirable to form by laminating under vacuum. In addition, the laminated body comprised from the electrically insulating layer which consists of such a film, a multilayer film, or a prepreg, and the conductor layer which consists of metal foil can be used also for a printed wiring board by a well-known subtractive method, for example.

  Then, in the same manner as described above, via holes and through holes penetrating the electrical insulating layer are formed in the prepared laminated body, and then the laminated body in which through holes are formed in order to remove the resin residue in the formed via holes. About desmear processing. Although the method of a desmear process is not specifically limited, For example, the method of contacting the solution (desmear liquid) of oxidizing compounds, such as a permanganate, is mentioned. Specifically, the laminated body in which the via hole is formed is immersed for 1 to 50 minutes in an aqueous solution at 60 to 80 ° C. adjusted to have a sodium permanganate concentration of 60 g / liter and a sodium hydroxide concentration of 28 g / liter. Thus, desmear processing can be performed.

  Subsequently, after performing a desmear process about a laminated body, a conductor layer is formed in a via hole inner wall surface. The method for forming the conductor layer is not particularly limited, and either an electroless plating method or an electrolytic plating method can be used. From the viewpoint that a conductor layer having excellent adhesion can be formed, metal plating is used as the above-described conductor layer. It can carry out by the electroless-plating method similarly to the method of forming.

  Next, after forming a conductor layer on the inner wall surface of the via hole, a resist pattern for plating is formed on the metal foil, and further, plating is grown on the metal foil by wet plating such as electrolytic plating (thick plating). Then, the metal foil is etched into a pattern by etching to form a conductor layer. Therefore, the conductor layer formed by this method usually consists of a patterned metal foil and plating grown thereon.

  The multilayer circuit board obtained as described above is used as a substrate for manufacturing the above-described laminate, and this is thermocompression-bonded with the above-described molded body or composite molded body and cured to form an electrical insulating layer. Further, by further forming a conductive layer in accordance with the above-described method and repeating these, further multilayering can be performed, and thereby a desired multilayer circuit board can be obtained.

  The composite thus obtained (and the multilayer circuit board as an example of the composite of the present invention) has an electrical insulating layer (cured product of the present invention) comprising the curable resin composition of the present invention. Since the electrical insulating layer has low linear expansion and is excellent in electrical characteristics, heat resistance, and wiring embedding flatness, the composite (and a multilayer circuit board as an example of the composite) is used in various applications. Can be suitably used.

(Electronic material substrate)
An electronic material substrate comprising the cured product or composite of the present invention can be obtained. Such a substrate for an electronic material comprising a cured product or a composite of the present invention includes a mobile phone, a PHS, a notebook computer, a PDA (personal digital assistant), a mobile video phone, a personal computer, a supercomputer, a server, a router, and a liquid crystal. Projector, engineering workstation (EWS), pager, word processor, TV, viewfinder type or monitor direct view type video tape recorder, electronic notebook, electronic desk calculator, car navigation device, POS terminal, device with touch panel, etc. It can use suitably for an electronic device.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, the part and% in each example are a basis of weight unless there is particular notice. Various physical properties were evaluated according to the following methods.

(1) Relative permittivity A small piece having a width of 2.6 mm, a length of 80 mm, and a thickness of 40 μm was cut out from the film-like cured product, and the relative permittivity at 10 GHz was measured using a cavity resonator perturbation method permittivity measurement apparatus. Evaluation was made according to the following criteria.
A: Relative permittivity is less than 3.2 B: Relative permittivity is 3.2 or more and less than 3.3 C: Relative permittivity is 3.3 or more

(2) Dielectric loss tangent A 2.6 mm wide, 80 mm long, 40 μm thick piece was cut out from the cured film and measured for dielectric loss tangent at 10 GHz using a cavity resonator perturbation method dielectric constant measurement device. Evaluated by criteria.
A: Dielectric tangent is less than 0.009 B: Dielectric tangent is 0.009 or more and less than 0.010 C: Dielectric tangent is 0.010 or more

(3) Linear expansion coefficient A small piece having a width of 6 mm, a length of 15.4 mm, and a thickness of 40 μm was cut out from the film-like cured product, and was subjected to a thermomechanical analyzer (TMA) under the conditions of a distance between supporting points of 10 mm and a heating rate of 10 ° C./min. / SDTA840: manufactured by METTLER TOLEDO), the linear expansion coefficient at 30 ° C. to 240 ° C. is measured, and the linear expansion coefficient α1 at 30 to 150 ° C. and the linear expansion coefficient α2 at 150 to 240 ° C. obtained as a result of the measurement. Sought for each.

(4) Glass transition temperature (Tg)
With respect to the glass transition temperature (Tg) of the film-like cured product, a tangent line was drawn on a curve before and after the glass transition temperature by a thermomechanical analyzer (TMA) under the above conditions, and Tg was determined from the intersection of the tangent lines.

Example 1
(Preparation of curable resin composition)
As a polyfunctional epoxy compound (A), 40 parts of a dicyclopentadiene type epoxy resin (A-1) (trade name “EPICLON HP-7200HH”, manufactured by DIC, epoxy group equivalent 250), as a polyfunctional epoxy compound (A) Epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone (A-2) (trade name “Epolide GT401”, manufactured by Daicel Chemical Industries, Ltd., epoxy group equivalent 183), active ester compound ( B) Active ester resin (B-1) (trade name “EPICLON HPC-8000-65T”, toluene solution with a nonvolatile content of 65% by weight, manufactured by DIC, active ester group equivalent 223) 134 parts, benzoxazine compound ( Pd-type benzoxazine (C-1) as C) (Shikoku Chemicals) In the above general formula (2), 44 parts by weight of a compound in which X ² is a methylene group, phenolic hydroxyl group equivalent 217, silica (D-1) as a filler (D) (trade name “SC2500-SXJ” 525 parts manufactured by Admatechs Co., Ltd.), 1.6 parts of a hindered phenolic antioxidant (trade name “Irganox 3114”, manufactured by BASF) as an anti-aging agent, and 110 parts of anisole are mixed. The mixture was stirred for 3 minutes with a planetary stirrer.
Furthermore, 13 parts (4 parts of curing accelerator) in terms of solid content was mixed with a solution obtained by dissolving 30% of 1-benzyl-2-phenylimidazole in anisole as a curing accelerator, and stirred for 5 minutes with a planetary stirrer. Thus, a varnish of the curable resin composition was obtained.

(Production of film molding)
Next, the varnish of the curable resin composition obtained above is a polyethylene terephthalate film having a size of 300 mm in length and 300 mm in width, a thickness of 38 μm, and a surface average roughness Ra of 0.08 μm, using a die coater. (Support: Lumirror (registered trademark) T60 manufactured by Toray Industries, Inc.) and then dried in a nitrogen atmosphere at 80 ° C. for 10 minutes to form a 43 μm thick resin composition film molding on the support. Obtained.

(Preparation of cured film)
Next, on a copper foil having a thickness of 10 μm, a small piece cut out from the film molded body of the obtained curable resin resin composition, with the support attached, the curable resin composition is on the inside, Using a vacuum laminator equipped with heat-resistant rubber press plates at the top and bottom, the pressure was reduced to 200 Pa, thermocompression laminated at a temperature of 110 ° C. and a pressure of 0.1 MPa for 60 seconds, and then heated and cured in air at 180 ° C. for 120 minutes. . After curing, the cured resin with a copper foil was cut out and the copper foil was dissolved in a 1 mol / L ammonium persulfate aqueous solution to obtain a film-like cured product. Using the obtained film-like cured product, the relative dielectric constant, dielectric loss tangent, linear expansion coefficient, and glass transition temperature were measured according to the above methods. The results are shown in Table 1.

Example 2
A varnish of the curable resin resin composition was obtained in the same manner as in Example 1 except that the blending amount of each component was as shown in Table 1, and the varnish of the obtained curable resin resin composition was used. Except for the above, a film molded body and a film-like cured product were produced in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

Comparative Examples 1-4
A varnish of the curable resin resin composition was obtained in the same manner as in Example 1 except that the blending amount of each component was as shown in Table 1, and the varnish of the obtained curable resin resin composition was used. Except for the above, a film molded body and a film-like cured product were produced in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 1.

  As shown in Table 1, by using the curable resin composition of the present invention, the obtained film-like cured product (electrical insulating layer) has low linear expansion, electrical characteristics (dielectric constant and dielectric loss tangent), and heat resistance. It can confirm that it can be set as the thing excellent in property (Example 1, 2). In particular, the film-like cured product (electrical insulating layer) obtained by using the curable resin composition of the present invention has a linear expansion coefficient on the high temperature side (that is, a line at 150 to 240 ° C.) as can be confirmed from Table 1. (Expansion coefficient) is low, and it can be confirmed that it is particularly excellent in low linear expansion under a high temperature environment.

On the other hand, when the benzoxazine compound (C) is not blended or when the blended amount of the benzoxazine compound (C) is too small, the obtained film-like cured product has a linear expansion coefficient on the low temperature side (30 to 30). 150 ° C.) and on the high temperature side (150 to 240 ° C.), both of which were inferior in low linear expansion (Comparative Examples 1 to 3).
Moreover, when there were too many compounding quantities of a benzoxazine compound (C), the film-form hardened | cured material obtained had a high dielectric loss tangent, and became inferior to an electrical property (comparative example 4).

Claims (6)

A polyfunctional epoxy compound (A), an active ester compound (B), a benzoxazine compound (C), and a filler (D);
The ratio of the active ester group of the active ester compound (B) to the phenolic hydroxyl group of the benzoxazine compound (C) is 0.3 to 0.9 in terms of an equivalent ratio of “phenolic hydroxyl group / active ester group”. A curable resin composition.   The ratio of the epoxy group of the polyfunctional epoxy compound (A), the active ester group of the active ester compound (B), and the phenolic hydroxyl group of the benzoxazine compound (C) is “(active ester group + phenolic). The curable resin composition according to claim 1, wherein the equivalent ratio of “hydroxyl group) / epoxy group” is 1.0 to 2.0.   The curable resin composition according to claim 1 or 2, wherein a content ratio of the benzoxazine compound (C) is 38 to 85 parts by weight with respect to 100 parts by weight of the polyfunctional epoxy compound (A).   The film which consists of a curable resin composition in any one of Claims 1-3.   A prepreg obtained by impregnating a fiber base material with the resin composition according to claim 1.   Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-3, the film of Claim 4, or the prepreg of Claim 5.