JP5135973B2 - Epoxy resin composition and cured product thereof - Google Patents

Description

  The present invention is excellent in flame retardancy of the obtained cured product, an epoxy resin composition that can be suitably used for a semiconductor encapsulant, a printed circuit board, a build-up film, a paint, a casting application, the cured product, and The present invention relates to a varnish for a printed circuit board.

  Epoxy resins are widely used in the fields of electronics such as semiconductor encapsulants and printed circuit boards because they provide cured products with low shrinkage during curing, dimensional stability of cured products, electrical insulation and chemical resistance. It is used. In the electronics field, with the enhancement of functionality of electronic components, printed wiring boards and electronic components that are compatible with high frequency bands in the gigahertz band are required. Therefore, insulating materials that have lower transmission loss are required. There is a need for an epoxy resin material having a lower dielectric loss tangent.

  As an epoxy resin material satisfying such performance, for example, an epoxy resin having a dicyclopentadiene skeleton in the molecular structure is known (see Patent Document 1 below). Such an epoxy resin has a low functional group concentration of the epoxy group and exhibits excellent dielectric performance, but is inferior in flame retardancy required for electronic component materials. Therefore, a halogen flame retardant and an antimony compound are further blended. In general, it is adjusted to an insulating material.

  However, among recent environmental and safety initiatives, there is a concern that halogen flame retardants generate dioxins. On the other hand, antimony compounds are also suspected of having carcinogenic properties, and there has been a strong demand for the development of flame retardant methods that are environmental and safety alternatives to halogen-based flame retardants and antimony compounds. As means for meeting these requirements, various techniques for imparting flame retardancy to the epoxy resin itself have been studied. For example, 2,7-dihydroxynaphthalene or β-hydroxynaphthalene is reacted with aldehydes. An epoxy resin having two naphthalene nuclei in one molecule obtained by glycidyl etherification of a polyphenol compound obtained in this manner is known (see Patent Document 2 below). Such a polyfunctional epoxy resin exhibits excellent flame retardancy because it has two naphthalene structures in one molecule, but does not reach the high level of flame retardancy required in recent years. A cured product with a sufficiently low dielectric loss tangent could not be obtained.

Japanese Patent Laid-Open No. 8-113628 JP-A-4-217675

  The problem to be solved by the present invention is to provide an epoxy resin composition having excellent flame retardancy and a low dielectric loss tangent in the cured product, and a cured product thereof.

  As a result of intensive studies to solve the above problems, the present inventors have achieved excellent flame retardancy by introducing a urethane bond together with a phenoxy group or a naphthoxy group into the resin structure of a high molecular weight bifunctional epoxy resin. As a result, the inventors have found that the dielectric loss tangent of the cured product is drastically reduced, and have completed the present invention.

  That is, the present invention relates to a bifunctional epoxy resin having a phenoxy group or naphthoxy group and a urethane bond in the molecular structure, and having an epoxy equivalent in the range of 300 to 2000 g / equivalent (A) And an epoxy resin composition characterized by comprising a curing agent (B) as an essential component.

  The present invention further relates to a cured product obtained by curing the epoxy resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding flame retardance in the hardened | cured material, an epoxy resin composition with a low dielectric loss tangent and its hardened | cured material can be provided.

Hereinafter, the present invention will be described in detail.
The epoxy resin composition of the present invention is a bifunctional epoxy resin having a phenoxy group or naphthoxy group and a urethane bond in the molecular structure, and the epoxy equivalent thereof is in the range of 300 to 2000 g / equivalent. It is characterized by using (A) as a main agent.

  Since the epoxy resin (A) has a phenoxy group or a naphthoxy group in the molecular structure and a urethane bond, the cured product exhibits excellent flame retardancy. Moreover, since it is a bifunctional type epoxy resin and an epoxy equivalent exists in the range of 300-2000 g / equivalent, the density | concentration of the hydroxyl group generate | occur | produced by hardening reaction in a hardened | cured material is reduced, and the dielectric loss tangent of hardened | cured material is reduced. Furthermore, in this invention, since it has a phenoxy group or a naphthoxy group in the molecular side chain of the epoxy resin (A), it exhibits excellent curability even when the epoxy equivalent is relatively high. Thus, it should be noted that the dielectric loss tangent can be reduced by increasing the epoxy equivalent without sacrificing the curability as an epoxy resin. The epoxy equivalent of the epoxy resin (A) is particularly 300 to 800 g / eq. It is preferable that

  The content of the phenoxy group or naphthoxy group in the epoxy resin (A) is in the range of 5 to 30% by mass in terms of the mass of the benzene ring constituting the phenoxy group or the mass of the naphthalene ring constituting the naphthoxy group. The ratio is preferably from the viewpoint of improving the flame retardancy and excellent curability.

  The content of urethane bonds in the epoxy resin (A) is such that the concentration of the urethane bond is 5 to 15% by weight, the cured product has good flame retardancy, and the viscosity of the epoxy resin (A) is high. It is preferable from the point of being reduced. Further, specifically, it is preferable that one molecule of the epoxy resin contains urethane bonds in an average ratio of 0.1 to 5.6 from the viewpoint of good flame retardancy of the cured product. Here, the mass of the benzene ring or naphthalene ring constituting the phenoxy group or naphthoxy group described above and the urethane bond content in the epoxy resin (A) are calculated values from the amount of raw materials charged.

  As a method for introducing a phenoxy group or a naphthoxy group and a urethane bond into the resin structure of the epoxy resin (A), for example, a bifunctional epoxy resin (a) is reacted with phenol or naphthol (b), and then The method of making the diisocyanate compound (c) react with the produced | generated hydroxyl group is mentioned.

  Examples of the bifunctional epoxy resin (a) used here include bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol A type epoxy resin, tetramethyl bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Biphenyl type epoxy resin; biphenyl type epoxy resin such as biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin; dicyclopentadiene-phenol addition reaction type epoxy resin; phenol aralkyl type epoxy resin; diglycidyloxynaphthalene; molecular structure of xanthene skeleton The epoxy resin which it has is mentioned.

  Among these, bisphenol-type epoxy resin or diglycidyloxynaphthalene is particularly preferable from the point that the flame retardant effect of the cured product becomes remarkable, especially liquid bisphenol-type epoxy resin is inexpensive and excellent in economy, and This is preferable from the viewpoint of excellent flame retardancy and dielectric properties of the cured product. Further, among the liquid bisphenol-type epoxy resins, those having a binuclear content of 80% by mass or more have low three-dimensional branching properties during the production of the epoxy resin (A), and a large amount of phenoxy groups or naphthoxy groups. Even if it contains, since there are few problems which lead to excessive thickening and gelatinization, it is especially preferable.

  Next, examples of phenol or naphthol (b) include phenol, α-naphthol, and β-naphthol. Among these, naphthol is preferable from the viewpoint of high effect of improving flame retardancy and curability, and β-naphthol is particularly preferable.

  Next, as the diisocyanate compound (c), for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,5-naphthalene diisocyanate And isophorone diisocyanate.

  Of these, aromatic diisocyanate compounds such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 1,5-naphthalene diisocyanate are particularly preferred. It is preferable from the point that the effect of flame retardancy becomes remarkable. Moreover, in this invention, the balance of adhesiveness and toughness can be aimed at by using together aliphatic diisocyanate, such as 1, 6- hexane diisocyanate, with the said aromatic diisocyanate compound suitably.

  More specifically, the epoxy resin (A) obtained by reacting the bifunctional epoxy resin (a) with phenol or naphthol (b) and then reacting the generated hydroxyl group with the diisocyanate compound (c) Structural formula 1

Structural formula 1

（構造式１中、Ｇはグリシジル基、Ａｒ^１は、ナフチレン基、又は、下記構造式２

(In Structural Formula 1, G is a glycidyl group, Ar ¹ is a naphthylene group, or the following Structural Formula 2

（構造式２中、Ｘは炭素原子数１〜３のアルキリデン基又はスルホニル基を表し、Ｒ^１〜Ｒ^４はそれぞれ独立的に水素原子又はメチル基を表す。）で表される２価の有機基、Ａｒ^２は芳香族炭化水素基、Ｙはフェノキシ基又はナフトキシ基をそれぞれ表し、ｎは繰り返し単位の平均で０．０５〜２．８である。）
で表される構造を有するエポキシ樹脂であることが本発明の効果が顕著なものとなる点から好ましい。

(In Structural Formula 2, X represents an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group, and R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group.) Group, Ar ² represents an aromatic hydrocarbon group, Y represents a phenoxy group or a naphthoxy group, and n is 0.05 to 2.8 on the average of the repeating units. )
An epoxy resin having a structure represented by the formula is preferable from the point that the effect of the present invention becomes remarkable.

  Among the epoxy resins (A) represented by the structural formula 1, in particular, the following structural formula 3

（構造式３中、Ｘは炭素原子数１〜３のアルキリデン基又はスルホニル基を表し、Ｒ^１〜Ｒ^４はそれぞれ独立的に水素原子又はメチル基を表し、Ａｒ^２は芳香族炭化水素基を表し、Ｙはフェノキシ基又はナフトキシ基を表し、ｎは繰り返し単位の平均で０．０５〜２．８である。）で表されるものが、硬化物の靱性向上の効果が顕著なものとなる点から好ましい。

(In Structural Formula 3, X represents an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group, and Ar ² represents an aromatic hydrocarbon group. Y represents a phenoxy group or a naphthoxy group, and n is 0.05 to 2.8 on the average of repeating units.), The effect of improving the toughness of the cured product becomes remarkable. It is preferable from the point.

  Here, Y represented by “Y” in Structural Formula 1 or Structural Formula 3 is, specifically, a phenoxy group or naphthoxy group represented by the following structural formulas p1 to p3.

これらのなかでもエポキシ樹脂（Ａ）の製造が容易であり、かつ、該エポキシ樹脂（Ａ）の難燃効果が顕著なものとなる点から前記ｐ２及びｐ３で表されるナフトキシ基が好ましく、特にｐ２で表されるβ−ナフトキシ基が好ましい。

Of these, the naphthoxy groups represented by p2 and p3 are preferred because the epoxy resin (A) can be easily produced and the flame retardant effect of the epoxy resin (A) is remarkable. The β-naphthoxy group represented by p2 is preferable.

  In addition, “X” in Structural Formula 2 or Structural Formula 3 is an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group as described above, and examples of the alkylidene group having 1 to 3 carbon atoms include a methylidene group and an ethylidene group. Group, and 2,2-propylidene group. Among these, a methylidene group is preferable because the effects of the present invention are remarkable.

The method for producing the epoxy resin (A) detailed above is as follows:
(i) A method in which the bifunctional epoxy resin (a), phenol or naphthol (b), and the diisocyanate compound (c) are mixed and reacted all at once, or
(ii) A method in which a bifunctional epoxy resin (a) is reacted with phenol or naphthol (b) (step 1), and then the resulting reaction product is reacted with a diisocyanate compound (c) (step 2). Can be mentioned.

  Here, in the methods (i) and (ii), the reaction ratio between the bifunctional epoxy resin (a) and phenol or naphthol (b) is the epoxy group 1 in the bifunctional epoxy resin (a). It is a ratio that the phenolic hydroxyl group in phenol or naphthol (b) is in the range of 0.2 to 0.8 equivalent, especially the ratio in the range of 0.3 to 0.6 equivalent to the equivalent. The concentration of the group or naphthoxy group can be adjusted to an appropriate range, the flame retardancy is good, and the moisture resistance reliability of the epoxy resin (A) is also good.

  The amount of the diisocyanate compound (c) used is such that the isocyanate group in the diisocyanate compound (c) is 0.2 to 0.8 equivalent relative to 1 equivalent of the epoxy group in the bifunctional epoxy resin (a). It is preferable from the point that the toughness of the hardened | cured material of an epoxy resin (A) is favorable that it is a ratio used as the range which becomes the range, especially 0.3-0.6 equivalent.

  Among the above-described methods, the latter method (ii) is particularly preferable because an epoxy compound having a high reaction selectivity and a molecular structure having a high linear structure can be obtained. Hereinafter, the method (ii) will be described in detail.

As the reaction conditions of step 1 of method (ii), for example, a bifunctional epoxy resin (a) and phenol or naphthol (b) are mixed and stirred at a temperature range of 50 to 200 ° C. for 1 to 20 hours. An intermediate can be obtained. In that case, an organic solvent can also be used as needed. Examples of organic solvents used include aromatic organic solvents such as xylene and toluene,
Examples include ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester organic solvents such as methyl acetate, ethyl acetate, and propyl acetate, and aliphatic hydrocarbon organic solvents such as normal hexane. It is preferable that the usage-amount is a ratio used as 10-500 mass parts with respect to 100 mass parts of raw materials.

  Moreover, a catalyst can also be used as needed. Examples of the catalyst that can be used here include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, triphenylphosphine, and tris (2,6-dimethoxyphenyl) phosphine. Examples thereof include phosphines, phosphonium salts such as ethyltriphenylphosphonium bromide, imidazoles such as 2methylimidazole and 2ethyl4methylimidazole, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The addition amount is preferably in the range of 10 ppm to 1% by mass with respect to the total of the raw material components.

  Next, as the step 2, in the reaction step of the intermediate and the diisocyanate compound (c), both are mixed and stirred at a temperature of 40 to 100 ° C. for 1 to 20 hours to obtain the target urethane-modified epoxy resin. Can be obtained. In that case, an organic solvent can also be used as needed. Specific examples of the organic solvent used include aromatic organic solvents such as xylene and toluene, ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester organic solvents such as methyl acetate, ethyl acetate, and propyl acetate. Examples of the solvent include aliphatic hydrocarbon organic solvents such as normal hexane. It is preferable that the usage-amount is a ratio used as 10-500 mass parts with respect to 100 mass parts of raw materials.

  Moreover, a catalyst can also be used as needed. Examples of the catalyst that can be used here include organometallic compounds such as tin octylate and dibutyltin laurate, 1,4-diaza-2,2,2-bicyclooctane, triethylamine, dimethylcyclohexylamine, diazabicycloundecane, And tertiary amines such as diethylbenzylamine. The addition amount is preferably in a range of 5 to 1000 ppm with respect to the total of the raw material components.

  The epoxy resin composition of the present invention may use other epoxy resins in combination with the epoxy resin (A).

Examples of other types of epoxy resins that can be used here include bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol novolac type epoxy resins, and cresol novolak type epoxy resins. Resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy Resin, naphthol-phenol co-condensed novolak epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, aromatic hydrocarbon formaldehyde Fat-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types. In particular, a biphenyl type epoxy resin, a naphthalene type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl novolac type epoxy resin, and an epoxy resin having a xanthene skeleton in the molecular structure are particularly preferable from the viewpoint of excellent flame retardancy.
It is preferable that the usage-amount of said other epoxy resin mentioned above is 5-70 mass% in an epoxy resin composition, especially 5-60 mass%.

  Next, examples of the curing agent (B) used in the present invention include amine compounds, amide compounds, acid anhydride compounds, phenol resins, and the like.

Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine.

  Acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydro And phthalic anhydride.

  Examples of phenolic resins include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins (commonly known as “Zylock resins”), naphthol aralkyl resins, and trimethylol. Methane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenol compound in which phenol nucleus is linked by bismethylene group), biphenyl Modified naphthol resin (polyvalent naphthol compound with phenol nucleus linked by bismethylene group), aminotriazine modified phenolic resin (melamine or benzoguana) Emissions polyhydric phenol compound phenol nuclei are connected by, etc.) the polyhydric phenol compound such as, and and modified products thereof. These may be used alone or in combination of two or more.

  Among these, phenolic resins are particularly preferable, and phenol novolac resins are particularly preferable from the viewpoint that the effect of improving the flame retardancy of the cured product becomes remarkable. In the present invention, a phenol novolac resin having a softening point of 90 to 130 ° C. is particularly preferable from the viewpoint of heat resistance and flame retardancy.

  The compounding quantity of the said hardening | curing agent (B) in the epoxy resin composition of this invention is a point in the hardening | curing agent (B) with respect to a total of 1 equivalent of the epoxy group of an epoxy resin from the point that the hardened | cured material characteristic obtained is favorable. The amount of the active group is preferably 0.7 to 1.5 equivalents. In the catalyst curing system such as imidazole, the range of 0.5 to 10% by mass with respect to the epoxy resin is preferable.

  Moreover, a hardening accelerator can also be suitably used together with the epoxy resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor sealing material, from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., triphenylphosphine is used for phosphorus compounds, and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  Since the epoxy resin composition of the present invention has the effect of imparting flame retardancy as described above, the epoxy resin (A) itself has good flame retardancy in the cured product even if no flame retardant is added. Although it can be expressed, in order not to lower the moldability in the sealing process and the reliability of the semiconductor device in order to exhibit a higher degree of flame retardancy, it is substantially free of halogen atoms. It is preferable to blend a halogen-based flame retardant.

  The flame retardant resin composition substantially not containing a halogen atom as used herein means a resin composition exhibiting sufficient flame retardancy without blending a halogen-based compound for the purpose of imparting flame retardancy. For example, halogen atoms due to a small amount of impurities of about 5000 ppm or less derived from epihalohydrin contained in an epoxy resin may be contained.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7-dihydro And cyclic organic phosphorus compounds such as oxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, curing agent, non-halogen type In 100 parts by mass of epoxy resin composition containing all of flame retardant and other fillers and additives, etc., when red phosphorus is used as a non-halogen flame retardant, it is blended in the range of 0.1 to 2.0 parts by mass. In the case of using an organophosphorus compound, it is preferably blended in the range of 0.1 to 10.0 parts by mass, and particularly in the range of 0.5 to 6.0 parts by mass. preferable.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, among which triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, melam sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol, nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine, formguanamine, and formaldehyde, (iii) (Ii) a mixture of a co-condensate and a phenol resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) or (iii) above with paulownia oil, isomerized linseed oil, etc. .

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass, especially in the range of 0.05 to 10 parts by mass, in 100 parts by mass of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix in the range of 5 parts by mass.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone flame retardant is appropriately selected according to the type of the silicone flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the epoxy resin composition containing all of the agent, non-halogen flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. For example, epoxy resin, cured It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the epoxy resin composition in which all of the agent, non-halogen flame retardant and other fillers and additives are blended. It is preferable to mix in the range of 15 parts by mass.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, the other components of the epoxy resin composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.005 to 10 parts by mass in 100 parts by mass of the epoxy resin composition containing all of the epoxy resin, the curing agent, the non-halogen flame retardant, and other fillers and additives.

  The epoxy resin composition of the present invention includes a semiconductor sealing material, an underfill material, a conductive paste, a varnish for a printed circuit board, a build-up film, an interlayer insulation material for a build-up board, a resist ink, an insulating powder paint, and a resin casting. It can be applied to various uses such as materials and adhesives.

  Among these, particularly when the epoxy resin composition of the present invention is used as a varnish for a printed circuit board, the excellent toughness of the cured product effectively prevents peeling and cracking in the soldering process after moisture absorption in printed wiring board production. It is preferable because it is possible.

  Examples of a method for producing a varnish for a printed circuit board from the epoxy resin composition of the present invention include a method of blending an organic solvent with each of the above-described components to form a varnish. As the organic solvent, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it can be used alone or as a mixed solvent of two or more kinds.

  To produce a copper clad laminate for a printed circuit board from the printed circuit board varnish described above, first, the printed circuit board varnish is made of paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass. A prepreg which is a cured product is produced by impregnating various reinforcing base materials such as roving cloth and heating at a heating temperature according to the solvent type used, preferably 50 to 170 ° C. At this time, the mass ratio of the epoxy resin composition and the reinforcing base is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Next, the prepreg obtained in this manner is laminated by a conventional method, and copper foil is appropriately laminated, and then subjected to thermocompression bonding under a pressure of 1 to 10 MPa at 170 to 250 ° C. for 10 minutes to 3 hours. A stretched laminate can be obtained.

  Moreover, the method for producing a build-up film from the epoxy resin composition of the present invention includes, for example, blending the above-described organic solvent with each of the above-described components to form a varnish, and applying this onto a support film to form a resin composition layer. The method of forming and making it the adhesive film for multilayer printed wiring boards is mentioned.

  When the epoxy resin composition of the present invention is used for a build-up film, the film is softened under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.) and exists on the circuit board at the same time as the circuit board lamination. It is important to show fluidity (resin flow) that allows resin filling in the via hole or through hole to be formed, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like epoxy resin composition of the present invention, coating the varnish-like composition on the surface of the support film and further heating, or It can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer of an epoxy resin composition.

  The thickness of the epoxy resin composition layer to be formed is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the layer of the epoxy resin composition may be protected with a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Next, as a method for obtaining an interlayer insulating material for a build-up substrate from the epoxy resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler, etc. is spray-coated on a wiring board on which a circuit is formed. After applying using a method, a curtain coating method, etc., it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

Moreover, the epoxy resin composition of this invention can manufacture a semiconductor sealing material or an electrically conductive paste by mix | blending an inorganic filler with said each component further.
Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like for semiconductor sealing materials, and conductive filler such as silver powder and copper powder for conductive paste applications. Agents.

  Here, it is preferable that the compounding quantity of the said inorganic filler is the range of 70-95 mass% of fillers with respect to 100 mass parts of epoxy resin compositions especially for a semiconductor sealing material use.

  When the epoxy resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the epoxy resin composition to obtain a composition for anisotropic conductive film, liquid at room temperature And a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  Moreover, the epoxy resin composition of the present invention can also be used as a resist ink. In this case, a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent (B) are blended with the epoxy resin (A), and a pigment, talc and filler are further added to form a resist. A method for forming a resist ink cured product after coating on a printed circuit board by a screen printing method after an ink composition is used.

  Moreover, when using the epoxy resin composition of this invention as an insulating powder coating material, in addition to the said epoxy resin (A) and a hardening | curing agent (B), the said inorganic filler, a coloring agent, a flame retardant as needed. In addition, various known and commonly used additive components such as a release agent or a coupling agent are sufficiently uniformly mixed by a mixer or the like, and then melt-kneaded with a hot roll or a kneader, and then pulverized after injection or cooling. Thus, the intended insulating powder coating material can be obtained. As a method of performing insulation coating of electrical and electronic parts using the salt powder coating material manufactured in this way, general powder such as fluidized immersion method, hot spray method, electrostatic spray method, electrostatic fluidized immersion method, etc. The body painting method is mentioned.

  In the epoxy resin composition of the present invention, various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier can be appropriately added according to the various uses described above.

  The epoxy resin composition of the present invention can be cured by a conventional method in accordance with the purpose or application to be used to obtain a cured product. Under the present circumstances, the method of obtaining hardened | cured material adds the various compounding components to the epoxy resin composition of this invention, and also mix | blends the composition obtained by mix | blending a hardening accelerator suitably, The temperature range of about 20-250 degreeC. The method of heating at is preferred. A general method of an epoxy resin composition can also be adopted as a molding method. The cured product thus obtained forms a laminate, cast product, adhesive layer, coating film, film and the like.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified. The melt viscosity at 150 ° C., GPC measurement, NMR, and MS spectrum were measured under the following conditions.
1) Melt viscosity at 150 ° C .: Conforms to ASTM D4287 2) Softening point measurement method: JIS K7234
3) GPC:
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
4) NMR: NMR “GSX270” manufactured by JEOL Ltd.
5) MS: Double Density Mass Spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

Example 1 (Synthesis of naphthyloxy group-containing urethane-modified epoxy resin (A-1))
A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was added to a bisphenol A type liquid epoxy resin (epoxy equivalent 188 g / eq, hydroxyl value 19.3 KOH mg / g, Dainippon Ink and Chemicals, Inc. Company "Epicron N850S") 188g (epoxy group 1.0 equivalent) and β-naphthol 48.4g were added, triphenylphosphine 0.07g was added, heated to 130 ° C and stirred for 5 hours. The intermediate was obtained by confirming that β-naphthol substantially disappeared by epoxy equivalent and GPC measurement. Next, 29.2 g (isocyanate group 0.3 equivalent) of tolylene diisocyanate (TDI: NCO equivalent 87 g / eq., Manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: Cosmonate T-100) was dropped into the reaction system at 90 ° C. Was stirred for 1 hour, and it was confirmed by IR measurement that the isocyanate group had substantially disappeared. Thus, the desired naphthyloxy group-containing urethane-modified epoxy resin (A-1) was obtained. The epoxy equivalent of the obtained epoxy resin was 425 g / eq., Softening point 80 ° C., content of naphthalene skeleton constituting naphthoxy group 15% by mass, aromatic ring concentration 50.2% by mass, urethane bond group concentration 5.3% by mass. Met.

Example 2 (Synthesis of naphthyloxy group-containing urethane-modified epoxy resin (A-2))
A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer was added to a bisphenol A type liquid epoxy resin (epoxy equivalent 188 g / eq, hydroxyl value 19.3 KOH mg / g, Dainippon Ink and Chemicals, Inc. Company "Epicron N850S") 188g (epoxy group 1.0 equivalent) and β-naphthol 58.5g were charged, and after adding 0.07g of triphenylphosphine, the temperature was raised to 130 ° C and stirred for 5 hours. The intermediate was obtained by confirming that β-naphthol substantially disappeared by epoxy equivalent and GPC measurement.
Thereafter, the reaction product containing the intermediate and 33 g of toluene were dissolved, and then 50.7 g of diphenylmethane diisocyanate (MDI: NCO equivalent 125 g / eq., “Millionate MT” manufactured by Nippon Polyurethane Industry Co., Ltd.) in the reaction system. (Isocyanate group 0.4 equivalent) was added dropwise and stirred at 90 ° C. for 1 hour, and it was confirmed by IR measurement that the isocyanate group had substantially disappeared. The target naphthyloxy group-containing urethane-modified epoxy resin ( A-2) was obtained. Subsequently, 94.4 g of methyl ethyl ketone was added to the reaction product containing the epoxy resin (A-2) to obtain a resin solution having a nonvolatile content of 70% by mass. Epoxy equivalent of the obtained epoxy resin (A-2) is 515 g / eq, content of naphthalene skeleton constituting naphthoxy group is 16.4% by mass, aromatic ring concentration is 53.4% by mass, urethane bond group concentration is 5.7% by mass. %Met. Moreover, the solution viscosity with the E-type viscosity meter of the obtained resin solution was 4,300 mPa * s.

Example 3 (Synthesis of naphthyloxy group-containing urethane-modified epoxy resin (A-3))
170 g of a bisphenol F type epoxy resin (epoxy equivalent 188 g / eq, “Epicron 830S” manufactured by Dainippon Ink & Chemicals, Inc.) attached to a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube and a stirrer Epoxy group 1.0 equivalent) and 61.8 g of β-naphthol were added, 0.07 g of triphenylphosphine was added, heated to 130 ° C., stirred for 5 hours, and β- An intermediate was obtained after confirming that naphthol had substantially disappeared.
Thereafter, the reaction product containing the intermediate is dissolved in 31.7 g of toluene, and then diphenylmethane diisocyanate (MDI: NCO equivalent 125 g / eq., “Millionate MT” manufactured by Nippon Polyurethane Industry Co., Ltd.) 53 is added to the reaction system. .6 g (0.4 equivalents of isocyanate groups) was added dropwise and stirred at 90 ° C. for 1 hour. After confirming that the isocyanate groups were substantially disappeared by IR measurement, the desired naphthyloxy group-containing urethane-modified epoxy Resin (A-3) was obtained. Next, 90.6 g of methyl ethyl ketone was added to the reaction product containing the epoxy resin (A-3) to obtain a resin solution having a nonvolatile content of 70% by mass. The epoxy equivalent of the obtained epoxy resin (A-3) was 515 g / eq, the content of naphthalene skeleton constituting the naphthoxy group was 16.4% by mass, the aromatic ring concentration was 53.4% by mass, and the urethane bond group concentration was 6.3% by mass. %Met. Moreover, the solution viscosity with the E-type viscosity meter of the obtained resin solution was 2,740 mPa * s.

Example 4 (Synthesis of naphthyloxy group-containing urethane-modified epoxy resin (A-4))
In the same manner as in Example 2, using 151 g of 1,6-dihydroxynaphthalene type epoxy resin (epoxy equivalent 151 g / eq, “Epicron HP-4032” manufactured by Dainippon Ink & Chemicals, Inc.) instead of the bisphenol A type liquid epoxy resin. The reaction product is reacted with 62.3 g of β-naphthol to obtain an intermediate, 65.4 g of toluene is added to the reaction product containing the intermediate, and then 1,5-diisocyanate naphthalene (NDI: NCO equivalent 105 g / eq, Mitsui). Chemical Co., Ltd. “Cosmonate ND”) 49.1 g (isocyanate group 0.4 equivalent) was dropped and reacted in the same manner as in Example 2 to obtain the desired urethane-modified epoxy resin (A-4). . Next, 108.9 g of methyl ethyl ketone was added to the reaction product containing the epoxy resin (A-4) to obtain a resin solution having a nonvolatile content of 60% by mass. The epoxy equivalent of the obtained epoxy resin is 563 g / eq. The naphthalene skeleton content was 59.4% by mass, the naphthalene skeleton content was 21% by mass, and the urethane bond group concentration was 7.4% by mass due to the β-naphthol. Moreover, the solution viscosity with the E-type viscosity meter of the obtained resin solution was 4,500 mPa * s.

Example 5 (Synthesis of phenoxy group-containing urethane-modified epoxy resin (A-5))
Other than using 43.4 g of phenol instead of 48.4 g of β-naphthol, and using 38.1 g of tolylene diisocyanate (TDI: NCO equivalent 87 g / eq., manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: Cosmonate T-100) Obtained an epoxy resin (A-5) in the same manner as in Example 1. The epoxy resin thus obtained had an epoxy equivalent of 511 g / eq, a softening point of 80 ° C., an aromatic ring concentration of 50.4% by mass, a benzene ring content of 12.3% by mass due to the phenol, and a urethane bond group concentration of 6.1. It was mass%.

Example 6 (Synthesis of phenoxy group-containing urethane-modified epoxy resin (A-6))
Example except that 41.2 g of phenol was used instead of 48.4 g of β-naphthol and 52.1 g of diphenylmethane diisocyanate (MDI: NCO equivalent 125 g / eq., “Millionate MT” manufactured by Nippon Polyurethane Industry Co., Ltd.) was used. In the same manner as in Example 1, an epoxy resin (A-6) was obtained. The epoxy resin thus obtained had an epoxy equivalent of 506 g / eq, a softening point of 80 ° C., an aromatic ring concentration of 53.1% by mass, a benzene ring content of 12.3% by mass due to the phenol, and a urethane bond group concentration of 6.2. It was mass%.

Examples 7-12 and Comparative Examples 1-3
According to the composition ratio (solid content mass ratio) shown in Tables 1 and 2, each component was blended, and further, methyl ethyl ketone was added so that the nonvolatile content of the composition was finally 55% by mass to produce a varnish. A curability test was performed using this. Moreover, the laminated board was created on the following laminated board creation conditions using each varnish, and the combustion test and the dielectric property were evaluated. In addition, about epoxy resin (A-2)-epoxy resin (A-4), another component is added to the resin solution obtained in Examples 2-4, and methyl ethyl ketone is finally added, and non volatile matter is 55 It adjusted so that it might become mass%, and it was set as the varnish.

[Laminate production conditions]
Substrate: 180 μm; Nitto Boseki Co., Ltd. glass cloth “WEA 7628 H258” ply number: 8, prepreg condition: 160 ° C./4 minutes, copper foil: 35 μm; Furukawa Sakito Wheel Co., Ltd., curing condition: After molding for 1.5 hours at 200 ° C. and 40 kg / cm ² Thickness: 1.6 mm, resin content: 40%

[Physical property test conditions]
Curability test: An amount of varnish with a solid mass of 0.15 g is placed on a cure plate heated to 160 ° C. (manufactured by THERMO ELECTRIC), and time measurement is started with a stopwatch. Stir the sample evenly with the tip of the rod and stop the stopwatch when the sample breaks into a string and remains on the plate. The time until this sample was cut and remained on the plate was defined as the gel time.
Combustion test: Based on the UL-94 vertical test, a combustion test was performed using five test pieces (laminated plates prepared by the above method) having a thickness of 1.6 mm.

Dielectric properties: Dielectric constant and dielectric loss tangent at frequencies of 100 MHz and 1 GHz were measured using a dielectric property evaluator (laminate test piece size: 75 × 25 × 2 mm)

In addition, the compounding component in Table 1 and Table 2 is as follows.
Phenol novolac resin: Phenol novolak resin (phenolic hydroxyl group equivalent 105 g / eq, softening point 120 ° C.)
2E4MZ: 2-ethyl-4-methylimidazole naphthalene type epoxy resin (x): 2,7-diglycidyloxynaphthalene (epoxy equivalent 142 g / eq.)
Naphthalene type epoxy resin (y): epoxidized naphthol dimer obtained by reacting 2,7-dihydroxynaphthalene with formaldehyde (epoxy equivalent 166 g / eq.)
Dicyclopentadiene type epoxy resin: Epoxidized product of dicyclopentadiene / phenol addition polymer (epoxy equivalent 275 g / eq.)

Claims (9)

An epoxy resin (A) having a structure represented by the following structural formula 1 and having an epoxy equivalent in the range of 300 to 2000 g / equivalent, and a curing agent (B) are essential components. Epoxy resin composition.

(In Structural Formula 1, G is a glycidyl group, Ar ¹ is a naphthylene group, or the following Structural Formula 2

(In Structural Formula 2, X represents an alkylidene group having 1 to 3 carbon atoms or a sulfonyl group, and R ^{1 to} R ⁴ each independently represents a hydrogen atom or a methyl group.) Group, Ar ² represents an aromatic hydrocarbon group, Y represents a phenoxy group or a naphthoxy group, and n is 0.05 to 2.8 on the average of the repeating units. ) The epoxy resin composition according to claim 1, wherein the epoxy resin (A) contains 5 to 15% by mass of a urethane bond group. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin (A) is obtained by reacting a bifunctional epoxy resin (a) with phenol or naphthol (b) and a diisocyanate compound (c). . In the reaction, the bifunctional epoxy resin (a) is reacted with phenol or naphthol (b), and then the resulting reaction product is reacted with the diisocyanate compound (c) at a temperature of 40 to 100 ° C. The epoxy resin composition according to claim 3. The epoxy resin composition according to claim 3, wherein the bifunctional epoxy resin (a) is a liquid bisphenol type epoxy resin. The epoxy resin composition according to claim 3, wherein the bifunctional epoxy resin (a) is diglycidyloxynaphthalene. The epoxy resin composition according to any one of claims 1 to 6 , wherein the curing agent (B) is a phenol novolac resin. The epoxy resin composition according to any one of claims 1 to 7 , further comprising an organic solvent in addition to the epoxy resin (A) and the curing agent (B). Hardened | cured material obtained by hardening the epoxy resin composition as described in any one of Claims 1-8 .