Composition, adhesive, cured product and electronic component

Abstract

To provide an epoxy resin-containing composition which suppresses occurrence of bleeding in heating treatment, to provide an adhesive using the composition, to provide a cured product of the composition, and to provide an electronic component using the composition.SOLUTION: A composition contains an epoxy resin, fumed silica having at least one selected from the group consisting of a dimethylsilyl group and a trimethylsilyl group, a curing accelerator, and a thiol compound exhibiting viscosity at 25°C of 0.2 Pa s or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to compositions, adhesives, cured products, and electronic components.

Background Art

[0002] Epoxy resins are used in various applications such as adhesives. For example, Patent Document 1 below discloses a composition containing a specific epoxy resin, a specific thiol compound as a curing agent, a solid dispersion type latent curing accelerator, and a borate ester compound.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] When a conventional composition containing an epoxy resin is used as an adhesive or the like, components contained in the composition may bleed out at the applied portion of the composition. The phenomenon of bleeding out of the components of the composition is generally called bleed. This problem of bleed becomes prominent particularly during heating when the composition is cured. When bleed occurs during heat curing, the composition components spread to parts that are not originally planned, which may lead to a reduction in yield in the manufacture of electronic devices and the like. For example, when bleed occurs near a wiring, the components that have oozed out from the composition may contaminate the wiring.

[0005] An object of the present disclosure includes providing an epoxy resin-containing composition that suppresses the occurrence of bleed during heat treatment, providing an adhesive using the above composition, providing a cured product of the above composition, and providing an electronic component using the above composition.

Means for Solving the Problems

[0006] <1> A composition comprising an epoxy resin, fumed silica having at least one selected from the group consisting of a dimethylsilyl group and a trimethylsilyl group, a curing accelerator, and a thiol compound having a viscosity of 0.2 Pa·s or more at 25°C. <2> The composition according to <1>, wherein the viscosity of the thiol compound is in the range of 0.2 Pa·s to 15 Pa·s at 25°C. <3> The composition according to <1> or <2>, wherein the content of the fumed silica is in the range of 0.1% by mass to 20% by mass based on the total mass of the composition. <4> The composition according to any one of <1> to <3>, wherein the content of the thiol compound is in the range of 1% by mass to 80% by mass based on the total mass of the composition. <5> The composition according to any one of <1> to <4>, wherein the thiol compound has no ring skeleton. <6> The composition according to any one of <1> to <4>, wherein the thiol compound has a ring skeleton. <7> The composition according to any one of <1> to <6>, wherein the thiol compound has no ester bond. <8> An adhesive comprising the composition according to any one of <1> to <7>. <9> A cured product of the composition according to any one of <1> to <7>. <10> An electronic component comprising the cured product according to <9>.

Advantages of the Invention

[0007] The present disclosure provides an epoxy resin-containing composition that suppresses the generation of bleed during heat treatment, an adhesive using the above composition, a cured product of the above composition, and an electronic component using the above composition.

Embodiments for Carrying Out the Invention

[0008] Hereinafter, embodiments of the present disclosure will be described in detail. At least one of the following embodiments may be appropriately changed without departing from the gist of the present disclosure.

[0009] <Composition> The composition in the present disclosure contains the following components (A) to (D). (A) Epoxy resin (B) Fumed silica having at least one selected from the group consisting of a dimethylsilyl group and a trimethylsilyl group (C) Curing accelerator (D) Thiol compound showing a viscosity of 0.2 Pa·s or more at 25°C

[0010] The composition containing components (A) to (D) suppresses the generation of bleed during heat treatment. This effect is presumably mainly due to the use of component (B) having a short-chain alkylsilyl group and component (D) having a relatively high viscosity. Component (D) showing a viscosity of 0.2 Pa·s or more at 25°C is considered to suppress the generation of bleed at a relatively low temperature (for example, normal temperature). Compared with a long-chain alkylsilyl group such as an octylsilyl group, the movement of a short-chain alkylsilyl group such as a dimethylsilyl group and a trimethylsilyl group is small even at a relatively high temperature. Since the influence of the short-chain alkylsilyl group of component (B) on the viscosity of the composition during the heating process is small, it is considered that bleed is less likely to occur even at a relatively high temperature. Therefore, the composition containing components (A) to (D) is considered to suppress the generation of bleed, particularly the generation of bleed during heat treatment.

[0011] (Epoxy resin) The composition contains an epoxy resin. One or more kinds of epoxy resins may be used.

[0012] The epoxy resin has at least one epoxy group. In a preferred embodiment, the epoxy resin contains an epoxy resin having at least two epoxy groups.

[0013] The epoxy equivalent of the epoxy resin is preferably in the range of 40 g / eq to 10,000 g / eq, more preferably 50 g / eq to 8,000 g / eq, and still more preferably 60 g / eq to 5,000 g / eq. In the present disclosure, "epoxy equivalent" means the mass of the epoxy resin per epoxy group, and the measuring method of the epoxy equivalent shall conform to "JIS K 7236 (2009)".

[0014] The type of the epoxy resin is not limited. The epoxy resin may be selected from the epoxy resins used in known epoxy resin-containing compositions. Examples of the epoxy resin include polyglycidyl ether, glycidyl ether ester, polyglycidyl ester, epoxidized phenol novolak resin, epoxidized cresol novolak resin, epoxidized polyolefin, cycloaliphatic epoxy resin, and urethane-modified epoxy resin.

[0015] Examples of the polyglycidyl ether include reaction products of polyhydric alcohols and epichlorohydrin. Examples of the polyhydric alcohols include polyhydric phenols, glycerin, and polyethylene glycol. Examples of the polyhydric phenols include bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol.

[0016] Examples of the glycidyl ether ester include reaction products of hydroxycarboxylic acids and epichlorohydrin. Examples of the hydroxycarboxylic acids include p-hydroxybenzoic acid and β-hydroxynaphthoic acid.

[0017] Examples of the polyglycidyl ester include reaction products of polycarboxylic acids and epichlorohydrin. Examples of the polycarboxylic acids include phthalic acid and terephthalic acid.

[0018] From the viewpoints of high heat resistance and low moisture permeability, in a preferred embodiment, the epoxy resin includes at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl aralkyl type epoxy resin, phenol aralkyl type epoxy resin, aromatic glycidylamine type epoxy resin, and epoxy resin having a dicyclopentadiene structure. In a preferred embodiment, the epoxy resin includes at least one selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin.

[0019] The epoxy resin may be a liquid epoxy resin or a solid epoxy resin. The liquid epoxy resin is in a liquid state at 25°C. The solid epoxy resin is in a solid state at 25°C. Both the liquid epoxy resin and the solid epoxy resin may be used. In a preferred embodiment, the epoxy resin includes a liquid epoxy resin. Preferably, the composition is in a liquid state at 25°C for use as an adhesive. From the viewpoints of coatability, processability, and adhesiveness, in a preferred embodiment, at least 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass, still more preferably 80% by mass, still more preferably 90% by mass, particularly preferably 100% by mass of the total mass of the epoxy resin is the liquid epoxy resin.

[0020] Examples of the liquid epoxy resin include bisphenol A type epoxy resin (for example, "jER828EL", "jER827", and "YL980" manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (for example, "jER807" manufactured by Mitsubishi Chemical Corporation), naphthalene type difunctional epoxy resin (for example, "HP4032" and "HP4032D" manufactured by DIC Corporation), a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (for example, "ZX-1059" manufactured by Nippon Steel Chemical & Material Co., Ltd.), and hydrogenated structure epoxy resin (for example, "jERYX8000" manufactured by Mitsubishi Chemical Corporation). Further, examples of commercially available products of the liquid epoxy resin include "YX7105" (manufactured by Mitsubishi Chemical Corporation) and "EXA-4850-150" (manufactured by DIC Corporation).

[0021] Examples of solid epoxy resins include naphthalene-type tetrafunctional epoxy resins (e.g., "HP4700" manufactured by DIC Corporation), dicyclopentadiene-type polyfunctional epoxy resins (e.g., "HP7200" manufactured by DIC Corporation), naphthol-type epoxy resins (e.g., "ESN-475V" manufactured by Nippon Steel Chemical & Material Co., Ltd.), epoxy resins having a butadiene structure (e.g., "PB-3600" manufactured by Daicel Corporation), and epoxy resins having a biphenyl structure (e.g., "NC3000H" and "NC3000L" manufactured by Nippon Kayaku Co., Ltd. or "jERYX4000" manufactured by Mitsubishi Chemical Corporation).

[0022] The epoxy resin may contain a linear hydrocarbon structural unit having 4 or more carbon atoms and / or a polyalkylene ether structural unit having 3 or more ether oxygen atoms. Examples of the linear hydrocarbon structural unit having 4 or more carbon atoms are -(CH2) x -. x is 4 or more. x may be in the range of 4 to 20 or 4 to 20. The number of ether oxygen atoms in the polyalkylene ether structural unit may be in the range of 3 to 20 or 3 to 10.

[0023] The epoxy resin may be an epoxy resin represented by the following formula (1) or the following formula (2).

[0024]

Chemical formula

[0025] In formula (1) and formula (2), X, X1, and X2 are each independently a divalent non-aromatic hydrocarbon group containing at least 4 -(CH2)- constituting the main skeleton of the epoxy resin, Ar, Ar1, and Ar2 are each independently a divalent hydrocarbon group containing a divalent aromatic group constituting the main skeleton of the epoxy resin, and n and m are each independently an integer of 1 to 20. The "main skeleton of the epoxy resin" means the longest skeleton connecting two epoxy groups located at the ends of the epoxy resin.

[0026] In a preferred embodiment, the "divalent non-aromatic hydrocarbon group containing at least 4 -(CH2)-" in X, X1 and X2 is -O-CH(-CH3)-(O-(CH2) p ) q -O-CH(-CH3)-, -(O-(CH2) r ) s -, -(O-CH2-CH(-CH3)) t -, -O-CH2-CH(-OH)-CH2-(O-(CH2) u ) v -O-CH2-CH(-OH)-CH2-, -(O-(CH2) w ) y -O-CH2-CH(-OH)- and -(O-CH2-CH(-CH3)) z -O-CH2-CH(-OH)-, and p, q, r, s, t, u, v, w, y and z are each independently an integer from 1 to 20.

[0027] Regarding the "divalent hydrocarbon group containing a divalent aromatic group" in Ar, Ar1 and Ar2, examples of the aromatic group include a phenylene group, a naphthalene group, an anthracene group and a biphenyl group. The phenylene group may be an orthophenylene group, a metaphenylene group or a paraphenylene group. The hydrocarbon group may contain two or more aromatic groups. When the hydrocarbon group contains two or more aromatic groups, the aromatic groups may be directly bonded to each other. The aromatic groups may be bonded to each other via an alkylene group, an ether bond, an ester bond, an amide bond or two carbons bonded by a double bond or a triple bond. Examples of preferred divalent hydrocarbon groups include divalent hydrocarbon groups represented by the following formula (3) or the following formula (4).

[0028]

Chemical formula

[0029] The epoxy resin may be a modified bisphenol type epoxy resin represented by the following formula (5).

[0030]

Chemical formula

[0031] In formula (5), Y is an aliphatic hydrocarbon, Z is CH2 or C(CH3), and n is from 0 to 10, preferably from 1 to 8.

[0032] The epoxy resin may be a flexible epoxy resin. Examples of commercially available flexible epoxy resins include "YX7105" (Mitsubishi Chemical Corporation), "YX7110" (Mitsubishi Chemical Corporation), "YX7400" (Mitsubishi Chemical Corporation), and "EXA-4850-150" (DIC Corporation).

[0033] The content of the epoxy resin is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, based on the total mass of the composition. Further, the content of the epoxy resin is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, based on the total mass of the composition. The content of the epoxy resin is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, based on the total mass of the composition. Further, the content of the epoxy resin is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, based on the total mass of the composition. For example, the content of the epoxy resin may be in the range of 5% by mass to 95% by mass based on the total mass of the composition.

[0034] (Fumed silica) The composition contains fumed silica having at least one selected from the group consisting of dimethylsilyl groups and trimethylsilyl groups. One type or two or more types of fumed silica may be used.

[0035] In a preferred embodiment, at least one selected from the group consisting of dimethylsilyl groups and trimethylsilyl groups is present at least on the surface of the fumed silica. The dimethylsilyl groups and trimethylsilyl groups in the fumed silica are detectable by time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0036] Examples of methods for introducing dimethylsilyl groups or trimethylsilyl groups into fumed silica include surface treatment using compounds having dimethylsilyl groups or trimethylsilyl groups. Examples of compounds having dimethylsilyl groups include dimethyldichlorosilane. Examples of compounds having trimethylsilyl groups include hexamethyldisilazane.

[0037] In a preferred embodiment, the specific surface area of fumed silica is in the range of 5 m 2 / g to 500 m 2 / g. The lower limit of the specific surface area may be 40 m 2 / g, 20 m 2 / g or 10 m 2 / g. The upper limit may be 200 m 2 / g, 300 m 2 / g or 400 m 2 / g. In the present disclosure, the specific surface area is measured by BET (nitrogen adsorption method).

[0038] Examples of commercially available fumed silica include "RX300" (manufactured by Nippon Aerosil Co., Ltd.), "R976S" (manufactured by Nippon Aerosil Co., Ltd.) and "R974" (manufactured by Nippon Aerosil Co., Ltd.).

[0039] From the viewpoint of further suppressing the occurrence of bleeding, in a preferred embodiment, the content of fumed silica is in the range of 0.1% by mass to 20% by mass based on the total mass of the composition. The lower limit of the content is preferably 2% by mass, more preferably 3% by mass, and still more preferably 5% by mass. The upper limit of the content is preferably 18% by mass, more preferably 16% by mass, and still more preferably 14% by mass.

[0040] (Curing accelerator) The composition contains a curing accelerator. One or more curing accelerators may be used.

[0041] The type of the curing accelerator is not limited. The curing accelerator may be selected from the curing accelerators used in known epoxy resin-containing compositions. In a preferred embodiment, the curing accelerator includes a latent curing accelerator. A latent curing accelerator is a compound that does not contribute to the curing of the epoxy resin at normal temperature (25 °C) and promotes the curing of the epoxy resin when heated.

[0042] In a preferred embodiment, the latent curing accelerator is a solid dispersion type latent curing accelerator. A solid dispersion type latent curing accelerator is a solid that is insoluble in the epoxy resin at normal temperature (25 °C) and becomes solubilized by heating and functions as a curing accelerator for the epoxy resin. Examples of the solid dispersion type latent curing accelerator include imidazole compounds that are solid at 25 °C and solid dispersion type amine adduct-based latent curing accelerators. The solid dispersion type amine adduct-based latent curing accelerator is preferred.

[0043] Examples of imidazole compounds that are solid at 25 °C include 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2’-methylimidazolyl-(1)’)-ethyl-S-triazine · isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole-trimeritate, 1-cyanoethyl-2-phenylimidazole-trimeritate, N-(2-methylimidazolyl-1-ethyl)-urea, and N,N’-(2-methylimidazolyl-(1)-ethyl)-adipoyldiamide.

[0044] Examples of the solid dispersion type amine adduct-based latent curing accelerator include reaction products of an amine compound and an epoxy compound and reaction products of an amine compound and an isocyanate compound or a urea compound.

[0045] Examples of amine compounds used as raw materials for solid dispersion type amine adduct-based latent curing accelerators include compounds having at least one active hydrogen capable of undergoing an addition reaction with an epoxy group and having at least one amino group selected from primary amino groups, secondary amino groups, and tertiary amino groups. Examples of amine compounds as described above include aliphatic amines (e.g., diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane), aromatic amine compounds (e.g., 4,4'-diaminodiphenylmethane and 2-methylaniline), and nitrogen atom-containing heterocyclic compounds (e.g., 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine).

[0046] Among amine compounds, compounds having a tertiary amino group in the molecule are raw materials that give potential curing accelerators with excellent curing acceleration ability. Examples of such compounds include dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2-mercaptopyridine, 2-benzimidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide.

[0047] Examples of epoxy compounds used as raw materials for solid dispersion-type amine adduct-based latent curing accelerators include polyglycidyl ethers, glycidyl ether esters, polyglycidyl esters, glycidyl amine compounds, epoxidized phenol novolak resins, epoxidized cresol novolak resins, epoxidized polyolefins, butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate. The epoxy compound may be a compound having one epoxy group or a compound having at least two epoxy groups.

[0048] Examples of polyglycidyl ethers include reaction products of polyhydric alcohols and epichlorohydrin. Examples of polyhydric alcohols include polyhydric phenols, glycerin, and polyethylene glycol. Examples of polyhydric phenols include bisphenol A, bisphenol F, catechol, and resorcinol.

[0049] Examples of glycidyl ether esters include reaction products of hydroxycarboxylic acids and epichlorohydrin. Examples of hydroxycarboxylic acids include p-hydroxybenzoic acid and β-hydroxynaphthoic acid.

[0050] Examples of polyglycidyl esters include reaction products of polycarboxylic acids and epichlorohydrin. Examples of polycarboxylic acids include phthalic acid and terephthalic acid.

[0051] Examples of glycidyl amine compounds include reaction products of 4,4'-diaminodiphenylmethane or m-aminophenol and epichlorohydrin.

[0052] When producing a latent curing accelerator by the reaction of an amine compound and an epoxy compound, an active hydrogen compound having at least two active hydrogens in the molecule may be added. Examples of the active hydrogen compound include polyhydric phenols (e.g., bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolak resin), polyhydric alcohols (e.g., trimethylolpropane), polyhydric carboxylic acids (e.g., adipic acid and phthalic acid), 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.

[0053] Examples of the isocyanate compound used as a raw material for the solid dispersion type amine adduct-based latent curing accelerator include monofunctional isocyanate compounds (e.g., n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate), polyfunctional isocyanate compounds (e.g., hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate), and terminal isocyanate group-containing compounds obtained by the reaction of a polyfunctional isocyanate compound and an active hydrogen compound. Examples of the terminal isocyanate group-containing compounds include addition compounds having terminal isocyanate groups obtained by the reaction of toluylene diisocyanate and trimethylolpropane, and addition compounds having terminal isocyanate groups obtained by the reaction of toluylene diisocyanate and pentaerythritol.

[0054] Examples of the urea compound used as a raw material for the solid dispersion type amine adduct-based latent curing accelerator include urea and thiourea.

[0055] Examples of commercially available products of the reaction product of an amine compound and an epoxy compound include "Amicure PN-40J" (manufactured by Ajinomoto Fine-Techno Co., Inc.), "Amicure PN-F" (manufactured by Ajinomoto Fine-Techno Co., Inc.), "Amicure PN-23" (manufactured by Ajinomoto Fine-Techno Co., Inc.), "Amicure PN-H" (manufactured by Ajinomoto Fine-Techno Co., Inc.), "Novacure HX-3742" (manufactured by Asahi Kasei Corporation), and "Novacure HX-3721" (manufactured by Asahi Kasei Corporation).

[0056] Examples of commercially available products of the reaction product of an amine compound and an isocyanate compound or a urea compound include "Fujicure FXR-1020" (manufactured by Fujikasei Co., Ltd.) and "Fujicure FXR-1030" (manufactured by Fujikasei Co., Ltd.).

[0057] The content of the curing accelerator is preferably in the range of 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and still more preferably 0.5% by mass to 5% by mass based on the total mass of the composition.

[0058] The ratio of the total mass of the curing accelerator to the total mass of the epoxy resin is preferably in the range of 0.1% by mass to 100% by mass, more preferably in the range of 1% by mass to 60% by mass, and still more preferably in the range of 5% by mass to 30% by mass.

[0059] (Thiol compound) The composition contains a thiol compound having a viscosity of 0.2 Pa·s or more at 25°C. One type or two or more types of thiol compounds may be used.

[0060] The viscosity of the thiol compound is 0.2 Pa·s or more at 25°C. From the viewpoint of further suppressing the occurrence of bleed, the lower limit of the viscosity of the thiol compound is preferably 0.4 Pa·s, more preferably 0.6 Pa·s, still more preferably 0.8 Pa·s. The lower limit of the viscosity of the thiol compound may be 1 Pa·s or 3 Pa·s. The upper limit of the viscosity of the thiol compound is preferably 40 Pa·s, more preferably 20 Pa·s, still more preferably 15 Pa·s. The upper limit of the viscosity of the thiol compound may be 10 Pa·s, 8 Pa·s or 6 Pa·s. For example, the viscosity of the thiol compound may be in the range of 0.2 Pa·s to 40 Pa·s at 25°C. In the present disclosure, the viscosity of the thiol compound is measured by a rheometer.

[0061] Examples of the thiol compound include tris(3-mercaptopropyl) isocyanurate (abbreviation: TMPIC), pentaerythritol tetrakis(3-mercaptobutyrate) (for example, "Karenz MT (registered trademark) PE1" manufactured by Resona Co., Ltd.), and pentaerythritol tripropane thiol (for example, "Multhiol Y-3" manufactured by SC Organic Chemistry Co., Ltd.).

[0062] The molecular weight of the thiol compound is preferably in the range of 200 to 700, more preferably 250 to 500, still more preferably 300 to 400.

[0063] The thiol compound has at least one thiol group. In a preferred embodiment, the thiol compound includes a compound having at least two thiol groups. The number of thiol groups in the thiol compound is preferably from 2 to 6, more preferably from 3 to 6, still more preferably from 3 to 5. Further, the number of thiol groups in the thiol compound is preferably 3 or 4, more preferably 3.

[0064] The thiol equivalent of the thiol compound is preferably in the range of 50 g / eq to 400 g / eq, more preferably in the range of 50 g / eq to 400 g / eq, and still more preferably in the range of 70 g / eq to 200 g / eq. Further, the thiol equivalent of the thiol compound is preferably in the range of 80 g / eq to 150 g / eq. In the present disclosure, "thiol equivalent" means the mass of the thiol compound per thiol group.

[0065] In a preferred embodiment, the thiol compound does not have an ester bond. The ester bond is a bond represented by "-C(=O)O-". Since hydrolysis based on the ester bond does not occur, the moisture resistance is improved and the reliability is increased.

[0066] In a preferred embodiment, the thiol compound does not have a hydroxy group. A thiol compound without a hydroxy group can improve the pot life of the composition. As a result, the composition can achieve both pot life and rapid curability.

[0067] In a preferred embodiment, the thiol compound does not have a ring skeleton. When the thiol compound does not have a ring skeleton, the skeleton of the thiol compound becomes flexible and the peel strength can be improved.

[0068] In a preferred embodiment, the thiol compound has a ring skeleton. A thiol compound having a ring skeleton can improve the shear adhesion strength. The thiol compound having a ring skeleton may be a monocyclic compound or a polycyclic compound. Examples of the ring skeleton include an alicyclic skeleton, an aromatic ring skeleton, and a heterocyclic skeleton. The ring skeleton is preferably an aromatic ring skeleton or a heterocyclic skeleton, more preferably a heterocyclic skeleton. Examples of the heterocyclic skeleton include a heterocyclic skeleton having a 5-membered ring to 8-membered ring containing at least one nitrogen atom. Specifically, examples of the heterocyclic skeleton include an isocyanuric skeleton and a glycoluril skeleton.

[0069] In a preferred embodiment, the thiol compound includes a compound represented by the following formula (6).

[0070] [Chemical formula]

[0071] In formula (6), R1, R2, and R3 each independently represent a linear or branched divalent hydrocarbon group having 1 to 6, preferably 1 to 5 carbon atoms. The hydrocarbon group may contain a divalent group represented by the following (6a) to (6c). The number of divalent groups may be one or two or more.

[0072] [Chemical formula]

[0073] Examples of the compound represented by formula (6) include tris(3-mercaptopropyl) isocyanurate (abbreviation: TMPIC).

[0074] From the viewpoint of the curability of the composition, in a preferred embodiment, the ratio of the number of thiol groups of the thiol compound to the number of epoxy groups of the epoxy resin (total number of thiol groups of the thiol compound / total number of epoxy groups of the epoxy resin) is preferably 0.1 to 2.0, more preferably 0.5 to 1.2. The "number of epoxy groups" refers to the value obtained by dividing the mass of the epoxy resin contained in the composition by the epoxy equivalent (mass of epoxy groups / epoxy equivalent). When a plurality of types of epoxy resins are contained in the composition, the number of epoxy groups represents the sum of the values obtained by dividing the mass of each epoxy resin by its respective epoxy equivalent. The "number of thiol groups" refers to the value obtained by dividing the mass of the thiol contained in the composition by the thiol equivalent (mass of thiol groups / thiol equivalent). When a plurality of types of thiols are contained in the composition, the number of thiol groups represents the sum of the values obtained by dividing the mass of each thiol by its respective thiol equivalent. When the composition contains a thiol compound other than a "thiol compound having a viscosity of 0.2 Pa·s or more at 25°C", the above ratio is calculated based on the number of thiol groups of all the thiol compounds contained in the composition.

[0075] From the perspective of further suppressing the occurrence of bleeding, in a preferred embodiment, the content of the thiol compound is in the range of 1% by mass to 80% by mass based on the total mass of the composition. The lower limit of the above content is preferably 3% by mass, more preferably 5% by mass, and still more preferably 7% by mass. The upper limit of the above content is preferably 75% by mass, more preferably 70% by mass, and still more preferably 60% by mass.

[0076] (Stabilizer) The composition may further contain a stabilizer. The stabilizer can improve the storage stability of the composition. One or more storage stabilizers may be used.

[0077] Examples of the stabilizer include borate ester compounds, titanate ester compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and mercapto organic acids. In a preferred embodiment, the composition contains at least one stabilizer selected from the group consisting of borate ester compounds, titanate ester compounds, aluminate compounds, zirconate compounds, isocyanate compounds, carboxylic acids, acid anhydrides, and mercapto organic acids.

[0078] Examples of the borate ester compound include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, tri-n-butyl borate, tripentyl borate, triallyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyl) borane, bis(1,4,7,10-tetraoxaundecyl)(1,4,7,10,13-pentaoxatetradecyl)(1,4,7-trioxaundecyl) borane, tribenzyl borate, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, and triethanolamine borate.

[0079] Examples of titanate compounds include tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, and tetraoctyl titanate.

[0080] Examples of aluminate compounds include triethyl aluminate, tripropyl aluminate, triisopropyl aluminate, tributyl aluminate, and trioctyl aluminate.

[0081] Examples of zirconate compounds include tetraethyl zirconate, tetrapropyl zirconate, tetraisopropyl zirconate, and tetrabutyl zirconate.

[0082] Examples of isocyanate compounds include n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 2,4-toluene diisocyanate, toluylene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, and bicycloheptane triisocyanate.

[0083] Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, acrylic acid, methacrylic acid, crotonic acid, monochloroacetic acid, dichloroacetic acid, glycolic acid, lactic acid, glyoxylic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, maleic acid, benzoic acid, halogenated benzoic acid, toluic acid, phenylacetic acid, cinnamic acid, mandelic acid, phthalic acid, and trimesic acid.

[0084] Examples of acid anhydrides include succinic anhydride, dodecenyl succinic anhydride, maleic anhydride, an adduct of methylcyclopentadiene and maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.

[0085] Examples of mercapto organic acids include mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptosuccinic acid, dimercaptosuccinic acid, mercapto aliphatic monocarboxylic acids and mercapto aromatic monocarboxylic acids (e.g., mercaptobenzoic acid) obtained by esterification of hydroxy organic acids and mercapto organic acids.

[0086] From the viewpoints of versatility, safety, and storage stability of the composition, the stabilizer is preferably a borate compound, more preferably triethyl borate, tri-n-propyl borate, triisopropyl borate, or tri-n-butyl borate, and even more preferably triethyl borate.

[0087] The content of the stabilizer is preferably in the range of 0.0005% by mass to 30% by mass, more preferably 0.02% by mass to 20% by mass, and even more preferably 0.1% by mass to 10% by mass based on the total mass of the composition.

[0088] (Other components) The composition may further contain other components as needed. Examples of other components include diluents, solvents, pigments, flexibility imparting agents, coupling agents, antioxidants, thixotropy imparting agents, and dispersants.

[0089] The composition may contain fumed silica that does not have dimethylsilyl groups and trimethylsilyl groups, as long as it does not deviate from the gist of the present disclosure. However, from the viewpoint of further suppressing the occurrence of bleeding, it is preferable to lower the content rate of fumed silica that does not have dimethylsilyl groups and trimethylsilyl groups. The content rate of fumed silica that does not have dimethylsilyl groups and trimethylsilyl groups with respect to the total mass of fumed silica contained in the composition is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less, and particularly preferably 0% by mass. In a preferred embodiment, the composition does not contain fumed silica that does not have dimethylsilyl groups and trimethylsilyl groups. The composition may contain inorganic fillers other than fumed silica, such as silica, calcium carbonate, alumina, zirconia, and aluminum nitride, as long as it does not deviate from the gist of the present disclosure.

[0090] The composition may contain a thiol compound having a viscosity of less than 0.2 Pa·s at 25°C, as long as it does not deviate from the gist of the present disclosure. However, from the viewpoint of further suppressing the occurrence of bleeding, it is preferable to lower the content rate of the thiol compound having a viscosity of less than 0.2 Pa·s at 25°C. The content rate of the thiol compound having a viscosity of less than 0.2 Pa·s at 25°C is preferably in the range of 0% by mass to 3% by mass, more preferably 0% by mass to 1% by mass, and still more preferably 0% by mass to 0.1% by mass, based on the total mass of the composition. From the viewpoint of further suppressing the occurrence of bleeding, the ratio of the total mass of the thiol compound having a viscosity of less than 0.2 Pa·s at 25°C to the total mass of the thiol compound having a viscosity of 0.2 Pa·s or more at 25°C is preferably in the range of 0% by mass to 5% by mass, more preferably 0% by mass to 3% by mass, and still more preferably 0% by mass to 1% by mass. In a preferred embodiment, the composition does not contain a thiol compound having a viscosity of less than 0.2 Pa·s at 25°C.

[0091] The composition may contain an organic solvent. However, from the perspective of suppressing the occurrence of bleeding, it is preferable to lower the content rate of the organic solvent. The content rate of the organic solvent is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and particularly preferably 0% by mass, based on the total mass of the composition. In a preferred embodiment, the composition does not contain an organic solvent.

[0092] (Properties of the composition) In a preferred embodiment, the composition is a liquid composition having fluidity at 25°C.

[0093] In a preferred embodiment, the composition exhibits a viscosity in the range of 1 Pa·s to 200 Pa·s under the measurement conditions of 25°C and 2 rpm. The lower limit of the above viscosity may be 20 Pa·s or 5 Pa·s. The upper limit of the above viscosity may be 75 Pa·s or 110 Pa·s. In the present disclosure, the viscosity of the composition is measured by an E-type viscometer. "rpm" is an abbreviation for "revolutions per minute".

[0094] In a preferred embodiment, the composition exhibits a viscosity in the range of 1 Pa·s to 60 Pa·s under the measurement conditions of 25°C and 20 rpm. The lower limit of the above viscosity may be 20 Pa·s or 5 Pa·s. The upper limit of the above viscosity may be 30 Pa·s or 40 Pa·s.

[0095] In a preferred embodiment, the thixotropy index represented by the following formula is in the range of 0.5 to 7. The lower limit of the above thixotropy index is preferably 0.6, more preferably 0.8, and still more preferably 1. The upper limit of the above thixotropy index is preferably 4, more preferably 5, and still more preferably 6. Formula: Thixotropy index = ([Viscosity of the composition obtained under the measurement conditions of 25°C and 2 rpm] ÷ [Viscosity of the composition obtained under the measurement conditions of 25°C and 20 rpm]) × 100

[0096] (Method for producing the composition) The manufacturing method of the composition is not limited as long as the target composition can be obtained. For example, the composition is manufactured by mixing an epoxy resin, fumed silica, a curing accelerator, a thiol compound, and other components as required.

[0097] (Uses and Applications of the Composition) Examples of the uses of the composition include casting agents, sealing agents, encapsulants, fiber-reinforcing resins, coating agents, underfill agents, die attach agents, electromagnetic wave shielding materials, paints, and adhesives. In a preferred embodiment, the composition is used as an adhesive. The composition may be used, for example, as an adhesive in the assembly of electronic components. Examples of electronic components include camera modules, printed circuit boards, semiconductor elements, and integrated circuits. The electronic components may include the cured product of the composition. The composition may be injected between at least two electronic components, for example, between a semiconductor element and a substrate.

[0098] The composition can provide a cured product. For example, the composition can be cured by heat treatment. The temperature of the heat treatment is preferably in the range of 70°C to 150°C, more preferably in the range of 75°C to 120°C, and even more preferably in the range of 80 to 100°C. The time of the heat treatment is preferably in the range of 1 minute to 60 minutes, more preferably in the range of 3 minutes to 45 minutes.

Examples

[0099] Hereinafter, the present disclosure will be described based on examples. However, the present disclosure is not limited to the following examples. The following technical matters may be appropriately changed without departing from the spirit of the present disclosure.

[0100] <Manufacture of the Composition> According to the following procedure, a composition containing the components described in Table 1 and Table 2 was manufactured. Epoxy resin and fumed silica were added to a dedicated container. The epoxy resin and fumed silica were thoroughly mixed using a mixer (manufactured by Shinky Co., ARE-310) at room temperature of 25°C and 2000 rpm for about 30 seconds to about 60 seconds, and then kneaded using three rolls to obtain a dispersion. A latent curing accelerator was added to the dispersion. The dispersion and the latent curing accelerator were thoroughly mixed using a mixer (manufactured by Shinky Co., ARE-310) at room temperature of 25°C and 2000 rpm for about 30 seconds to about 60 seconds to obtain a masterbatch. A thiol compound was added to the masterbatch. The masterbatch and the thiol compound were mixed using a mixer (manufactured by Shinky Co., ARE-310) at room temperature of 25°C and 2000 rpm for 20 seconds. The obtained mixture was defoamed using a stirring defoaming machine (manufactured by Kyoritsu Seiki Co., HM-200W) under vacuum at 900 rpm for 2 minutes to obtain a composition. Regarding the control of pressure, the vacuum condition of the stirring defoaming machine was set to "0".

[0101] Details of the materials of the composition are as follows. The name of each material is represented by an abbreviation of the compound name or a product name. The viscosity represents the viscosity at 25°C unless otherwise specified.

[0102] (Epoxy resin) "YL980": Bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent = 186 g / eq, viscosity = 13 Pa·s, molecular weight = 372 "YX7105": Flexible epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent = 489 g / eq, viscosity = 69 Pa·s, molecular weight = 978 "ZX-1059": Bisphenol A type / bisphenol F type epoxy resin manufactured by Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent = 165 g / eq, viscosity = 2 Pa·s, molecular weight = 330 "EXA-4850-150": Manufactured by DIC Corporation, epoxy equivalent = 450 g / eq, viscosity = 15 Pa·s, molecular weight = 900

[0103] (Fumed silica) "RX300": Manufactured by Nippon Aerosil Co., Ltd., fumed silica, surface-modified with trimethylsilyl groups, specific surface area = 180 m 2 / g to 220 m 2 / g, specific gravity = approximately 40 g / L "R976S": Manufactured by Nippon Aerosil Co., Ltd., fumed silica, surface-modified with dimethylsilyl groups, specific surface area = 215 m 2 / g to 265 m 2 / g, specific gravity = approximately 50 g / L "R974": Manufactured by Nippon Aerosil Co., Ltd., fumed silica, surface-modified with dimethylsilyl groups, specific surface area = 150 m 2 / g to 190 m 2 / g, specific gravity = approximately 50 g / L "RY300": Manufactured by Nippon Aerosil Co., Ltd., fumed silica, surface-treated with silicone oil, specific surface area = 110 m 2 / g to 140 m 2 / g, specific gravity = approximately 50 g / L "RY200": Manufactured by Nippon Aerosil Co., Ltd., fumed silica, surface-treated with silicone oil, specific surface area = 80 m 2 / g to 120 m 2 / g, specific gravity = approximately 50 g / L "R805": Manufactured by Nippon Aerosil Co., Ltd., fumed silica, surface-modified with octylsilyl groups, specific surface area = 125 m 2 / g to 175 m 2 / g, specific gravity = 60 g / L

[0104] (Latent curing accelerator) "PN-23": Manufactured by Ajinomoto Fine-Techno Co., Inc., Amicure (registered trademark), solid-dispersion type amine adduct-based latent curing accelerator "PN-40J": Manufactured by Ajinomoto Fine-Techno Co., Inc., Amicure (registered trademark), solid-dispersion type amine adduct-based latent curing accelerator

[0105] (Thiol compound) "TMPIC": Manufactured by Kawaguchi Chemical Industry Co., Ltd., tris(3-mercaptopropyl)isocyanurate, trifunctional thiol having an isocyanuric skeleton, thiol equivalent = 117 g / eq, viscosity = 4.9 Pa·s, molecular weight = 351 "PE1": Resonaq, pentaerythritol tetrakis(3-mercaptobutyrate), 4-functional secondary ester thiol, thiol equivalent = 136 g / eq, viscosity = 0.9 Pa s, molecular weight = 544 "MR-123": Daito Sangyo Co., Ltd., trifunctional non-ester thiol, thiol equivalent = 300g / eq, viscosity = 14.2Pa s, molecular weight = 900 "PEPT" (Multhiol Y-3): SC Organic Chemicals, trifunctional thiol with a pentaerythritol skeleton, thiol equivalent = 124 g / eq, viscosity = 0.2 Pa s, molecular weight = 372 "TMTP": Yodo Chemical Co., Ltd., trimethylolpropane tris(3-mercaptopropionate, trifunctional primary ester thiol, thiol equivalent = 140 g / eq, viscosity = 0.1 Pa s, molecular weight = 420 "BD1": Resonaq Corporation, 1,4-bis(3-mercaptobutyryloxy)butane, bifunctional secondary ester thiol, thiol equivalent = 147g / eq, viscosity = 0.02Pa s, molecular weight = 147

[0106] The method for measuring the viscosity of each of the above-mentioned thiol compounds is as follows. A rheometer (Thermo Fisher Scientific Inc., RheoStress 6000) was used as a viscosity measuring device. A cone plate was used as a measuring tool, and the viscosity was measured at 25° C. with a shear rate of 400 s -1 The viscosity was measured when the cone plate was a C20 / 1-TiL with a diameter of 20 mm. In the viscosity measurement, the distance between the cone tip and the plate was set to 0.052 mm, and 0.04 mL of the sample was used.

[0107] <Measurement of Viscosity and Thixotropy Index> The temperature of the composition was kept at 25°C, and the viscosity of the composition was measured using an E-type viscometer (RE-85U, manufactured by Toki Sangyo Co., Ltd.). Regarding the rotor of the viscometer, an appropriate rotor was selected from the following three types of rotors based on the viscosity at 2 rpm. The specific measurement conditions are shown below. (1) Rotor of viscometer: "1.34°×R24" (when the viscosity at 2 rpm is less than 20 Pa·s), "3°×R14" (when the viscosity at 2 rpm is 20 Pa·s or more and less than 50 Pa·s), or "3°×R9.7" (when the viscosity at 2 rpm is 50 Pa·s or more) (2) Rotational speed: 2 rpm or 20 rpm (3) Measurement time: 2 minutes (4) Sample volume: 1.2 mL (when the rotor is "1.34°×R24"), 0.4 mL (when the rotor is "3°×R14"), or 0.22 mL (when the rotor is "3°×R9.7")

[0108] Next, the thixotropy index was calculated according to the following formula. Formula: Thixotropy index = ([Viscosity of the composition obtained under the measurement conditions of 25°C and 2 rpm]÷[Viscosity of the composition obtained under the measurement conditions of 25°C and 20 rpm])×100

[0109] <Measurement of bleed width> The composition was filled into a dispenser syringe (manufactured by Musashi Engineering Co., Ltd., PSY-10E), and then centrifugal degassing was performed using a centrifugal degassing machine (manufactured by Musashi Engineering Co., Ltd., AWATRON3 AW-50-3). The composition was applied to a copper substrate using an air dispenser (manufactured by Musashi Engineering Co., Ltd., IMAGE MASTER 350PC Smart). Specifically, the composition was applied to the copper substrate so that the diameter of the composition on the substrate was approximately 500 μm. The surface roughness Ra of the copper substrate was 600 μm ± 50 μm. Next, the composition on the copper substrate was heated at 80°C for 30 minutes using a thermal circulation oven (manufactured by Yamato Scientific Co., Ltd., DF-610). Next, the heated composition was observed using a digital microscope (manufactured by Keyence Corporation, VHX-7000), and the maximum diameter of the heated composition in plan view and the maximum diameter of the bleed (the maximum diameter of the portion where the components in the composition oozed out outside the application range of the composition) in plan view were measured. According to the following formula, the width of each bleed was calculated and calculated as the average value of 6 times. Formula: Bleed width = ([Maximum diameter of bleed] - [Maximum diameter of heated composition])÷2

[0110] The width of the bleed was evaluated according to the following criteria. A, B, and C are the passing levels. A: Less than 600 μm B: 600 μm or more and less than 700 μm C: 700 μm or more and less than 800 μm D: 800 μm or more

[0111]

Table 1

[0112]

Table 2

[0113] The compositions used in Examples 1 to 10 contain fumed silica having at least one selected from the group consisting of dimethylsilyl groups and trimethylsilyl groups, and a thiol compound having a viscosity of 0.2 Pa·s or more at 25°C. As shown in Table 1 and Table 2, Examples 1 to 10 achieved a smaller bleed width than Comparative Examples 1 to 8. That is, Examples 1 to 10 suppressed the occurrence of bleed more than Comparative Examples 1 to 8.

[0114] In Comparative Examples 1 and 2 where a thiol compound having a viscosity of 0.2 Pa·s or more at 25°C was not used, the bleed width was large and the occurrence of bleed was not sufficiently suppressed. In Comparative Examples 3 to 8 where fumed silica having at least one selected from the group consisting of dimethylsilyl groups and trimethylsilyl groups was not used, the bleed width was large and the occurrence of bleed was not sufficiently suppressed.

Claims

1. An epoxy resin, fumed silica having at least one selected from the group consisting of a dimethylsilyl group and a trimethylsilyl group, a curing accelerator, and a thiol compound having a viscosity of 0.2 Pa·s or more at 25°C, a composition.

2. The composition according to claim 1, wherein the viscosity of the thiol compound is in the range of 0.2 Pa·s to 15 Pa·s at 25°C.

3. The composition according to claim 1, wherein the content of the fumed silica is in the range of 0.1% by mass to 20% by mass based on the total mass of the composition.

4. The composition according to claim 1, wherein the content of the thiol compound is in the range of 1% by mass to 80% by mass based on the total mass of the composition.

5. The composition according to claim 1, wherein the thiol compound has no ring skeleton.

6. The composition according to claim 1, wherein the thiol compound has a ring skeleton.

7. The composition according to claim 1, wherein the thiol compound has no ester bond.

8. An adhesive comprising the composition according to any one of claims 1 to 7.

9. A cured product of the composition according to any one of claims 1 to 7.

10. An electronic component comprising the cured product according to claim 9.

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