Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
  • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/02—Polythioethers; Polythioether-ethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
  • C09J181/02—Polythioethers; Polythioether-ethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins

Definitions

• the present invention relates to a resinous composition, an adhesive containing the same, a cured product thereof, a semiconductor device and an electronic component containing the cured product.
• Adhesives that are temporarily fixed by ultraviolet (UV) irradiation and fully cured by heat are used in many fields (for example, Patent Documents 1 and 2), and are particularly often used for image sensor modules.
• Image sensor modules are used as camera modules for mobile phones and smart phones.
• Adhesives used in the manufacture of image sensor modules are also used to prevent moisture from penetrating into electronic components, so they are also required to exhibit sufficient moisture resistance.
• Patent Document 3 as a photo- and thermosetting resin composition that suppresses a decrease in adhesive strength in a moisture resistance test of the resin composition after curing and has a sufficiently long pot life, (A) an acrylic resin , (B) a polyfunctional nitrogen-containing heterocyclic compound having a specific formula, (C) a latent curing agent, (D) a radical polymerization inhibitor, and (E) an anionic polymerization inhibitor.
• a resin composition is disclosed.
• Patent Literature 3 describes suppression of decrease in adhesive strength in a moisture resistance test of a resin composition after UV curing and heat curing, but does not describe moisture resistance after only heat curing.
• an object of the present invention is to provide a resin composition and an adhesive that have high moisture resistance after thermosetting.
• a first embodiment of the present invention is the following resin composition.
• (1) (A) (meth)acrylate compound, (B) a polythiol compound, (C) a cyclic carbodiimide compound, (D) a curing catalyst; and (E) a resin composition containing a coupling agent.
• (2) The resin composition according to (1) above, wherein the content of (C) the cyclic carbodiimide compound is 5% by mass or more relative to the total mass of the resin composition.
• a second embodiment of the present invention is (6) an adhesive comprising the resin composition according to any one of (1) to (5) above.
• a third embodiment of the present invention is (7) a cured product obtained by curing the resin composition according to any one of (1) to (5) above or the adhesive according to (6) above.
• a fourth embodiment of the present invention is (8) a semiconductor device comprising the cured product according to (7) above.
• a fifth embodiment of the present invention is an electronic component including the semiconductor device according to (8) above.
• the first embodiment of the present invention it is possible to obtain a resin composition having high moisture resistance after heat curing.
• the second embodiment of the present invention it is possible to obtain an adhesive having high moisture resistance after heat curing.
• a cured product having high moisture resistance can be obtained.
• the fourth aspect of the present invention it is possible to obtain a semiconductor device containing a cured product having high moisture resistance.
• an electronic component including a semiconductor device having high moisture resistance can be obtained.
• the resin composition which is the first embodiment of the present invention, (A) (meth)acrylate compound, (B) a polythiol compound, (C) a cyclic carbodiimide compound, (D) a curing catalyst; and (E) a coupling agent. According to this embodiment, it is possible to obtain a resin composition having high moisture resistance after thermosetting.
• the resin composition of the present embodiment contains (A) (meth)acrylate compound (hereinafter also referred to as “(A) component”).
• (A) The (meth)acrylate compound can impart transparency and appropriate hardness to the cured resin composition.
• the (meth)acrylate compound as component (A) is not particularly limited as long as it has one or more (meth)acryloyl groups. In consideration of ensuring heat resistance, compounds having two or more (meth)acryloyl groups are preferred, compounds having 2 to 6 (meth)acryloyl groups are more preferred, and two (meth)acryloyl groups.
• component (A) preferably has a structure that does not have a hydrolyzable partial structure such as an ester bond in the molecule, but in the present embodiment, (C) By including a cyclic carbodiimide compound, hydrolysis of ester bonds and the like can be suppressed, and even if the molecular chains are cut by hydrolysis, they can be rebonded, so the molecules may have ester bonds and the like.
• (meth)acrylate compounds include tris(2-hydroxyethyl)isocyanurate diacrylate and/or dimethacrylate; tris(2-hydroxyethyl)isocyanurate triacrylate and/or trimethacrylate; trimethylol Propane triacrylate and/or trimethacrylate, or oligomers thereof; pentaerythritol triacrylate and/or trimethacrylate, or oligomers thereof; polyacrylates and/or polymethacrylates of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone modification tris(acryloxyethyl) isocyanurate; caprolactone-modified tris(methacryloxyethyl) isocyanurate; alkyl-modified dipentaerythritol polyacrylate and/or polymethacrylate; caprolactone-modified dipentaerythritol polyacrylate and/or polymethacrylate
• the component (A) is preferably an acrylate compound and does not substantially contain a methacrylate compound.
• the (A) (meth)acrylate compound any one of the (meth)acrylate compounds described above may be used, or two or more thereof may be used in combination.
• the component (A) preferably has a viscosity of 0.01 to 80 Pa ⁇ s from the viewpoint of the preparation and dispensing properties of the resin composition.
• viscosity refers to a value measured at a measurement temperature of 25°C using an appropriate viscometer depending on the viscosity range.
• component (A) Commercially available products of component (A) include, for example, polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Ornex Co., Ltd., polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., and dimethylol-tricyclodecanedi manufactured by Kyoeisha Chemical Co., Ltd. Acrylate (Product name: Light Acrylate DCP-A) can be mentioned.
• component may use any one type, and may use 2 or more types together.
• the content of component (A) is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, based on the total mass of the resin composition.
• the resin composition of the present embodiment contains (B) a polythiol compound (hereinafter also referred to as “component (B)").
• component (B) The polythiol compound imparts elasticity and moisture resistance to the resin composition.
• Component (B) is not particularly limited as long as it has two or more thiol groups.
• component (B) preferably has a structure that does not have a hydrolyzable partial structure such as an ester bond in the molecule, but in the present embodiment, (C) By including a cyclic carbodiimide compound, hydrolysis of ester bonds and the like can be suppressed, and even if the molecular chains are cut by hydrolysis, they can be rebonded, so the molecules may have ester bonds and the like.
• Polythiol compounds having an ester bond in the molecule include, for example, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate butyrate), pentaerythritol tetrakis(3-mercaptobutyrate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3- mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptobutyrate), tri
• component (B) having an ester bond in the molecule examples include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP) and tris-[(3-mercaptopropionyloxy).
• a (B) polythiol compound that does not have an ester bond in its molecule can also be used.
• examples of such component (B) include glycoluril compounds represented by the following general formula (1).
• R 1 and R 2 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.
• n is an integer from 0 to 10;
• the (B) component may be a compound represented by the following chemical formula (2) or chemical formula (3).
• the compound represented by chemical formula (2) or chemical formula (3) is a more preferable compound as component (B).
• examples of (B) polythiol compounds that do not have an ester bond or the like in the molecule include polythiol compounds represented by general formula (4).
• R 3 , R 4 , R 5 and R 6 are each independently hydrogen or C n H 2n SH (n is 2 to 6). Further, at least one of R 3 , R 4 , R 5 and R 6 is C n H 2n SH (n is 2-6). From the viewpoint of curability, n of the polythiol compound (B) represented by the general formula (4) is preferably 2 to 4. Moreover, it is more preferable that this polythiol compound is a mercaptopropyl group in which n is 3 from the viewpoint of the balance between the physical properties of the cured product and the curing speed.
• the (B) component represented by the general formula (4) itself has a sufficiently flexible skeleton, and is effective when it is desired to lower the elastic modulus of the cured product.
• the elastic modulus of the cured product can be controlled, so that the adhesive strength (especially peel strength) after curing can be increased.
• component (B) that do not have an ester bond in the molecule
• Shikoku Kasei Co., Ltd.'s thiol glycol uril derivative product name: TS-G (equivalent to chemical formula (2), thiol equivalent: 100 g/eq)
• C3 TS -G equivalent to chemical formula (3), thiol equivalent: 114 g / eq
• SC organic chemical thiol compound product name: PEPT (equivalent to general formula (4), thiol equivalent: 124 g / eq)) be done.
• any one type may be used, or two or more types may be used in combination.
• a component (B) having an intramolecular ester bond and a component (B) having no intramolecular ester bond may be used in combination.
• the ester bond When using a polythiol compound having an ester bond in the molecule as the component (B), the ester bond hydrolyzes to form a carboxyl group and a hydroxyl group. These functional groups react with the cyclic carbodiimide compound (C) to form polar groups in the resin composition, thereby improving the adhesive strength under high humidity.
• the content of the polythiol compound having an ester bond in the molecule is preferably less than 60 parts by mass, more preferably less than 70 parts by mass, per 100 parts by mass of component (B). , is more preferably less than 80 parts by mass.
• the component (B) does not have an ester bond.
• (B) Per 100 parts by mass of component 70 to 100 parts by mass of a compound having no ester bond is included, from the viewpoint of maintaining the shear strength under high humidity for a long time after curing of the resin composition. preferable.
• the content of the polythiol compound having no ester bond in component (B) is more preferably 80 to 100 parts by mass, more preferably 90 to 100 parts by mass, relative to 100 parts by mass of component (B). preferable.
• [number of thiol group equivalents of component (B)]/[(meth)acryloyl group equivalent number of component (A)] is preferably from 0.5 to 2.0, and from 0.5 to 1.5 is more preferred.
• functional group equivalents such as (meth) acryloyl equivalents and thiol equivalents represent the molecular weight of a compound per functional group
• functional groups such as (meth) acryloyl group equivalents and thiol group equivalents
• the number of equivalents represents the number of functional groups (number of equivalents) per compound mass (amount charged).
• the thiol equivalent of component (B) is theoretically the number obtained by dividing the molecular weight of component (B) by the number of thiol groups in one molecule.
• the actual thiol equivalent weight can be determined, for example, by potentiometrically determining the thiol number.
• (A) The (meth)acryloyl equivalent of a (meth)acrylate compound is theoretically equal to the molecular weight of the (meth)acrylate compound divided by the number of acryloyl groups (or methacryloyl groups) in one molecule.
• the actual (meth)acryloyl equivalent can be measured, for example, by NMR.
• the (meth)acryloyl group equivalent number of component (A) is the number (number of equivalents) of (meth)acryloyl groups per mass (amount charged) of component (A), and the mass of (A) (meth)acrylate compound (g) divided by the (meth)acryloyl equivalent of the (meth)acrylate compound (if more than one (meth)acrylate compound is involved, the sum of such quotients for each (meth)acrylate compound) be.
• the thiol group equivalent number of component (B) is the number of thiol groups (equivalent number) per mass (amount charged) of component (B), and the mass (g) of the thiol compound (B) is It is the quotient divided by the thiol equivalent (if more than one thiol compound is involved, the sum of such quotients for each thiol compound).
• [Number of thiol group equivalents of component (B)]/[Number of (meth)acryloyl group equivalents of component (A)] is in the range of 0.5 to 2.0. reacts in a certain amount or more, sufficient molecular cross-linking is formed, and high adhesive strength can be easily developed.
• the resin composition of the present embodiment is a resin composition containing (A) a (meth)acrylate compound as a main component prepolymer compound.
• the resin composition of the present embodiment may contain other prepolymer compounds such as epoxy compounds.
• [(B) thiol group equivalent number of component] / [epoxy group equivalent number of epoxy compound] is not included in the embodiment in which it is 10.0 or less.
• a cured product of a (meth)acrylate compound-rich resin composition as a main component prepolymer compound has better moisture resistance than an epoxy compound-rich resin composition, especially when hydrolyzable ester bonds are formed in the polymer molecule. was more serious.
• the epoxy equivalent of an epoxy compound is theoretically a number obtained by dividing the molecular weight of the epoxy compound by the number of epoxy groups in one molecule.
• the actual epoxy equivalent can be determined by the method described in JIS K7236.
• the number of epoxy group equivalents of an epoxy compound is the number of epoxy groups (number of equivalents) per mass (amount charged) of the epoxy compound, and is the quotient obtained by dividing the mass (g) of the epoxy compound by the epoxy equivalent of the epoxy compound ( If more than one epoxy compound is included, the sum of such quotients for each epoxy compound).
• the resin composition of the present embodiment contains (C) a cyclic carbodiimide compound (hereinafter also referred to as “component (C)”).
• a cyclic carbodiimide compound has a cyclic structure.
• One cyclic structure has only one carbodiimide group.
• the number of atoms in the ring structure is preferably 8-50, more preferably 10-30, still more preferably 10-20.
• the cyclic carbodiimide compound may have multiple cyclic structures.
• the cyclic carbodiimide compound used in this embodiment is preferably a cyclic carbodiimide compound represented by the following general formula (5).
• Ar 1 to Ar 4 each independently represent an aromatic group.
• the aromatic group may be substituted with an alkyl group having 1 to 6 carbon atoms or an aryl group.
• Examples of the aromatic group include aromatic groups such as phenylene group and naphthalenediyl group.
• Ar 1 to Ar 4 are phenyl groups because the film formability is improved.
• X is a divalent or tetravalent group. q is 0 when X is divalent and q is 1 when X is tetravalent. X is one of the following formulas (5-i), (5-ii), (5-iii), (5-iv), (5-v), (5-vi), and (5-vii) is preferred.
• n is an integer of 1-6.
• (5-i) is exemplified by a methylene group, ethylene group, 1,3-propylene group, 1,4-butylene group, 1,5-pentane group and 1,6-hexane group.
• m and n are each independently an integer of 0 to 4.
• R 1 and R 2 are each independently an alkyl group or an aryl group having 1 to 6 carbon atoms.
• Alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, sec-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group and iso-butyl group.
• X is the above-described (5-i), (5-ii), (5-iii), (5-iv), (5-v), (5-vi), ( 5-vii) is preferable.
• Y and Z are each independently a substituent other than an alkyl group having 1 to 6 carbon atoms or a phenyl group.
• substituents other than alkyl groups having 1 to 6 carbon atoms or phenyl groups conventionally known substituents can be applied, for example, alkyl groups having 7 or more carbon atoms, aryl groups other than phenyl groups, alkoxy groups, hydroxy groups, and aldehydes.
• the compound represented by the following chemical formula (5-1) or the following chemical formula (5-2) is preferable.
• the mechanism of moisture resistance improvement by the cyclic carbodiimide compound is not limited, but is presumed as follows. Hydrolyzable partial structures such as ester bonds are contained in some (A) (meth)acrylate compounds and some (B) polythiol compounds. For example, an ester bond hydrolyzes to produce a carboxylic acid and an alcohol. As shown below, the carbodiimide group has the effect of suppressing hydrolysis by reacting with the carboxylic acid produced by hydrolysis and capturing the acid that serves as a catalyst for the decomposition reaction.
• (C) a polycarbodiimide compound that is not a cyclic carbodiimide compound, although the carbodiimide group reacts with the carboxylic acid to suppress hydrolysis, decomposition occurs when heat is applied thereafter, resulting in high irritation and sensitization. A substance known as isocyanate gas is generated.
• the cyclic carbodiimide compound (C) when the carbodiimide group present in the cyclic skeleton reacts with the carboxylic acid, the bond is not broken even when heat is applied thereafter, and the resulting isocyanate forms a cyclic skeleton. remain in the polymer via Isocyanate groups form bonds between isocyanate groups or with thiol groups. As a result, the polymer chains cut off by hydrolysis can be recombined with other polymer chains, thereby maintaining or strengthening the adhesive strength. It is thought to be larger than the carbodiimide compound.
• the (C) cyclic carbodiimide compound does not generate isocyanate gas when heated, a voidless cured film can be produced. If there are voids in the cured film, cracks are likely to progress, and it is also a cause of deterioration in reliability, such as easier passage of moisture, so it is preferable that there are no voids in the cured film.
• the content of the cyclic carbodiimide compound is preferably 5% by mass or more, more preferably 8% by mass or more, and more preferably 10% by mass or more, relative to the total mass of the resin composition.
• the upper limit of the content of the cyclic carbodiimide compound (C) is not particularly limited, but from the viewpoint of viscosity, it is, for example, 60% by mass or less, 50% by mass or less, or 40% by mass or less.
• the method for producing the cyclic carbodiimide compound is not particularly limited, and it can be produced by a conventionally known method (for example, the method described in International Publication No. 2010/071211, Japanese Patent Application Laid-Open No. 2011-256139, etc.). can.
• a method for producing an amine form via an isocyanate form for example, a method for producing an amine form for an isothiocyanate form, a method for producing an amine form for a triphenylphosphine form, and a method for producing a urea form from an amine form.
• a commercially available product may be used as the cyclic carbodiimide compound.
• the resin composition of the present embodiment contains (D) a curing catalyst (hereinafter also referred to as “component (D)”).
• component (D) a curing catalyst
• the (D) curing catalyst used in the present embodiment is not particularly limited as long as it is a curing catalyst for a (meth)acrylate compound, and a known one can be used, but a latent curing catalyst is preferred.
• the latent curing catalyst of component (D) is a compound that is inactive at room temperature and is activated by heating to function as a curing catalyst.
• imidazole compounds that are solid at room temperature
• solid-dispersed amine adduct-based latent curing catalysts such as reaction products with epoxy compounds (amine-epoxy adduct systems); reaction products of amine compounds with isocyanate compounds or urea compounds (urea-type adduct systems); .
• Examples of the epoxy compound used as one of raw materials for producing the solid-dispersed amine adduct-based latent curing catalyst include bisphenol A, bisphenol F, catechol, polyhydric phenols such as resorcinol, or glycerin.
• Polyglycidyl ethers obtained by reacting polyhydric alcohols such as polyhydric alcohols and polyethylene glycol with epichlorohydrin; reaction of epichlorohydrin with hydroxycarboxylic acids such as p-hydroxybenzoic acid and ⁇ -hydroxynaphthoic acid polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; 4,4'-diaminodiphenylmethane, m-aminophenol, etc.
• An amine compound used as another raw material for producing a solid-dispersed amine adduct-based latent curing catalyst has in its molecule one or more active hydrogens capable of undergoing an addition reaction with an epoxy group, and has a primary amino group, a secondary Any compound having at least one functional group selected from an amino group and a tertiary amino group in the molecule may be used. Examples of such amine compounds are shown below, but are not limited thereto.
• Aliphatic amines such as, for example, diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diamino-dicyclohexylmethane; 4,4'-diaminodiphenylmethane, 2 -aromatic amine compounds such as methylaniline; nitrogen atom-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine; etc., but not limited to these.
• compounds having a tertiary amino group in the molecule are particularly raw materials that provide latent curing catalysts having excellent curing accelerating ability.
• examples of such compounds include, for example, dimethylaminopropylamine , diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine and other amine compounds, 2-methylimidazole, 2-ethylimidazole, 2-ethyl- Primary or secondary amines having a tertiary amino group in the molecule, such as imidazole compounds such as 4-methylimidazole and 2-phenylimidazole; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylamin
• isocyanate compounds used as solid-dispersed amine adduct-based latent curing catalysts and as another manufacturing raw material include monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; methylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc.
• monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate
• terminal isocyanate group-containing compounds obtained by reacting these polyfunctional isocyanate compounds with active hydrogen compounds can also be used.
• Examples of such terminal isocyanate group-containing compounds include an addition compound having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, and a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and pentaerythritol. but not limited thereto.
• urea compounds include urea and thiourea, but are not limited to these.
• the solid-dispersed latent curing catalyst that can be used in the present embodiment includes, for example, the above (a) two components of an amine compound and an epoxy compound, (b) three components of these two components and an active hydrogen compound, or (c ) Binary or ternary combinations of amine compounds and isocyanate compounds and/or urea compounds. These components are mixed and reacted at a temperature from room temperature to 200° C., then solidified by cooling and pulverized, or reacted in a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc., and after removing the solvent, , can be easily produced by pulverizing the solid content.
• a solvent such as methyl ethyl ketone, dioxane, tetrahydrofuran, etc.
• Typical examples of commercially available solid dispersion type latent curing catalysts include amine-epoxy adduct system (amine adduct system) such as "Amicure PN-23” (product name of Ajinomoto Fine-Techno Co., Ltd.), “Amicure PN-40” (Ajinomoto Fine-Techno Co., Ltd. product name), “Amicure PN-50” (Ajinomoto Fine-Techno Co., Ltd. product name), “Hardner X-3661S” (ACR Co., Ltd. product name), “Hardener X-3670S” ” (ACR Co., Ltd.
• urea-type adducts include "Fujicure FXE-1000" (T&K TOKA Co., Ltd. product name), "Fujicure FXR- 1030" (product name of T&K TOKA Co., Ltd.), but not limited to these.
• Component (D) may be used either singly or in combination of two or more.
• the content of the curing catalyst is preferably 0.1 to 40% by mass, preferably 1 to 20% by mass, based on the total mass of the resin composition, from the viewpoint of the curing speed and pot life of the resin composition. % is more preferred.
• the resin composition of the present embodiment contains (E) a coupling agent (hereinafter also referred to as “component (E)”).
• the coupling agent has two or more different functional groups in the molecule, one of which is a functional group that chemically bonds with the inorganic material, and the other of which chemically bonds with the organic material. It is a functional group.
• (E) a coupling agent is also necessary for improving moisture resistance.
• the reason is not limited, it is considered as follows.
• water, heat, ions, vibration, load, etc. are applied to the metal material bonding portion, the bonding strength is lowered.
• water is positioned as an extremely important deterioration factor, and when water molecules enter and accumulate at the metal/adhesive interface, the effects of other deterioration factors such as heat, ions, vibrations and loads are further accelerated, resulting in the final adhesion. Partial destruction.
• (E) the coupling agent suppresses the penetration of water into the adhesion interface, which is thought to improve the moisture resistance.
• Examples of (E) coupling agents include, but are not limited to, silane coupling agents, aluminum coupling agents, titanium coupling agents, etc., depending on the type of functional group that chemically bonds with the inorganic material.
• Examples of coupling agents include various types of coupling agents such as epoxy, amino, vinyl, methacrylic, acrylic, and mercapto, depending on the type of functional group that chemically bonds with the organic material. It is not limited to these.
• an epoxy coupling agent containing an epoxy group, a methacrylic coupling agent containing a methacryloyl group, an acrylic coupling agent containing an acryloyl group, and a mercapto coupling agent containing a thiol group have improved moisture resistance. It is preferable because In particular, an epoxy-based coupling agent containing an epoxy group is more preferable from the viewpoint of both heat curing and moisture resistance after UV+heat curing.
• epoxy-based silane coupling agents include 3-glycidoxypropyltrimethoxysilane (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (product name: KBE-403, Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldiethoxysilane (product name: KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldimethoxysilane (product name: KBM402, manufactured by Shin-Etsu Chemical Co., Ltd.) , 8-glycidoxyoctyltrimethoxysilane (product name: KBM-4803, Shin-Etsu Chemical Co., Ltd.), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (product name: Sila Ace S530, JNC Corporation), etc. mentioned.
• methacrylic silane coupling agents include 3-methacryloxypropyltrimethoxysilane (product name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropylmethyldimethoxysilane (product name: KBM502, manufactured by Shin-Etsu Chemical Co., Ltd.). ), 3-methacryloxypropylmethyldiethoxysilane (product name: KBE502, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltriethoxysilane (product name: KBE503, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
• acrylic silane coupling agents include 3-acryloxypropyltrimethoxysilane (product name: KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.).
• mercapto-based silane coupling agents include 3-mercaptopropyltrimethoxysilane (product name KBM803, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-mercaptopropylmethyldimethoxysilane (product name KBM802, manufactured by Shin-Etsu Chemical Co., Ltd.). mentioned.
• any one of the coupling agents may be used, or two or more may be used in combination.
• the content of component (E) is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, and still more preferably 0.3 to 5% by mass, relative to the total mass of the resin composition. is.
• the resin composition of the present embodiment may contain (F) a photoinitiator (hereinafter also referred to as "(F) component") within a range that does not impair the effects of the present invention.
• a photoinitiator hereinafter also referred to as "(F) component
• photoinitiators that generate radicals by UV absorption are preferred.
• photoinitiators examples include alkylphenone photoinitiators and acylphosphine oxide photoinitiators. Specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino and propan-1-one.
• the resin composition of the present embodiment is photo- and heat-curable, but UV curing can be accelerated by using a photoinitiator.
• component (F) is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, relative to 100 parts by mass of the (meth)acrylate compound, from the viewpoint of UV curability. is.
• the resin composition of the present embodiment may contain (G) an inorganic filler (hereinafter also referred to as "(G) component") within a range that does not impair the effects of the present invention.
• An inorganic filler consists of a granular body formed of an inorganic material.
• Inorganic materials include silica, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, Zinc oxide, silicon carbide, silicon nitride, boron nitride and the like can be used. Any one of the inorganic fillers may be used, or two or more thereof may be used in combination.
• a silica filler is preferably used as the inorganic filler.
• Silica is preferably amorphous silica.
• the shape of the inorganic filler is not particularly limited, and may be spherical, scaly, acicular, irregular, and the like. A spherical shape is preferable from the viewpoint of fluidity.
• the average particle size of the inorganic filler is preferably 0.01-15 ⁇ m, more preferably 0.01-10 ⁇ m.
• the maximum particle size of the inorganic filler is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
• the average particle size is the particle size at 50% of the integrated value in the volume-based particle size distribution measured by the laser diffraction/scattering method.
• the maximum particle size is the maximum particle size in a volume-based particle size distribution measured by a laser diffraction/scattering method.
• the content of the inorganic filler is preferably 0.5 to 80% by mass, more preferably 1 to 70% by mass, relative to the total mass of the resin composition.
• the resin composition of the present embodiment may contain (H) a stabilizer (hereinafter also referred to as “(H) component”) within a range that does not impair the effects of the present invention.
• (H) Stabilizers are used to increase the storage stability of the resin composition, and are added to suppress the occurrence of polymerization reactions caused by unintended radicals and basic components.
• a known stabilizer can be used, for example, a boric acid ester compound, a strong acid, or a radical scavenger can be used.
• specific (H) stabilizers include trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, difluoroacetic acid, trichloroacetic acid, phosphorus acids, dichloroacetic acid, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, 4-methoxyphenol, and hydroquinone.
• the preferred (H) stabilizer is at least one selected from maleic acid, methanesulfonic acid, N-nitroso-N-phenylhydroxylamine aluminum and 4-methoxyphenol.
• (H) stabilizer known ones disclosed in JP-A-2010-117545, JP-A-2008-184514, JP-A-2017-171804, etc. can also be used.
• (H) Stabilizers may be used alone or in combination of two or more.
• the content of component (H) is preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, relative to the total mass of the resin composition.
• the resin composition contains at least one of (G) an inorganic filler and (H) a stabilizer.
• the resin composition may optionally contain a solvent, carbon black, titanium black, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a thixotropic agent, and a viscosity modifier as long as the object of the present embodiment is not impaired. , flame retardants, and/or other additives.
• the resin composition includes, for example, components (A) to (E), optionally components (F), (G) and/or (H), and optionally other additives, etc. at the same time. Alternatively, they can be obtained separately by stirring, melting, mixing and/or dispersing while optionally applying heat treatment.
• Devices for mixing, stirring, dispersing, etc. are not particularly limited. As this device, a Laikai machine, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc., equipped with a stirring and heating device can be used. Also, these devices may be used in combination as appropriate.
• the resin composition obtained in this way has both photocurability and thermosetting properties, and is sufficiently cured only by thermosetting.
• the thermosetting temperature of the resin composition is preferably 70 to 90° C. when the resin composition is used for an image sensor module.
• the resin composition of the present embodiment can be used, for example, as an adhesive for joining parts together or as a raw material thereof.
• the adhesive which is the second embodiment of the present invention, contains the resin composition of the first embodiment described above. This adhesive allows good bonding to engineering plastics, ceramics and metals.
• the cured product of the third embodiment of the present invention is a cured product obtained by curing the resin composition of the first embodiment or the adhesive of the second embodiment.
• semiconductor device of the fourth embodiment of the present invention contains the cured product of the third embodiment, it has high moisture resistance. Since the electronic component of the fifth embodiment of the present invention includes the semiconductor device of the fourth embodiment, it has high moisture resistance.
• (A) (meth)acrylate compound (component (A)) (A1): Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., acryloyl equivalent: 188 g/eq) (A2): Polyester acrylate (product name: M7100, manufactured by Toagosei Co., Ltd., acryloyl equivalent: 152 g/eq) - (B) polythiol compound (component (B)) (B1): Pentaerythritol tetrakis(3-mercaptopropionate) represented by the following formula (product name: PEMP, manufactured by SC Organic Chemical, thiol equivalent: 122 g/eq) (B2): a glycoluril derivative represented by formula (3) (product name: C3 TS-G, manufactured by Shikoku Kasei Kogyo Co., Ltd., thiol equivalent: 114
• the properties of the cured product obtained by curing the resin composition were measured as follows.
• the curing conditions at this time are: 80°C/60 minutes in a blower dryer for "heat only”; After an amount of 2000 mJ/cm 2 (UV wavelength: 365 nm, LED lamp), 80° C./60 min in a blower dryer.
• the alumina chip on this glass plate was poked from the side with a MODEL-1605HTP type strength tester manufactured by Aikoh Engineering Co., Ltd., and the shear strength was calculated from the numerical value when the alumina chip was peeled off.
• the cured test pieces were subjected to a pressure cooker test (PCT) (2 atm, 121° C., 100% RH, 20 hours). After that, the shear strength was calculated in the same manner. Table 1 shows the results (unit: N).
• a PCT test is a reliability test in which a cured resin composition is held at 121° C., 2 atmospheres, and 100% relative humidity.
• the retention rate (%) of the adhesive strength after a pressure cooker test (PCT) was calculated for the initial adhesive strength.
• the adhesive strength retention rate is preferably 50% or more, more preferably 60% or more. Table 1 shows the results.
• Both (A1) and (A2) of component (A) are (meth)acrylate compounds containing an ester bond.
• Component (B) (B1) is a polythiol compound containing an ester bond, and (B2) and (B3) are polythiol compounds that do not contain an ester bond. All of Examples 1 to 9 and Comparative Examples 1 to 4 contain (A1), (A2) and (B1), and are examined under conditions that facilitate hydrolysis. It should be noted that the scope of the present invention is not necessarily limited to embodiments in which component (A) and component (B) contain ester bonds.
• the present invention is a light and thermosetting resin composition that exhibits high moisture resistance after UV+thermal curing as well as high moisture resistance even after thermal curing alone, and is particularly applicable to locations where UV curing is difficult. Very useful as an adhesive.

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• 2022
  • 2022-06-21 JP JP2023531832A patent/JPWO2023276773A1/ja active Pending
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