Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/226—Mixtures of di-epoxy compounds
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • 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
  • 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
  • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
  • C09J133/04—Homopolymers or copolymers of esters
  • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09J133/08—Homopolymers or copolymers of acrylic acid esters
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/66—Mercaptans
• • 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
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen

Definitions

• the present invention relates to a resinous composition, an adhesive or sealing material containing the same, a cured product thereof, a semiconductor device and an electronic component containing the cured product.
• a photo- and thermosetting resin composition is known that can be temporarily fixed by light irradiation and further can be fully cured by heating. More specifically, adhesives that are temporarily fixed by ultraviolet (UV) irradiation and then fully cured by heat are used in many fields (for example, Patent Documents 1 and 2). This type of adhesive is especially popular in image sensor module applications.
• UV ultraviolet
• Patent Document 3 discloses a light and A resin composition containing (A) an acrylic resin, (B) a thiol compound, and (C) a latent curing accelerator is disclosed as a thermosetting resin composition.
• thermosetting resin compositions or adhesives that are cured in a two-step curing process of thermal curing (second-stage curing) after UV irradiation curing (first-stage curing), even after the second-stage thermal curing , it was found that not a little unreacted low-molecular-weight components remained in the cured product. This is because most of the molecules are fixed in the region cured by UV radiation curing in the first stage, and molecular movement is suppressed in the second stage heat curing, which is different from the case of heat curing alone. In comparison, it is believed that more heat energy is required for the thermosetting component to react.
• an object of the present invention is to provide a resin composition and an adhesive that provide a cured product in which unreacted components are less likely to remain after the second stage of thermal curing following the first stage of UV curing.
• a first embodiment of the present invention is the following resin composition.
• Ratio of (meth)acryloyl group equivalent number of component (A) to thiol group equivalent number of component (B) ([(meth)acryloyl group equivalent number of component (A)]/[thiol of component (B) Group equivalent number]) is 0.25 to 3.0, the resin composition according to the above (1).
• a second embodiment of the present invention is the following adhesive or sealing material.
• a third embodiment of the present invention is the following cured product.
• a fourth embodiment of the present invention is the following semiconductor device or electronic component.
• the remaining unreacted components are suppressed, bleed out and outgassing are suppressed, and during additional heating, It is possible to obtain a resin composition that provides a cured product having high dimensional stability.
• the remaining unreacted components are suppressed, bleed out and outgassing are suppressed, and additional heating is performed. It is possible to obtain an adhesive or encapsulant that provides a cured product with high dimensional stability during the process.
• the third embodiment of the present invention it is possible to obtain a cured product that suppresses the generation of bleed-out and outgassing and has high dimensional stability during additional heating.
• the fourth embodiment of the present invention it is possible to obtain a semiconductor device or an electronic component containing a cured product that suppresses bleed-out and outgassing and has high dimensional stability during additional heating.
• the resin composition which is the first embodiment of the present invention, (A) (meth)acrylate compound, (B) a polyfunctional thiol compound, (C) a photoradical polymerization initiator, and (D) a thermosetting accelerator containing an azabicyclo ring compound having a bridgehead nitrogen.
• a resin composition that provides a high cured product can be obtained.
• the resin composition of the present embodiment contains (A) a (meth)acrylate compound (hereinafter also referred to as “component (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.
• a compound having one (meth)acryloyl group can also be used to adjust the viscosity and physical properties of the cured product (adhesive strength, flexibility, etc.). can.
• (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
• component (A) is preferably an acrylate compound that 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 100 Pa ⁇ s from the viewpoint of 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) examples include polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Ornex Co., Ltd., ditrimethylolpropane tetraacrylate (product name: EBECRYL140) manufactured by Daicel-Ornex Co., Ltd., and polyester acrylate manufactured by Toagosei Co., Ltd. (product name: M7100), Kyoeisha Chemical Co., Ltd. dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A), Nippon Kayaku Co., Ltd. neopentyl glycol-modified trimethylolpropane diacrylate (product name: Kayarad R-604) etc., but not limited to these.
• 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 polyfunctional thiol compound (hereinafter also referred to as "component (B)").
• component (B) The polyfunctional thiol compound imparts high photocurability to the resin composition.
• Component (B) is not particularly limited as long as it is bifunctional or more, that is, it has two or more thiol groups.
• the component (B) preferably contains a tri- or higher functional thiol compound, and more preferably contains a tri- and/or tetra-functional thiol compound.
• the trifunctional and tetrafunctional thiol compounds are thiol compounds having three and four thiol groups, respectively.
• polyfunctional thiol compounds include pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and pentaerythritol.
• component (B) Commercially available products of component (B) include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP) and tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate.
• TMMP trimethylolpropane tris(3-mercaptopropionate)
• TMMP tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate.
• Polyfunctional thiol compounds 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;
• component (B) may be a compound represented by the following chemical formula (2) or chemical formula (3).
• a compound represented by chemical formula (2) or chemical formula (3) is a more preferable compound as component (B).
• polyfunctional thiol compounds include polyfunctional thiol 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 polyfunctional thiol compound (B) represented by the general formula (4) is preferably 2 to 4. Moreover, it is more preferable that this polyfunctional thiol 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 component (B) 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) Commercially available products of component (B) include Shikoku Kasei Co., Ltd.'s thiol glycol uril derivative (product name: TS-G (corresponding to chemical formula (2), thiol equivalent: 100 g/eq), product name: C3 TS-G (chemical formula ( 3), thiol equivalent: 114 g/eq)), and a thiol compound manufactured by SC Organic Chemical (Product name: PEPT (corresponding to general formula (4), thiol equivalent: 124 g/eq))). Not limited.
• component (B) examples include 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1, 3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6- Tetrakis(mercaptomethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(3- mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,6-tetrakis(3- mercaptopropyl)-3a,6a-dimethylglycoluril, 1,3,4,
• any one type may be used, or two or more types may be used in combination.
• functional group equivalents such as thiol equivalents and (meth) acryloyl equivalents represent the molecular weight of the compound per functional group
• functional groups such as thiol group equivalents and (meth) acryloyl group equivalents
• the number of equivalents represents the number of functional groups (number of equivalents) per compound mass (amount charged).
• the ratio of the (meth)acryloyl group equivalent number of component (A) to the thiol group equivalent number of component (B) is preferably from 0.25 to 3.0, more preferably from 0.4 to 2.0, and even more preferably from 0.5 to 1.5.
• the thiol equivalent weight of component (B) is theoretically the molecular weight of component (B) divided 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.
• the number of thiol group equivalents of component (B) is the number of thiol groups (number of equivalents) per mass (amount charged) of component (B), and the mass (g) of the polyfunctional thiol compound (B) is the thiol It is the quotient divided by the thiol equivalent weight of the compound (if more than one thiol compound is included, the sum of such quotients for each thiol compound).
• 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 number of (meth)acryloyl group equivalents 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.
• Component (A) (meth)acryloyl group equivalents]/[Component (B) thiol group equivalents] is in the range of 0.25 to 3.0, whereby (meth)acryloyl groups and thiol Since a certain amount or more of reaction with groups occurs, sufficient molecular cross-linking is formed, and high adhesive strength can be easily developed.
• the resin composition of the present embodiment contains (C) a radical photopolymerization initiator (hereinafter also referred to as “component (C)”).
• component (C) a radical photopolymerization initiator
• UV curing is accelerated by including a photoradical polymerization initiator.
• Photoradical polymerization initiators include, but are not limited to, alkylphenone-based compounds, acylphosphine oxide-based compounds, and the like.
• alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available: Omnirad 651 manufactured by IGM Resins B.V.); ⁇ -aminoalkylphenones such as 2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available from IGM Resins B.V. Omnirad 907); 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available ⁇ -hydroxyalkylphenone such as IGM Resins B.V.
• Omnirad 184 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)- Butan-1-one (as a commercial product Omnirad 379EG manufactured by IGM Resins B.V.), 2-benzyl-2-(dimethylamino)-4'-morpholinobtyrophenone (as a commercial product Omnirad manufactured by IGM Resins B.V.) 369), etc., but are not limited to these.
• acylphosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H manufactured by IGM Resins B.V.), bis(2,4,6- trimethylbenzoyl)-phenylphosphine oxide (as a commercial product, Omnirad 819 manufactured by IGM Resins B.V.), etc., but not limited thereto.
• Photoradical polymerization initiators include, in addition to the photoradical polymerization initiators described above, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4- isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl ( 2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether , benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone
• the content of component (C) is preferably 0.01 to 40% by mass, preferably 0.1 to 20%, based on the total mass of the resin composition, from the viewpoint of curing speed and pot life of the resin composition. % by mass is more preferred.
• the resin composition of the present embodiment contains (D) a thermal curing accelerator containing an azabicyclo ring compound having a bridgehead nitrogen (hereinafter also referred to as "component (D)").
• component (D) By containing a heat curing accelerator containing an azabicyclo ring compound having a head position nitrogen, the remaining unreacted components are suppressed after the second stage heat curing following the first stage UV curing, and bleed out and outgassing It is possible to obtain a resin composition that suppresses the occurrence of , and provides a cured product having high dimensional stability during additional heating. In this way, bleed-out and outgassing are suppressed, so contamination of peripheral members is suppressed. Further, since the dimensional stability during additional heating is high, misalignment and misalignment of the optical axis are suppressed.
• thermosetting accelerator examples include compounds represented by the following general formula (5).
• Q is CR (wherein R is a hydrogen atom (H) or a hydrocarbon chain such as an alkyl group), a nitrogen atom (N) or the following formula (6):
• R is a hydrogen atom (H) or a hydrocarbon chain such as an alkyl group
• N nitrogen atom
• formula (6) each single bond of the carbon atom is bonded to X and Y in formula (5), respectively, and the single bond of the nitrogen atom is bonded to Z in formula (5).
• Substituents of the optionally substituted alkyl group are an alkyl group, a hydroxy group and an amino group.
• R is a hydrogen atom (H) or a hydrocarbon chain such as an alkyl group
• N nitrogen atom
• Q is the following formula (6):
• each single bond of the carbon atom is bonded to X and Y in formula (5), respectively, and the single bond of the nitrogen atom is bonded to Z in formula (5).
• Unsaturated azabicyclo compounds with a bridgehead nitrogen optionally substituted or substituted with an oxygen atom (O) to form a carbonyl group together with the carbon atoms of the hydrocarbon chain .
• the azabicyclo ring compound having a bridgehead nitrogen also includes a compound containing a moiety represented by general formula (5).
• a compound containing a moiety represented by general formula (5) is a compound in which a compound represented by general formula (5) is bound or linked to a second moiety through a covalent bond.
• the second moiety is not particularly limited and includes, for example, saturated or unsaturated cyclic hydrocarbons, saturated or unsaturated heterocycles, aryls, heteroaryls and the like.
• Compounds of formula (5) include, for example, 1,4-diazabicyclo[2.2.2]octane (DABCO (registered trademark)), 1-azabicyclo[2.2.2]octan-3-ol (common name: 3-quinuclidinol), 1,4-diazabicyclo[2.2.2]octane-2-methanol, 1-azabicyclo[2.2.2]octan-3-one (common name: 3-quinuclidinone), 1,4 -diazabicyclo[2.2.2]octan-2-ol, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU®), 1,5-diazabicyclo[4.3.0 ] non-5-ene (DBN (registered trademark)). Any one of component (D) may be used, or two or more thereof may be used in combination.
• D 1,4-diazabicyclo[2.2.2]octane
• DBN registered trademark
• thermosetting resin compositions when using a heat curing accelerator containing an imidazole compound, only heat curing shows sufficient reactivity, whereas UV curing It was found that the reactivity in the subsequent heat curing was not high, and not a little low-molecular-weight components remained in the cured product. This is because most of the molecules are fixed in the region cured by UV radiation curing in the first stage, and molecular movement is suppressed in the second stage heat curing, which is different from the case of heat curing only. In comparison, it is believed that more heat energy is required for the thermosetting component to react.
• thermosetting resin compositions or adhesives that are cured in a two-stage curing process, there are areas of incomplete UV curing after the first-stage UV irradiation.
• the thermal curability of the thermosetting functional groups remaining in the incompletely UV-cured region depends on the type of the thermosetting accelerator.
• the azabicyclo ring compound having a bridgehead nitrogen is highly basic, a reaction is likely to occur even in the thermal curing step after UV curing.
• a saturated azabicyclo ring compound having a bridgehead nitrogen is preferable because the steric hindrance of the bridgehead nitrogen is small.
• a saturated diazabicyclo ring compound having a bridgehead nitrogen has two bridgehead nitrogens, and therefore has a high reaction probability and is more preferable.
• commonly used heat curing accelerators such as imidazole compounds and their derivatives have sufficient curability as heat curing accelerators if only the heat curing process is performed, but they are not compatible with azabicyclo ring compounds having bridgehead nitrogen. Because of its low basicity, the thermosetting reaction is less likely to occur after UV curing.
• the present inventors also found that the use of (D) a heat curing accelerator containing an azabicyclo ring compound having a bridgehead nitrogen enables heat curing of the resin composition at a lower temperature.
• a heat curing accelerator containing an imidazole-based compound when used, although the low-temperature curability of the resin composition is excellent, curing at about 80° C. is the limit.
• the resin composition can be heat cured at a temperature of less than 80°C, for example, 50°C or more and less than 80°C.
• the resin composition of this embodiment can also be thermoset at a temperature of 80° C. or higher.
• thermosetting accelerator containing an azabicyclo ring compound having a bridgehead nitrogen is used to cure at a lower temperature. Since the resin composition can be thermally cured, it is possible to prevent thermal damage to module parts (such as lenses).
• the azabicyclo ring compound having a bridgehead nitrogen contained in (D) the heat curing accelerator is preferably a saturated azabicyclo ring compound having a bridgehead nitrogen from the viewpoint of curability.
• Saturated azabicyclo ring compounds having a bridgehead nitrogen include compounds having a 1,4-diazabicyclooctane skeleton and compounds having a quinuclidine skeleton. From the viewpoint of increasing the reaction probability, a compound having a 1,4-diazabicyclooctane skeleton, which is a compound having two bridgehead nitrogens, is preferable.
• Such compounds include 1,4-diazabicyclo[2.2.2]octane, 1,4-diazabicyclo[2.2.2]octane-2-methanol, 1,4-diazabicyclo[2 .2.2]octan-2-ol, 1,4-diazabicyclo[2.2.2]octane.
• a compound having a quinuclidine skeleton which is a compound having one bridgehead nitrogen, is preferable.
• the content of component (D) is preferably 0.01 to 40% by mass, preferably 0.05 to 20%, based on the total mass of the resin composition, from the viewpoint of curing speed and pot life of the resin composition. % by mass is more preferred.
• the thermosetting accelerator may be a thermosetting accelerator dispersed in an epoxy compound or supported between layers of a layered inorganic compound from the viewpoint of latentization.
• the latent curing accelerator is inactive at room temperature and activated by heating to function as a curing catalyst.
• a representative example of a commercially available latent thermosetting accelerator containing component (D) is "Novacure HXA5945HP" (product name of Asahi Kasei Corporation).
• the epoxy compound may be the following (E) epoxy compound.
• the resin composition of this embodiment may contain a thermosetting accelerator other than component (D) as long as it does not impair the effects of the present invention.
• a thermosetting accelerator other than component (D) for example, an imidazole compound that is solid at room temperature; a solid-dispersed amine adduct-based latent curing catalyst such as a reaction product of an amine compound and an epoxy compound (amine-epoxy adduct system); a reaction between an amine compound and an isocyanate compound or a urea compound. products (urea-type adduct system) and the like.
• thermosetting accelerators other than component (D) include amine-epoxy adduct-based (amine adduct-based) 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), “Hardner X- 3670S” (ACR Co., Ltd. product name), “Novacure HX-3742” (Asahi Kasei Co., Ltd.
• component (D) and a thermosetting accelerator other than component (D) that is provided in the form of a dispersion dispersed in an epoxy compound the amount of the epoxy compound in which it is dispersed is also , is included in the amount of component (E) in the resin composition of this embodiment.
• Epoxy Compound The resin composition of the present embodiment may further contain (E) an epoxy compound (hereinafter also referred to as "component (E)").
• component (E) The epoxy compound is not particularly limited as long as it has two or more functional groups, that is, two or more epoxy groups, and conventionally commonly used epoxy resins can be used as component (E).
• Epoxy resin is a general term for thermosetting resins that can be cured by forming a crosslinked network with epoxy groups present in the molecule, and includes prepolymer compounds before curing.
• component (E) comprises a difunctional epoxy compound.
• the epoxy compound cannot undergo a cross-linking reaction upon excitation of the photoradical polymerization initiator (C), it remains in an unreacted state and suppresses molecular movement in the cured region of the resin composition after UV irradiation. It is Therefore, the curing reaction of the epoxy compound becomes difficult in the second stage of heat curing. Since the resin composition of the present embodiment contains (D) a thermosetting accelerator containing an azabicyclo ring compound having a bridgehead nitrogen, the thermosetting of the epoxy compound in a state in which molecular motion is suppressed can be accelerated. can.
• Epoxy compounds are roughly divided into aliphatic epoxy compounds and aromatic epoxy compounds.
• the epoxy compound preferably contains an aromatic epoxy compound.
• aliphatic epoxy compounds include - (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, poly Diepoxy compounds such as tetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether; - triepoxy compounds such as trimethylolpropane triglycidyl ether, glycerine triglycidyl ether; - cycloaliphatic epoxy compounds such as vinyl (3,4-cyclo
• cyclohexane-type diglycidyl ether means that two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having one cyclohexane ring as a base structure.
• a compound having a structure is meant.
• dicyclopentadiene-type diglycidyl ether refers to a compound having a structure in which two glycidyl groups are each bonded via an ether bond to a divalent saturated hydrocarbon group having a dicyclopentadiene skeleton as a base structure. means.
• the aliphatic polyfunctional epoxy compound preferably has an epoxy equivalent of 90 to 450 g/eq.
• cyclohexanedimethanol diglycidyl ether is particularly preferred.
• aromatic epoxy compound is an epoxy compound having a structure containing an aromatic ring such as a benzene ring.
• Many conventional epoxy resins such as bisphenol A type epoxy resin, are of this type.
• aromatic epoxy compounds include - bisphenol A type epoxy compound; - branched polyfunctional bisphenol A type epoxy compounds such as p-glycidyloxyphenyldimethyltrisbisphenol A diglycidyl ether; - bisphenol F type epoxy compound; - a novolac type epoxy compound; - Tetrabromobisphenol A type epoxy compound; - a fluorene-type epoxy compound; - biphenyl aralkyl epoxy compounds; - diepoxy compounds such as 1,4-phenyldimethanol diglycidyl ether; -biphenyl-type epoxy compounds such as 3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; -glycidylamine type epoxy compounds such as diglycidylani
• the aromatic epoxy compound is preferably a bisphenol F type epoxy compound, a bisphenol A type epoxy compound, or a glycidylamine type epoxy compound, more preferably having an epoxy equivalent of 90 to 300 g/eq, and having an epoxy equivalent of 110 to 300 g. /eq are particularly preferred, and those with epoxy equivalent weights between 150 and 220 g/eq are most preferred.
• Epoxy compounds may be used alone or in combination of two or more.
• the number of (meth)acryloyl group equivalents of component (A) and the number of epoxy group equivalents of component (E) with respect to the number of thiol group equivalents of component (B) (((Meth) acryloyl group equivalent number of component (A)] + [epoxy group equivalent number of component (E)]) / [thiol group equivalent number of component (B)]) is 0 0.25 to 3.0, more preferably 0.4 to 2.0, even more preferably 0.5 to 1.5.
• the ratio of the (meth)acryloyl group equivalent number of component (A) to the epoxy group equivalent number of component (E) (of component [A) (Meth)acryloyl group equivalent number]/[(E) component epoxy group equivalent number]) is preferably 1 to 100, more preferably 2 to 80, and further preferably 3 to 50. It is preferably 3-40, most preferably 5-35.
• the epoxy equivalent of component (E) is the number obtained by dividing the molecular weight of component (E) 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 component (E) is the number of epoxy groups (number of equivalents) per mass (amount charged) of component (E), and the mass (g) of the epoxy compound of component (E) is It is the quotient divided by the epoxy equivalent weight of the compound (if more than one epoxy compound is involved, the sum of such quotients for each epoxy compound).
• the resin composition contains (E) an epoxy compound, it is preferably 1.5 to 40% by mass, more preferably 2 to 30% by mass, based on the total mass of the resin composition. It is more preferably 3 to 20% by mass.
• the resin composition of the present embodiment may contain (F) a filler (hereinafter also referred to as “component (F)”) within a range that does not impair the effects of the present invention.
• component (F) a filler
• the coefficient of linear expansion of the cured product obtained by curing the resin composition can be lowered, and the thermal cycle resistance is improved.
• the filler has a low elastic modulus, the stress generated in the cured product can be relaxed, improving long-term reliability.
• Fillers are roughly classified into inorganic fillers and organic fillers.
• the inorganic filler is not particularly limited as long as it is composed of particles made of an inorganic material and has the effect of lowering the coefficient of linear expansion when added.
• Inorganic materials include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, oxide Titanium, 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. As the inorganic filler, it is preferable to use a silica filler because the filling amount can be increased.
• Silica is preferably amorphous silica.
• the surface of the inorganic filler is preferably treated with a coupling agent such as a silane coupling agent.
• a coupling agent such as a silane coupling agent.
• organic fillers examples include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, and styrene fillers.
• PTFE polytetrafluoroethylene
• silicone fillers examples include silicone fillers, acrylic fillers, and styrene fillers.
• the organic filler may be surface-treated.
• the shape of the filler is not particularly limited, and may be spherical, scaly, acicular, amorphous, or the like.
• the average particle size of the filler is preferably 5.0 ⁇ m or less, more preferably 4.0 ⁇ m or less, and even more preferably 3.0 ⁇ m or less.
• the average particle diameter refers to a volume-based median diameter (d 50 ) measured by a laser diffraction method in accordance with ISO-13320 (2009), or a transmission electron microscope (TEM) or scanning electron microscope. It refers to a value obtained as a number average of 50 measured values arbitrarily selected from observation images acquired by (SEM).
• the lower limit of the average particle size of the filler is not particularly limited, it is preferably 0.005 ⁇ m or more, more preferably 0.1 ⁇ m or more, from the viewpoint of the viscosity of the resin composition.
• the (F) filler preferably has an average particle size of 0.01 ⁇ m to 5.0 ⁇ m, more preferably 0.1 ⁇ m to 3.0 ⁇ m. Fillers having different average particle sizes may be used in combination. For example, a filler with an average particle size of 0.005 ⁇ m or more and less than 0.1 ⁇ m and a filler with an average particle size of 0.1 ⁇ m to 5.0 ⁇ m may be used in combination.
• the content of (F) filler in the resin composition of the present embodiment 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 (G) a stabilizer (hereinafter also referred to as “component (G)”) within a range that does not impair the effects of the present invention.
• (G) 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.
• Typical (G) stabilizers include radical polymerization inhibitors and anionic polymerization inhibitors.
• radical polymerization inhibitors can be used, and examples include, but are not limited to, N-nitroso-N-phenylhydroxylamine aluminum, triphenylphosphine, p-methoxyphenol, and hydroquinone. Further, known radical polymerization inhibitors disclosed in JP-A-2010-117545, JP-A-2008-184514, etc. can also be used. Any one of the radical polymerization inhibitors may be used, or two or more thereof may be used in combination.
• the content of the radical polymerization inhibitor is preferably 0.0001 to 5% by mass with respect to the total mass of the resin composition from the viewpoint of pot life, and 0.001 It is more preferably ⁇ 3% by mass.
• a known anionic polymerization inhibitor can be used, for example, a boric acid ester compound and a strong acid can be used.
• specific anionic polymerization inhibitors include trimethylborate, triethylborate, tri-n-propylborate, triisopropylborate, trifluoromethanesulfonic acid, maleic acid, methanesulfonic acid, barbituric acid, difluoroacetic acid, and trichloroacetic acid. , phosphoric acid, dichloroacetic acid, and the like.
• the preferred anionic polymerization inhibitor is at least one selected from tri-n-propylborate, triisopropylborate, and barbituric acid.
• anionic polymerization inhibitors disclosed in JP-A-2010-117545, JP-A-2008-184514, JP-A-2017-171804, etc. can also be used. Any one of the anionic polymerization inhibitors may be used, or two or more thereof may be used in combination.
• the content of the anionic polymerization inhibitor is preferably 0.001 to 5% by mass, more preferably 0.01 to 3% by mass, relative to the total mass of the resin composition. be.
• the resin composition of the present embodiment contains (H) a thermal radical polymerization initiator (hereinafter also referred to as “component (H)”) within a range that does not impair the effects of the present invention. may be By including a thermal radical polymerization initiator in the resin composition, it becomes possible to cure the resin composition by heating for a short period of time.
• a thermal radical polymerization initiator hereinafter also referred to as “component (H)
• Usable thermal radical polymerization initiators are not particularly limited. Known materials can be used.
• thermal radical polymerization initiators include dicumyl peroxide, t-butylcumyl peroxide, 1,3-bis(2-t-butylperoxyisopropyl)benzene, or 2,5-dimethyl-2,5-bis Dialkyl peroxides such as (t-butylperoxy)hexane, 1,1-bis(t-butylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1 -bis(t-amylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, n-butyl 4,4-bis(t-butylperoxy)valerate, or ethyl 3,3-(t-butylperoxy) ) peroxyketals such as butyrate and t-butylperoxy 2-ethylhexanoate, 1,1,3,3-tetra
• the content of (H) the thermal radical polymerization initiator is preferably 0.01 to 5% by mass, more preferably 0, based on the total mass of the resin composition. .1 to 3% by mass.
• the resin composition may contain carbon black, titanium black, a silane coupling agent, and an ion trap agent as long as the properties of the resin composition of the present embodiment are not impaired, and if necessary. , a leveling agent, an antioxidant, an antifoaming agent, or other additives. Further, the resin composition may be blended with a viscosity modifier, a flame retardant, a solvent, or the like.
• carbon black and titanium black can be used as light-shielding agents. Titanium black is preferably used from the viewpoint of achieving both light-shielding properties and UV curability (curing depth).
• titanium black examples include titanium black 12S (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), titanium black 13M (manufactured by Mitsubishi Materials Corporation), and titanium black 13M-C (manufactured by Mitsubishi Materials Corporation), TilacD (Ako Kasei Co., Ltd. company), but are not limited to these. Titanium Black 13M is particularly preferred. The type and amount of each additive are as per conventional methods.
• the method for producing the resin composition of this embodiment is not particularly limited.
• the resin composition includes, for example, component (A) to component (D), optionally component (E), component (F), component (G), component (H), and/or (I) other additives etc. can be obtained by stirring, melting, mixing and dispersing simultaneously or separately while optionally applying heat treatment.
• Devices for mixing, stirring, dispersing, etc. of these are not particularly limited.
• a Laikai machine, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, or a bead mill equipped with a stirring device and a heating device can be used. Also, these devices may be used in combination as appropriate.
• the resin composition thus obtained is both photocurable and thermosetting.
• the thermosetting temperature of the resin composition is preferably 50 to 120°C, more preferably 50 to 90°C, even more preferably 50 to 80°C, and particularly preferably 50 to 70°C when used in an image sensor module. be.
• the resin composition of the present embodiment is not only heat-cured at 80 ° C. but also heat-cured at 60 ° C. during the second-stage heat curing after the first-stage UV curing. Curing is possible.
• the resin composition of the present embodiment can be used, for example, as an adhesive, a sealing material, a damming agent, and raw materials thereof for fixing, adhering or protecting parts, and is suitable as a one-liquid type.
• the damming agent is formed in advance on the outer periphery of the substrate, for example, before sealing a plurality of semiconductor chips or the like on the substrate with a low-viscosity filling agent or the like. Formation of the dam by the dam agent can suppress subsequent outflow of the low-viscosity filling agent that seals the plurality of semiconductor chips.
• the adhesive containing the resin composition of the present embodiment enables good bonding to engineering plastics, ceramics, and metals.
• the adhesive or encapsulant of the second embodiment of the present invention contains the resin composition of the first embodiment described above. This adhesive or encapsulant allows good bonding to engineering plastics, ceramics and metals.
• the adhesive or sealing material of the present embodiment is preferably used for fixing, adhering or protecting parts that constitute an image sensor or camera module.
• 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 or sealing material of the second embodiment.
• a semiconductor device or electronic component according to the fourth embodiment of the present invention includes the cured product of the third embodiment described above.
• semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic equipment, and the like.
• semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, camera modules, semiconductor modules, and integrated circuits.
• the semiconductor device or electronic component can be an image sensor or a camera module.
• A-1 Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd., acryloyl equivalent: 152 g/eq)
• A-2 Neopentyl glycol-modified trimethylolpropane diacrylate (product name: Kayarad R-604, manufactured by Nippon Kayaku Co., Ltd., acryloyl equivalent: 163 g/eq)
• A-3 Ditrimethylolpropane tetraacrylate (product name: EBECRYL 140, manufactured by Daicel-Ornex Co., Ltd., acryloyl equivalent: 117 g/eq)
• C- (C) photoradical initiator component (C)
• C-1 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Omnirad 184, manufactured by IGM Resins)
• C-2 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (product name: Omnirad TPO H, manufactured by IGM Resins B.V.)
• thermosetting accelerator containing an azabicyclo ring compound having a bridgehead nitrogen (component (D))
• D-1 Thermal curing accelerator containing 1,4-diazabicyclo[2.2.2]octane (DABCO (registered trademark)) (product name: Novacure HXA5945HP, manufactured by Asahi Kasei Corporation)
• D-2 Thermal curing accelerator containing 1,4-diazabicyclo[2.2.2]octane (DABCO (registered trademark)) (1,4-diazabicyclo[2.2.2]octane itself, Tokyo Obtained from Kasei Kogyo Co., Ltd.)
• D-3) A heat curing accelerator (1-azabicyclo[2.2.2]octane-3-) containing 1-azabicyclo[2.2.2]octan-3-ol (common name: 3-quinuclidinol) oar itself, obtained from Tokyo Chemical Industry Co., Ltd.) (D-1): Thermal cu
• D' Heat curing accelerator other than component (D) (component (D'))
• D'-1 Thermal curing accelerator containing an imidazole compound (product name: Novacure HXA3922HP, manufactured by Asahi Kasei E-Materials Co., Ltd.)
• D'-2) A thermosetting accelerator containing 2-ethyl-4-methylimidazole (trade name: CURESOL 2E4MZ, manufactured by Shikoku Kasei Co., Ltd.)
• the component (D-1) and the component (D'-1) are fine particle curing accelerator compounds containing epoxy compounds (bisphenol A type epoxy compound and bisphenol It is provided in the form of a dispersion dispersed in a mixture of epoxy compounds of type F.
• the parts by mass of component (D-1) and component (D'-1) in Table 1 are the parts by mass of the dispersion to the epoxy compound.
• the epoxy compound constituting this dispersion is treated as a part of component (E), and the epoxy compound in (D-1) is the component ( E-1), and the epoxy compound in (D'-1) is component (E-2), and the parts by mass of (E-1) and (E-2) in Table 1 are component (D-1) and parts by mass of the epoxy compound in component (D'-1).
• Epoxy compound (component (E)) - (E-1) a mixture of a bisphenol A type epoxy compound and a bisphenol F type epoxy compound (epoxy equivalent: 180 g/eq)
• E-2 a mixture of a bisphenol A type epoxy compound and a bisphenol F type epoxy compound (epoxy equivalent: 180 g/eq) -
• E-3 A mixture of a bisphenol A type epoxy compound and a bisphenol F type epoxy compound (product name: EXA-835LV, manufactured by DIC Corporation, epoxy equivalent: 165 g/eq)
• ⁇ Filler (component (F)) (F-1): Silica filler (product name: SE2300, average particle size 0.6 ⁇ m, manufactured by Admatechs Co., Ltd.) (F-2): Calcium carbonate filler (product name: CS4NA, average particle size: ⁇ 0.5 ⁇ m, manufactured by Ube Material Industries, Ltd.) (F-3): Hydrophobic fumed silica (product name: CAB-O-SIL (registered trademark) TS720, manufactured by CABOT, average particle size: 12 nm) ⁇ Stabilizer (component (G)) (G-1): Triisopropyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.) (G-2): N-nitroso-N-phenylhydroxylamine aluminum (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
• the residual calorific value is 25 J/g or less, it is judged that the remaining unreacted component is suppressed and is rated as "A”, and if it is greater than 25 J/g, it is judged that the remaining unreacted component is greater. and "F".
• the 60° C. curability of the prepared resin composition was evaluated by dropping one drop of the resin composition to obtain a sample, and then heating the sample at a temperature of 60° C. for 60 minutes, and then observing the state of the sample. If the sample is solid and there is no stringiness, it is judged to be sufficiently cured and marked as "A”. ", and when the hemispherical sample did not become solid, it was judged to be uncured and rated as "F”. Table 1 shows the results.
• the resin compositions of Examples 1 to 15 contained (D) a heat curing accelerator containing an azabicyclo ring compound having a bridgehead nitrogen, so that curing after heat curing in the second stage following UV curing in the first stage Remaining of unreacted components in the product was suppressed, and the resin composition could be heat-cured at 60°C.
• a heat curing accelerator containing an azabicyclo ring compound having a bridgehead nitrogen so that curing after heat curing in the second stage following UV curing in the first stage Remaining of unreacted components in the product was suppressed, and the resin composition could be heat-cured at 60°C.
• Comparative Examples 1 and 2 in which the resin composition contains a thermosetting accelerator other than the component (D), unreacted components are contained in the cured product after the second stage of thermal curing following the first stage of UV curing. Residual was higher and the resin composition could not be cured at 60°C.
• Example 1 [Ratio of increase in strength of cured product by additional heating]
• the curing conditions at this time were as follows: UV LED irradiation device AC475 manufactured by Excelitas Technologies Inc.
• alumina chip on this LCP 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.
• a test piece prepared in the same manner was additionally heated at 120° C. for 1 hour in a blower dryer, and the shear strength was calculated in the same manner as the shear strength B.
• the resin composition is irradiated with UV using a UV LED irradiation device AC475 manufactured by Excelitas Technologies Inc.
• Example 1 The cured product obtained in Example 1 had almost no change in shrinkage rate due to additional heating, and the cured product obtained in Comparative Example 1 had an increase in shrinkage rate due to additional heating of 0.2%. From this, it is considered that the amount of change over time is smaller in the example, and problems such as misalignment are less likely to occur.
• Example 1 and Comparative Example 1 were UV-cured at a UV dose of 2000 mJ/cm 2 (UV wavelength: 365 nm, LED lamp) to prepare resin cured products.
• 10 mg of the resulting resin cured product was sampled and measured using a simultaneous differential thermogravimetric measurement device (TG8120 manufactured by Rigaku Corporation), and the outgas generated during heating at 80 ° C. for 60 minutes under air conditions (generated in normal curing outgas), and the amount of outgas generated from the initial heating of 80 ° C for 60 minutes to the time of reaching 120 ° C when the temperature is increased from 80 ° C to 120 ° C at 10 ° C / min as additional heating (generated by additional heating possible outgas) was measured.
• TG8120 manufactured by Rigaku Corporation
• UV Curability in UV Curing Insufficient Area When an adhesive containing a photo- and thermosetting resin composition is used in the assembly process of a semiconductor module (e.g., an image sensor module or a camera module), in UV irradiation curing, UV irradiation is performed from the outside of the semiconductor module, so the semiconductor The inside of the module is hard to be exposed to UV light, and there may be an insufficiently UV-cured area in which the adhesive is partly UV-cured but not completely UV-cured. It has been found that the unreacted components remaining in the UV curing insufficient region do not proceed with the curing reaction even during the next heat curing, and are particularly likely to remain as residual components.
• a semiconductor module e.g., an image sensor module or a camera module
• Comparative Example 3 is an example in which the component (D-2) in the resin composition of Example 13 was replaced with the component (D'-2).
• the resin compositions of Example 13 and Comparative Example 3 were defoamed in vacuum, UV-cured at a UV dose of 40 mJ/cm 2 (UV wavelength: 365 nm, LED lamp), and then dried in a blower dryer at 60° C./60 minutes. and heat curing at 80° C./60 minutes to obtain a cured resin.
• the cured product of the resin composition obtained in Example 13 had almost no residual heat generation, whereas the cured product of the resin composition obtained in Comparative Example 3 had a large amount of residual heat generation. From this, it can be seen that the examples containing the component (D) show high thermosetting properties even in the incompletely cured region that reproduces the region that is difficult to be exposed to UV light, and therefore the amount of unreacted components is small. was confirmed. It is believed that the small amount of unreacted components has the effect of suppressing the displacement and outgassing described above.
• the present invention is a resin composition that suppresses the residual of unreacted components in the cured product after the second stage of heat curing following the first stage of UV curing, and that can be heat cured at 60 ° C. , as an adhesive or sealing material used for fixing, adhering or protecting parts constituting an image sensor or camera module.

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• 2023
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