Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • 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
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
• • 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
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/38—Epoxy compounds containing three or more epoxy groups together with 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
  • C08G59/40—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
• • 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
  • C08G59/50—Amines
  • C08G59/5046—Amines heterocyclic
  • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
  • C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
• • 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
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
  • C08G59/623—Aminophenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen
• • 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
  • C09J11/04—Non-macromolecular additives inorganic
• • 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
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
• • 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
  • H10W74/473—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins containing a filler

Definitions

• the present invention relates to an epoxy resin composition, a resin paste, a resin film, and a semiconductor device.
• Epoxy resins have traditionally been used for a wide range of applications, including as insulating materials for electrical and electronic components such as semiconductor elements, sealing materials, adhesives, conductive materials, matrix resins for fiber-reinforced plastics, and impregnating adhesives for motor coils.
• epoxy resin compositions that have excellent adhesion and high reliability are used as sealing materials and adhesives for semiconductor devices.
• the components of the epoxy resin composition generally include, for example, an epoxy resin, a curing agent such as a phenolic resin that is reactive with the epoxy resin, and a curing accelerator that promotes the reaction between the epoxy resin and the curing agent.
• the sealing material for semiconductor devices requires resin pastes that can penetrate and fill narrow gaps, and resin films that can seal and bond entire large-area chips at the same time.
• the sealing materials and adhesive materials used in these semiconductor devices are required to have a high glass transition temperature and to have a small decrease in elastic modulus in a high temperature range above the glass transition temperature. If there is a large difference in elastic modulus between room temperature and above the glass transition temperature, the physical properties of the cured layer will change significantly when the electronic device generates heat, and the reliability of sealing and adhesion will tend to decrease.
• stacked MCPs Multi Chip Packages
• Resin films are mainly used for bonding between the circuit board and the semiconductor chips in stacked MCPs and for bonding between the semiconductor chips themselves, because of the advantages of having a uniform thickness and being less likely to cause tilting of the chips.
• thinner resin films are required for miniaturization and high integration.
• films that have a high glass transition temperature and suppress the decrease in elastic modulus in the high temperature range, as described above.
• a sealing material or adhesive for a semiconductor device for example, a paste-like resin composition consisting of a trifunctional epoxy resin, a curing agent such as an aromatic amine, a filler, etc. is known as a material that is filled into the gap between various electronic components and a circuit board and then cured (see, for example, Patent Document 1).
• electrical connection and sealing may be performed simultaneously by thermocompression bonding and curing a semiconductor chip that has been previously supplied with a resin film to a circuit board.
• a film-type adhesive consisting of a multifunctional epoxy resin, a curing agent, a filler, etc. is known (see, for example, Patent Document 2).
• a resin film for bonding semiconductor chips to circuit boards, and semiconductor chips to each other for example, a film-type adhesive made of a multifunctional epoxy resin, a hardener such as imidazole, a filler, etc. is known (for example, Patent Document 3).
• a curable composition containing a curing agent for an anionic curable compound consisting of an imidazole-based compound having a substituted phenyl group at the 2-position of the imidazole ring has been disclosed (see, for example, Patent Document 4). It has been disclosed that such a curable composition can selectively carry out a curing reaction of the epoxy resin in a high temperature range around 150° C. and also has excellent storage stability.
• Patent Documents 1 to 3 In general, in order to achieve a high glass transition temperature and suppress the decrease in elastic modulus at high temperatures, as disclosed in Patent Documents 1 to 3, it is effective to blend a polyfunctional epoxy resin having three or more functionalities (hereinafter, also simply referred to as "polyfunctional epoxy resin") into an epoxy resin composition to increase the crosslink density of the cured layer.
• polyfunctional epoxy resin having three or more functionalities
• the inventors of the present invention have confirmed that in the presence of a polyfunctional epoxy resin, the initial thickening during heating is rapid, so that the epoxy resin and the curing agent cure before their functional groups have completely reacted, and sufficient crosslink density cannot be obtained, resulting in a lower glass transition temperature than expected and a significant decrease in elastic modulus at high temperatures.
• the glass transition temperature it has been difficult to obtain a glass transition temperature above the curing temperature even when a polyfunctional epoxy resin is blended, and there is room for improvement.
• the curing agent for anionic curing compounds disclosed in Patent Document 4 is shown to be capable of achieving both stability during storage and curability in a high temperature range around 150° C., but does not clearly indicate any composition that satisfies both the high glass transition temperature and the suppression of decrease in elastic modulus at high temperatures, which are required for applications such as sealing materials and adhesives for increasingly dense semiconductor devices, and there is still room for further study.
• the present inventors have confirmed that there is a problem with filling property when only using the curing agent for anionic curing compounds disclosed in Patent Document 4. Filling property is important for spreading the epoxy resin composition without gaps according to the gaps, the shapes of each semiconductor chip, and the electronic components when sealing or bonding electronic components.
• the epoxy resin composition can maintain a low viscosity state for a certain period of time when heated to, for example, 110°C to 130°C. If the time for which the low viscosity state can be maintained is short, filling failure occurs, and sealing or bonding with excellent reliability cannot be performed.
• the present invention aims to provide an epoxy resin composition that is completely uniform, has sufficient filling properties, and has a high glass transition temperature and can suppress a decrease in elastic modulus at high temperatures even when a multifunctional epoxy resin is blended.
• the present inventors have found that an epoxy resin composition containing a tri- or higher functional polyfunctional epoxy resin and an imidazole compound having a specific structure can be obtained, and when the temperature T°C is kept constant and satisfies 130 ⁇ T ⁇ 150, and the time t minutes until the viscosity reaches 10,000 Pa s is taken as the reference temperature from the time when the temperature T°C is reached, the slope ⁇ of the straight line obtained by plotting Lnt (vertical axis) against 1/T (horizontal axis) satisfies 690 ⁇ 1000, and the epoxy resin composition is completely uniform and has sufficient filling property, and when a polyfunctional epoxy resin is blended therein, it has a significantly high glass transition temperature that exceeds the curing temperature and is capable of suppressing a decrease in elastic modulus at high temperatures, and has thus completed the present invention. That is, the present invention is as follows.
• Component (A) an epoxy resin
• Component (B) A compound represented by the following formula (1) and/or a compound represented by the following formula (2)
• the component (A) contains at least one polyfunctional epoxy resin having a functionality of three or more
• R 1 and R 2 are each independently any one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent;
• R 1 and R 2 may be the same or different, and R 1 and R 2 may be bonded to form a fused ring having no aromaticity;
• X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent,
• X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent
• Y and Z are any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an
• the component (A) further contains a difunctional or lower epoxy resin.
• the blending ratio (mass ratio) of the trifunctional or higher polyfunctional epoxy resin to the difunctional or lower epoxy resin is in the range of 1:0.1 to 1:10.
• the component (A) contains an epoxy resin having an aromatic ring, The resin composition according to any one of [1] to [3].
• the component (A) contains an epoxy resin having no aromatic ring, The resin composition according to any one of [1] to [4].
• Y is one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms and no substituent, an alkyl group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an alkoxy group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an aryl group having 6 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an aryloxy group having 6 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, and an acyl group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent,
• Y and Z are each one selected from the group consisting
• the compound represented by the formula (1) any one selected from the group consisting of 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole, and 2-(2-hydroxy-3(5)-methoxyphenyl)imidazole; and/or
• the compound represented by the formula (2) The epoxy resin composition according to any one of [1] to [5], which is any one selected from the group consisting of 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphthalen-2-yl)benzimidazole, 2-(2-hydroxynaphthalen-1-
• Component (C) Further containing a filler, The epoxy resin composition according to any one of [1] to [7].
• the component (G) is an aminosilane coupling agent.
• Component (H) Further containing a non-epoxy-terminated compound having a polyalkylene oxide structure, The epoxy resin composition according to any one of [1] to [11].
• the terminal of the component (H) is a hydroxyl group.
• the component (H) is a compound represented by the following formula (3): The epoxy resin composition according to [13].
• R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms, and R 3 and R 4 may be the same or different.
• p and q are each independently an integer of 1 or more.
• R 5 and R 6 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent.
• R 5 and R 6 may be the same or different.
• the present invention provides an epoxy resin composition that is completely uniform, has sufficient filling properties, and has a high glass transition temperature and can suppress a decrease in elastic modulus at high temperatures even when a multifunctional epoxy resin is blended.
• the present embodiment a DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
• the present embodiment an embodiment for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail.
• the following embodiments are merely illustrative for explaining the present invention, and are not intended to limit the present invention to the following contents.
• the present invention can be practiced with appropriate modifications within the scope of the gist thereof.
• the epoxy resin composition of the present embodiment comprises: Component (A): an epoxy resin, Component (B): A compound represented by the following formula (1) and/or a compound represented by the following formula (2),
• the component (A) contains at least one polyfunctional epoxy resin having a functionality of three or more, When the temperature is kept constant at T°C satisfying 130 ⁇ T ⁇ 150, and the time it takes for the viscosity to reach 10,000 Pa s is taken as t minutes from the time when the temperature reaches T°C, the slope ⁇ of the straight line obtained by plotting Lnt (vertical axis) against 1/T (horizontal axis) satisfies 690 ⁇ 1,000.
• R 1 and R 2 are each independently any one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent;
• R 1 and R 2 may be the same or different, and R 1 and R 2 may be bonded to form a fused ring having no aromaticity;
• X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent,
• X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent
• Y and Z are any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an
• the epoxy resin composition of the present embodiment is completely uniform and has sufficient filling property, and even if a polyfunctional epoxy resin is blended, in addition to having a high glass transition temperature, it is possible to suppress a decrease in elastic modulus at high temperatures.
• the epoxy resin composition of the present embodiment contains an epoxy resin (hereinafter, may be referred to as epoxy resin (A) or component (A)).
• the epoxy resin (A) contains at least one polyfunctional epoxy resin having a functionality of three or more.
• the tri- or higher functional polyfunctional epoxy resins are not particularly limited as long as they are epoxy resins having three or more epoxy groups in one molecule.
• trifunctional epoxy resins examples include trifunctional glycidylamine type epoxy resins such as triglycidyl-p-aminophenol, triazine type epoxy resins, trimethylolpropane triglycidyl ether, and glycerin triglycidyl ether; tetrafunctional epoxy resins such as naphthalene type tetrafunctional epoxy resins, tetraglycidyldiaminodiphenylmethane type epoxy resins, tetraglycidylbis(aminomethyl)cyclohexane, diaminobenzene type epoxy resins, and pentaerythritol type epoxy resins; and polyfunctional epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadiene type
• the resin paste to contain a polyfunctional glycidylamine-type epoxy resin such as triglycidyl-p-aminophenol or tetraglycidyldiaminodiphenylmethane-type epoxy resin, or tetraglycidylbis(aminomethyl)cyclohexane, or a pentaerythritol-type epoxy resin.
• a polyfunctional glycidylamine-type epoxy resin such as triglycidyl-p-aminophenol or tetraglycidyldiaminodiphenylmethane-type epoxy resin, or tetraglycidylbis(aminomethyl)cyclohexane, or a pentaerythritol-type epoxy resin.
• the resin film preferably contains a polyfunctional glycidylamine-type epoxy resin, such as triglycidyl-p-aminophenol or tetraglycidyldiaminodiphenylmethane-type epoxy resin, or tetraglycidylbis(aminomethyl)cyclohexane, or a pentaerythritol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a phenol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a biphenyl novolac-type epoxy resin, a triphenylmethane-type epoxy resin, a tetraphenylethane-type epoxy resin, or a pentaerythritol-type epoxy resin.
• a polyfunctional glycidylamine-type epoxy resin such as triglycidyl-p-aminophenol or tetraglycidyldiamino
• polyfunctional epoxy resins having three or more functionalities include, but are not limited to, DIC product names: HP-4700, HP-4710 (naphthalene-type tetrafunctional epoxy resins), N-690, N-695 (cresol novolac-type epoxy resins), HP-7200, HP-7200H, HP-7200HH (dicyclopentadiene-type epoxy resins), HP-6000, HP-6000L, EXA-7311, EXA-7 311-G3, EXA-7311-G4, EXA-7311-G4S (naphthylene ether type epoxy resin), Chang Chun Co., Ltd. product name: CNE220 (cresol novolac type epoxy resin), Nippon Kayaku Co., Ltd.
• EPPN-502H triphenylmethane type epoxy resin
• NC3000, NC3000H, NC3000L, NC3100 biphenyl type epoxy resin
• NC-7000L naphthol novolac type epoxy resin
• Epoxy resins (A) other than trifunctional or higher polyfunctional epoxy resins are not particularly limited as long as they are epoxy resins having two or less epoxy groups in one molecule, but examples include bisphenol A type, bisphenol F type, bisphenol E type epoxy resins, bisphenol AD type epoxy resins, bisphenol AF type epoxy resins, tetrabromobisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidylamine type epoxy resins, silicone modified epoxy resins, biphenyl type epoxy resins, bixylenol type epoxy resins, tetrabromobiphenyl type epoxy resins, fluorene type epoxy resins, diphenyl ether bifunctional epoxy resins such as benzophenone type epoxy resins, phenyl benzoate type epoxy resins, diphenyl sulfide type epoxy resins, diphenyl sulfoxide type epoxy resins, diphenyl sulfone type epoxy resins, diphenyl disulfide type epoxy resin
• examples of the diglycidyl ether include N,N-diglycidylaminobenzene, o-(N,N-diglycidylamino)toluene, 2-ethylhexyl glycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, butanediol diglycidyl ether, glycerin diglycidyl ether, cyclohexane type diglycidyl ether, dicyclopentadiene type diglycidyl ether, vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane, 1,3-diglycid
• the resin paste preferably contains an epoxy resin having an aromatic ring from the viewpoints of fluidity and strength, and more preferably contains a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a fluorene type epoxy resin, p-tert-butylphenyl glycidyl ether, N,N-diglycidylaminobenzene, or o-(N,N-diglycidylamino)toluene.
• a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, a naphthalene type epoxy resin, a fluorene type epoxy resin, p-tert-butylphenyl glycidyl ether, N,N-diglycidylaminobenzene, or o-(N,N-diglycidylamino)toluene.
• the epoxy resin in cases where the amount of filler is large, when the filling ability is to be increased, or from the viewpoint of reducing warpage of the cured product, it is preferable for the epoxy resin to contain an epoxy resin having no aromatic ring or an epoxy resin having a polyalkylene oxide structure, and it is more preferable for the epoxy resin to contain a hydrogenated bisphenol A type epoxy resin, a cyclohexane type diglycidyl ether, a dicyclopentadiene type diglycidyl ether, or a polytetramethylene glycol diglycidyl ether.
• the resin film preferably contains an epoxy resin having an aromatic ring, and preferably contains a bifunctional epoxy resin having a bisphenol A type structure, a bisphenol F type structure, a bisphenol AF type structure, a naphthalene structure, a fluorene structure, or a glycidylamine structure.
• the epoxy resin contains a bifunctional epoxy resin having a cyclohexane structure, a cyclohexanedimethanol structure, a polyalkylene oxide structure or a butadiene structure, or an alicyclic bifunctional epoxy resin having an ester skeleton.
• the epoxy resin (A) other than the trifunctional or higher polyfunctional epoxy resin is not particularly limited, and examples thereof include trade names of EXA850CRP (BisA type epoxy resin), EXA830CRP (BisF type epoxy resin), HP4032, HP4032D, and HP4032SS (naphthalene type epoxy resin) manufactured by DIC Corporation, and trade names of jER828US, jER828EL, jER825, and YL980 (bisphenol A type epoxy resin), jER807, jER1750, and YL983U (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation.
• YX7400N polytetramethylene glycol type epoxy resin
• YX4000, YX4000H, YX4000HS, YL6121 biphenyl type epoxy resin
• YX4000HK biixylenol type epoxy resin
• YX8800 anthracene type epoxy resin
• YX7760 fluorine-containing special epoxy resin
• product name: ZX1059 mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin
• ZX1658, ZX1658GS liquid 1,4-glycidylcyclohexane type epoxy resin
• epoxy resins include bisphenol A bis(triethylene glycol glycidyl ether) ether (trade name: BEO-60E, manufactured by New Japan Chemical Co., Ltd.), EX-721 (glycidyl ester type epoxy resin, manufactured by Nagase ChemteX Corporation), CELLOXIDE 2021P (alicyclic epoxy resin having an ester skeleton, manufactured by Daicel Corporation), OGSOL PG-100, CG-500, EG-280 (fluorene type epoxy resin, manufactured by Osaka Gas Chemicals Co., Ltd.), EPOGOSE PT (polytetramethylene glycol type epoxy resin, manufactured by Yokkaichi Chemical Co., Ltd.), and AER9000 (specially modified epoxy resin, manufactured by Asahi Kasei Corporation).
• the epoxy resin (A) contains at least one polyfunctional epoxy resin having three or more functionalities, and is preferably used in combination with an epoxy resin having two or less functionalities.
• the viscosity can be appropriately lowered, resulting in good handleability and filling properties, (ii) improved adhesion to circuit components, and (iii) sufficient flexibility is obtained and improved crack resistance.
• the mass ratio therebetween is not particularly limited, but from the viewpoint of the effects (i) to (vi) above, it is preferably in the range of 1:0.1 to 1:10, more preferably in the range of 1:0.2 to 1:9, even more preferably in the range of 1:0.3 to 1:8, even more preferably in the range of 1:0.4 to 1:7, and even more preferably in the range of 1:0.5 to 1:6.
• the epoxy equivalent of the tri- or higher functional epoxy resin is preferably 50 g/eq. to 500 g/eq., more preferably 50 g/eq. to 450 g/eq., even more preferably 80 g/eq. to 400 g/eq., even more preferably 80 g/eq. to 350 g/eq., and still more preferably 85 to 300 g/eq.
• the crosslink density of the cured product of the epoxy resin composition of the present embodiment when used in combination with component (B) falls within an appropriate range, and a cured product layer having an excellent balance between the glass transition temperature of the cured product, suppression of decrease in elastic modulus at high temperatures, and cured product strength tends to be obtained.
• the epoxy equivalent of a di- or lower-functional epoxy resin is not particularly limited and can be appropriately set depending on the desired performance, but from the viewpoint of ensuring a sufficient range of crosslink density when used in combination with a tri- or higher-functional epoxy resin and balancing the elongation, toughness, and strength of the cured product, the epoxy equivalent is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., even more preferably 80 g/eq. to 2000 g/eq., still more preferably 100 g/eq. to 1000 g/eq., and even more preferably 120 to 900 g/eq.
• the epoxy equivalent is the mass of a resin that contains one equivalent of an epoxy group.
• the epoxy equivalent can be measured in accordance with JIS K7236.
• the total chlorine content contained in the epoxy resin (A) is preferably 2500 ppm or less, more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and still more preferably 900 ppm or less.
• the total chlorine content in the epoxy resin (A) is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, even more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, and particularly preferably 0.5 ppm or more.
• the total chlorine content herein refers to the total amount of organic chlorine and inorganic chlorine contained in the epoxy resin (A), and is a value based on the mass of the epoxy resin (A).
• the total chlorine content of the epoxy resin (A) is measured by the following method. Epoxy resin (A) is repeatedly washed with xylene and filtered until no epoxy resin remains in the xylene washing solution. The filtrate is then distilled under reduced pressure at 100°C or less to obtain the epoxy resin.
• 1-10 g of the obtained epoxy resin sample is precisely weighed out so that the titer is 3-7 mL, dissolved in 25 mL of ethylene glycol monobutyl ether, and 25 mL of 1N KOH propylene glycol solution is added to this, boiled for 20 minutes, and titrated with an aqueous silver nitrate solution to calculate the titer.
• the content of the total epoxy resin (A) in the epoxy resin composition of this embodiment which is the sum of the trifunctional or higher epoxy resins and the difunctional or lower epoxy resins, can be appropriately set according to the desired performance and is not particularly limited, but is preferably 5% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 90% by mass or less, and particularly preferably 15% by mass or more and 85% by mass or less, of all non-volatile components excluding the solvent.
• the epoxy resin composition of this embodiment tends to have high adhesion.
• Component (B) a compound represented by the following formula (1) or (2)
• the epoxy resin composition of the present embodiment contains a compound represented by the following formula (1) and/or a compound represented by the following formula (2) (hereinafter, may be referred to as compound (B) or component (B)).
• R 1 and R 2 are each independently any one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent;
• R 1 and R 2 may be the same or different, and R 1 and R 2 may be bonded to form a fused ring having no aromaticity;
• X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent,
• X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent
• Y and Z are any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an
• R 1 and R 2 in the above general formula (1) are each independently one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, a cyano group, a nitro group, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, or a structure in which R 1 and R 2 are on the same condensed ring which does not have aromaticity, and R 1 and R 2 may be the same or different.
• the alkyl group having 1 to 20 carbon atoms may be linear or branched, and the number of carbon atoms in the alkyl group is preferably 1 to 18, more preferably 1 to 15, and even more preferably 1 to 10.
• the alkyl group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group.
• the number of carbon atoms in the cycloalkyl group having 6 to 20 carbon atoms is preferably 6 to 18, and more preferably 6 to 15.
• the cycloalkyl group having 6 to 20 carbon atoms is not particularly limited, and examples thereof include a cyclohexyl group, a cycloheptane group, and a cyclooctane group.
• Specific examples of the structure in which R 1 and R 2 are on the same condensed ring that does not have aromaticity include cyclopentane, cyclohexane, and dicyclopentadiene.
• the alkyl group, the cycloalkyl group, and the structure in which R 1 and R 2 are on the same condensed ring that does not have aromaticity may have a substituent.
• the substituent is not particularly limited, but examples thereof include a halogen atom, a hydroxyl group, an alkoxy group, and a nitro group, and preferably a hydroxyl group or an alkoxy group.
• X is any one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a heteroarylalkyl group having 4 to 20 carbon atoms which may have a substituent.
• the alkyl group having 1 to 20 carbon atoms represented by X may be linear or branched, and the number of carbon atoms of the alkyl group is preferably 1 to 18, and more preferably 1 to 15.
• Examples of the alkyl group having 1 to 20 carbon atoms include, but are not limited to, a methyl group, an ethyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group.
• the alkenyl group having 2 to 20 carbon atoms represented by X may be linear or branched, and the number of carbon atoms of the alkenyl group is preferably 2 to 18, and more preferably 2 to 15.
• the alkenyl group having 2 to 20 carbon atoms is not particularly limited, but examples thereof include a vinyl group, an aryl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 3-butenyl group, a 2-pentenyl group, and a 2-hexenyl group.
• the aralkyl group having 7 to 20 carbon atoms as X may be linear or branched, and the number of carbon atoms in the aralkyl group is preferably 7 to 18, and more preferably 7 to 15.
• the aralkyl group having 7 to 20 carbon atoms is not particularly limited, but examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
• the heteroarylalkyl group having 4 to 20 carbon atoms as X may be linear or branched, and the number of carbon atoms of the heteroarylalkyl group is preferably 4 to 18, and more preferably 4 to 15.
• Examples of heteroarylalkyl groups having 4 to 20 carbon atoms include, but are not limited to, a triazinylmethyl group, a triazinylethyl group, a 2-pyridylmethyl group, a 2-pyridylethyl group, a 3-pyridylmethyl group, a 3-pyridylethyl group, a 4-pyridylmethyl group, and a 4-pyridylethyl group.
• the alkyl group, alkenyl group, aralkyl group, or heteroarylalkyl group may have a substituent.
• the substituent is not particularly limited, but examples thereof include a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkoxy group, an amino group, an ester group, an arylsulfonyl group, an alkylsulfonyl group, and a phenyl group, and is preferably a cyano group, an alkoxy group, an amino group, an ester group, or a phenyl group.
• Y in the general formula (1) and Y and Z in the general formula (2) are any one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a substituent, and an acyl group having 1 to 20 carbon atoms which may have a substituent.
• two or more Ys may be bonded to each other to form a monocyclic ring or a condensed ring.
• two or more Ys and two or more Zs may be bonded to each other to form a monocyclic ring or a condensed ring.
• m is an integer of 1 to 4.
• m and n are each independently an integer of 1 to 4.
• the alkyl group having 1 to 20 carbon atoms as Y and Z may be linear or branched, and the number of carbon atoms of the alkyl group is preferably 1 to 18, and more preferably 1 to 15.
• Examples of the alkyl group having 1 to 20 carbon atoms include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a decyl group, and an undecyl group.
• the alkoxy groups having 1 to 20 carbon atoms as Y and Z may be linear or branched, and the number of carbon atoms is preferably 1 to 18, and more preferably 1 to 15.
• Examples of the alkoxy groups having 1 to 20 carbon atoms include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy, and 2-ethylhexyloxy.
• the alkenyl groups having 2 to 20 carbon atoms as Y and Z may be linear or branched, and the number of carbon atoms of the alkenyl group is preferably 2 to 18, and more preferably 2 to 15.
• the alkenyl group having 2 to 20 carbon atoms is not particularly limited, but examples thereof include vinyl groups, aryl groups, 1-propenyl groups, isopropenyl groups, 2-butenyl groups, 3-butenyl groups, 2-pentenyl groups, and 2-hexenyl groups.
• the number of carbon atoms in the aryl group having 6 to 20 carbon atoms represented by Y and Z is preferably 6 to 18, and more preferably 6 to 15.
• the aryl group having 6 to 20 carbon atoms is not particularly limited, but examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, and a biphenyl group.
• examples of structures in which two or more Y's or two or more Z's are bonded to form a single ring or a condensed ring include, but are not limited to, naphthyl groups, anthracenyl groups, etc.
• the carbon number of the 1-20 carbon atom acyl group represented by Y and Z is preferably 1-18, more preferably 1-15.
• Examples of the 1-20 carbon atom acyl group include, but are not limited to, an acetyl group, a benzoyl group, and a pivaloyl group.
• the alkyl group, alkoxy group, alkenyl group, aryl group, aryloxy group, and acyl group may have a substituent.
• substituents include an alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, an alkoxy group, a nitro group, an ester group, and a phenyl group, and preferably an alkyl group, a hydroxyl group, a carboxyl group, or an alkoxy group.
• Y may be substituted at any of the ortho, meta, or para positions of the phenyl group which is the substituent at the 2-position of the imidazole, but if it has a substituent, it is preferably substituted at a position other than the ortho position, and more preferably at least the meta position, and more preferably the meta position is substituted with a hydroxyl group or an alkoxy group having 1 to 20 carbon atoms which may have a substituent.
• Y is one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms and no substituent, an alkyl group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an alkoxy group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an aryl group having 6 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an aryloxy group having 6 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, and an acyl group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent.
• Y and Z in general formula (2) are more preferably one selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms without a substituent, an alkyl group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an alkoxy group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an aryl group having 6 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an aryloxy group having 6 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, and an acyl group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent.
• Y and Z are hydrogen atoms, the dielectric loss tangent of the cured product obtained using the epoxy resin composition of the present embodiment tends to be further reduced. Furthermore, when Y and Z are a hydroxyl group, a carboxy group, an alkoxy group having 1 to 20 carbon atoms without a substituent, an alkyl group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an alkoxy group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an aryl group having 6 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, an aryloxy group having 6 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substituent, or an acyl group having 1 to 20 carbon atoms and having a hydroxyl group and/or a carboxy group as a substitu
• the compound represented by the general formula (1) is not limited to the following imidazole compounds: For example, 2-(2-hydroxyphenyl)imidazole, 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxyphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxyphenyl)imidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole, 2-(2-hydroxy-3-methylphenyl)imidazole, 2-(2-hydroxy-3-methylphenyl)-4(5)-methylimidazole, 4(5)-ethyl 2-(2-hydroxy-3-methylphenyl)imidazole, 4,5-dimethyl-2-(2-hydroxy-3-methylphenyl)imidazole, 4-ethyl-(2-hydroxy-3-methylphenyl
• 4,5-dimethyl-2-(2-hydroxy-4-methylphenyl)imidazole 4-ethyl-(2-hydroxy-4-methylphenyl)-5-methylimidazole, (2-hydroxy-4-methylphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxy-4-methylphenyl)-5-methylimidazole, 2-(2-hydroxy-5-methylphenyl)imidazole, 2-(2-hydroxy-5-methylphenyl)-4(5)-methylimidazole, 4(5)-ethyl-2-(2-hydroxy-5-methylphenyl)imidazole, 4, Examples include 5-dimethyl-2-(2-hydroxy-5-methylphenyl)imidazole, 4-ethyl-(2-hydroxy-5-methylphenyl)-5-methylimidazole, (2-hydroxy-5-methylphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxy-5-methylphenyl)-5-methylimidazole
• 2-(3-t-butyl-2-hydroxyphenyl)-4,5-dimethylimidazole 2-(3-t-butyl-2-hydroxyphenyl)-4-ethyl-5-methylimidazole, 2-(3-t-butyl-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(3-t-butyl-2-hydroxyphenyl)-5-methylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4(5)-methylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4,5-dimethylimidazole, 4-ethyl-2-(4-fluoro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-fluoro-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(
• 2-(4-chloro-2-hydroxyphenyl)-4,5-dimethylimidazole 2-(4-chloro-2-hydroxyphenyl)-4-ethyl-5-methylimidazole, 2-(4-chloro-2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-2-(4-chloro-2-hydroxyphenyl)-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)imidazole, 2-(4-bromo-2-hydroxyphenyl)-4(5)-methylimidazole, azole, 2-(4-bromo-2-hydroxyphenyl)-4(5)-ethylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4,5-dimethylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-ethyl-5-methylimidazole, 2-(4-bromo-2-hydroxyphenyl)-4-
• the compound represented by the general formula (2) is not limited to the following imidazole compounds: For example, 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3-methylphenyl)benzimidazole, 2-(2-hydroxy-4-methylphenyl)benzimidazole, 2-(2-hydroxy-5-methylphenyl)benzimidazole, 2-(3-t-butyl-2-hydroxyphenyl)benzimidazole, 2-(4-fluoro-2-hydroxyphenyl)benzimidazole, 2-(4-chloro-2-hydroxyphenyl)benzimidazole, 2-(4-bromo-2-hydroxyphenyl)benzimidazole, 2-(2,3-dihydroxyphenyl)benzimidazole, 2-(2,5-dihydroxyphenyl)benzimidazole, 2-(2-hydroxy-4-methoxyphenyl)benzimidazole, 2-(2-hydroxy-3-methoxyphenyl)benzimidazole, 2-(2-hydroxy-5-methoxyphen
• R 1 and R 2 are both hydrogen atoms or have different substituents in the compound represented by the general formula (1).
• 2-(2-hydroxyphenyl)imidazole 2-(2-hydroxyphenyl)-4(5)-methylimidazole, 4-ethyl-(2-hydroxyphenyl)-5-methylimidazole, (2-hydroxyphenyl)-4-isopropyl-5-methylimidazole, 4-butyl-(2-hydroxyphenyl)-5-methylimidazole, and 2-(2-hydroxy-3(5)-methoxyphenyl)imidazole are more preferable, and 2-(2-hydroxyphenyl)imidazole is even more preferable.
• the compound represented by the general formula (2) is preferably 2-(2-hydroxyphenyl)benzimidazole, 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole, 2-(1-hydroxynaphthalen-2-yl)benzimidazole, 2-(2-hydroxynaphthalen-1-yl)benzimidazole, or 2-(2-hydroxyphenyl)benzimidazole-6-carboxylic acid, and more preferably 2-(2-hydroxyphenyl)benzimidazole or 2-(2-hydroxy-3(5)-methoxyphenyl)benzimidazole.
• Component (B) has a structural feature in which a hydroxyphenyl group is substituted at the 2-position of the imidazole structure that reacts with epoxy groups, and therefore has excellent compatibility with resins having aromatic rings and polar solvents, and can be dissolved well in various epoxy resins and solvents.
• a hydroxyphenyl group is substituted at the 2-position of the imidazole structure that reacts with epoxy groups, and therefore has excellent compatibility with resins having aromatic rings and polar solvents, and can be dissolved well in various epoxy resins and solvents.
• Patent Document 4 it is believed that by forming an intramolecular hydrogen bond between the nitrogen, which is the reaction point of imidazole, and the adjacent hydroxyphenyl group, the nucleophilicity of the nitrogen on the imidazole is suppressed during storage, making the composition stable, but when heated, the hydrogen bond dissociates, allowing the composition to react.
• solid-dispersed imidazole compounds having reduced compatibility with epoxy resins are known.
• such imidazole compounds have concerns that the uniformity of hardening may decrease due to their solid nature.
• the filling ability may decrease due to clogging.
• the film-forming ability may decrease due to residual particles. The compounds cannot be applied to extremely thin films.
• even solid-dispersed imidazole compounds may dissolve and not be stable.
• the component (B) used in the epoxy resin composition of the present embodiment which can be uniformly dissolved in a resin or solvent while simultaneously achieving both stability and reactivity, is particularly suitable for applications such as a resin paste that is used by filling narrow gaps, or a resin film that is thinned using a solvent.
• component (B) as a catalyst in the epoxy resin composition of this embodiment, it is surprisingly possible to impart a significantly high glass transition temperature that exceeds the curing temperature when a polyfunctional epoxy resin is blended, and to suppress the decrease in elastic modulus at high temperatures. Such an effect cannot be easily predicted from the structure of component (B).
• the inventors of the present invention have verified the effects of imidazole compounds having various structures in the process of arriving at the present invention, and have found that, among the curing agents or curing accelerators that can be dissolved in resins or solvents and completely homogenized, the only compound that can impart a glass transition temperature that exceeds the curing temperature and significantly suppress the decrease in elastic modulus at high temperatures is the one that contains component (B), and that combining a polyfunctional epoxy resin with component (B) is extremely useful in achieving the above effect.
• component (B) when component (B) is used, it is considered that, due to its structural characteristics, the adjacent hydroxyphenyl group plays a role as a chain transfer agent by donating a proton to the anion generated when the epoxy group reacts with imidazole to open the ring, thereby stabilizing it.
• the rapid generation and thickening of high molecular weight substances can be suppressed, and a chain extension reaction can occur in the entire system. Therefore, even when a multifunctional epoxy resin is used, the thickening during curing can occur slowly and uniformly, and unreacted epoxy groups are unlikely to remain, resulting in a high crosslink density and a cured layer with a high glass transition temperature and a modulus that is unlikely to decrease even at high temperatures.
• the hydroxyphenyl group in component (B) undergoes an addition reaction with the epoxy group to form a bond.
• component (B) when a compound that is not involved in the bond remains in the polymer, it weakens the intermolecular force between polymer chains, which causes a decrease in the glass transition temperature, but in the case of component (B), it is bonded and incorporated into the crosslinked structure, so the glass transition temperature is not decreased. Furthermore, since component (B) has an aromatic ring, it exerts a stacking effect with the epoxy resin, which also has a large amount of aromatic rings, and further strengthens the intermolecular force between polymer chains, thereby further improving the glass transition temperature and further suppressing the decrease in elastic modulus in the high temperature range.
• component (B) having the structural characteristics represented by general formula (1) and/or (2) in combination with a wide range of polyfunctional epoxy resins having three or more functional groups, including those with various functional group substitutions.
• the mass ratio of the tri- or higher functional polyfunctional epoxy resin to component (B) is not particularly limited and can be appropriately set based on the curing conditions and the desired reaction rate and performance.
• the mass ratio is preferably 100:0.001 to 100:20, more preferably 100:0.005 to 100:15, even more preferably 100:0.005 to 100:10, even more preferably 100:0.01 to 100:5, even more preferably 100:0.015 to 100:4, and particularly preferably 100:0.02 to 100:3.
• the curing ability of the polyfunctional epoxy resin due to component (B) can be obtained in the right amount, and since the curability is good, the resin can be cured uniformly and the storage stability tends to be good.
• the content of component (B) in the entire epoxy resin composition of this embodiment is not particularly limited, but from the viewpoint of obtaining sufficient curability, it is preferably 0.001 mass% or more of all non-volatile components excluding the solvent, more preferably 0.01 mass% or more, even more preferably 0.02 mass% or more, even more preferably 0.04 mass% or more, and even more preferably 0.05 mass% or more. From the viewpoint of maintaining an appropriate curing speed and maintaining the uniformity of the cured layer, it is preferably 40 mass% or less, more preferably 30 mass% or less, even more preferably 20 mass% or less, even more preferably 15 mass% or less, and even more preferably 10 mass% or less.
• component (B) catalytically reacts with component (A): epoxy resin, a person skilled in the art can set an appropriate amount in consideration of the materials and composition used and the desired performance.
• the rheometer As the rheometer, a HAAKE MARS manufactured by Thermo Scientific or the like can be used.
• the value of the parameter ⁇ varies depending on the type and amount of the epoxy resin and curing agent. When the parameter ⁇ satisfies 690 ⁇ 1000, the epoxy resin composition has good filling properties and, after curing, can achieve both a high glass transition temperature and a decrease in elastic modulus at high temperatures.
• the mechanism by which the above effect is obtained when the parameter ⁇ is within the above range is presumed by the present inventors to be as follows, although it is not intended to be limited to the following.
• the parameter ⁇ is a parameter that depends on the time required to reach a gel state with a high viscosity of 10,000 Pa ⁇ s at a given temperature, and is considered to indicate the reaction sensitivity when the epoxy resin composition is heated. For example, it is considered that the smaller the value of the parameter ⁇ , the smaller the reaction sensitivity to the heating temperature, that is, the smaller the temperature-dependent change in reactivity of the epoxy resin composition.
• the epoxy resin composition can maintain its filling property by suppressing the increase in viscosity in a temperature range of, for example, 130°C or less, and can be sufficiently cured by having sufficient reactivity when the temperature is increased, thereby obtaining the desired glass transition temperature and the effect of suppressing the decrease in elastic modulus.
• the epoxy resin composition exhibits extremely large changes in reactivity depending on temperature. If the parameter ⁇ is 1000 or less, the reaction is not too fast when the epoxy resin composition is heated, and filling properties are ensured and a uniform cured structure can be maintained.
• the curing reaction proceeds sufficiently without requiring an excessive amount of heat to cause a change in reactivity, and the desired glass transition temperature and effect of suppressing a decrease in elastic modulus can be obtained. From the above, it is considered that there is an optimum range for the parameter ⁇ in terms of the filling property of the epoxy resin composition and the physical properties of the cured product, and that this range is 690 ⁇ 1000.
• the parameter ⁇ is controlled by the combination of the types and amounts of the epoxy resin, the curing agent, the curing accelerator, etc., used in the epoxy resin composition.
• epoxy resins having aromatic rings tend to reduce ⁇
• aliphatic epoxy resins tend to increase ⁇ .
• the curing agent or curing accelerator is appropriately adjusted by selecting the component (D) and other curing agents described below. For example, a curing agent with higher reactivity tends to reduce ⁇ , while a curing agent with lower reactivity tends to increase ⁇ .
• the parameter ⁇ is 690 or more, more preferably 695 or more, and even more preferably 700 or more. From the same viewpoint, the parameter ⁇ is 1000 or less, more preferably 990 or less, even more preferably 980 or less, even more preferably 970 or less, even more preferably 960 or less, and particularly preferably 950 or less.
• the epoxy resin composition of the present embodiment may further contain a filler (hereinafter, may be referred to as filler (C) or component (C)).
• a filler hereinafter, may be referred to as filler (C) or component (C)).
• the filler (C) is not particularly limited, and examples of the filler include, from the viewpoint of reducing warpage, inorganic fillers (inorganic bulking agents) and inorganic fillers pretreated with a silane coupling agent (G) described below, and, from the viewpoint of improving adhesive strength and crack resistance, one or more types selected from the group consisting of organic fillers can be used. These may be used alone or in combination of two or more.
• the shape of the filler (C) is not particularly limited, and may be, for example, any of an irregular shape, a spherical shape, and a scaly shape. From the viewpoint of bringing the linear expansion coefficients of the epoxy resin composition of the present embodiment closer to those of a substrate to be adhered and reducing warping, it is preferable for the epoxy resin composition to contain an inorganic filler.
• inorganic fillers include, but are not limited to, ceramics such as silica, alumina, glass, cordierite, silicone oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate; carbons such as carbon nanotubes and graphene; metals or alloys such as gold, silver, copper, nickel, aluminum, zinc, tin, lead, solder, indium, and palladium; and particles in which
• silica examples include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc., and from the viewpoint of improving the filling property and the handleability of the epoxy resin composition, it is more preferable that the shape of the silica is spherical.
• Commercially available spherical fused silica is not particularly limited, but examples include those manufactured by Admatechs Co., Ltd. under the trade names SO-C2, SO-C1, SO-E2, and SO-E1.
• the inorganic filler preferably contains, for example, thermally conductive ceramic particles or metal particles.
• thermally conductive ceramic particles or metal particles it is preferable to contain, for example, alumina particles, aluminum nitride particles, boron nitride particles, zinc oxide particles, silicon nitride particles, silicon carbide particles, magnesium oxide particles, gold particles, silver particles, nickel particles, and particles coated with a thin metal film of these.
• alumina particles, aluminum nitride particles, boron nitride particles, gold particles, and silver particles are more preferable.
• the average particle size of the filler (C) is not particularly limited, but from the viewpoint of the ability to fill fine gaps and the adhesiveness and adhesion when an epoxy resin composition containing component (C) is used, the average particle size is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, even more preferably 2 ⁇ m or less, even more preferably 1 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
• the average particle size of component (C): the filler is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, even more preferably 0.05 ⁇ m or more, still more preferably 0.07 ⁇ m or more, and particularly preferably 0.1 ⁇ m or more.
• the average particle size of the filler can be measured by a laser diffraction scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the filler is created on a volume basis using a laser diffraction particle size distribution measuring device, and the median diameter is taken as the average particle size.
• the laser diffraction particle size distribution measuring device a product name: HELOS manufactured by Sympatec, etc. can be used.
• the content of the filler (C) can be appropriately set depending on the contents of the components (A) and (B).
• the content of the inorganic filler in the epoxy resin composition of the present embodiment can be appropriately set depending on the desired performance and is not particularly limited, but is preferably 5 to 98 mass %, more preferably 10 to 95 mass %, even more preferably 15 to 90 mass %, still more preferably 20 to 88 mass %, still more preferably 25 to 85 mass %, and particularly preferably 30 to 80 mass %, of all non-volatile components excluding the solvent.
• the epoxy resin composition of the present embodiment can further exhibit the effects (i) to (iii), such as: (i) an appropriate viscosity can be maintained, resulting in excellent handleability; (ii) the resin component and the inorganic filler are within a proper range, resulting in excellent adhesiveness, adhesion and dimensional stability; and (iii) suppression of warping when the resin composition is cured and reduction in elastic modulus in a high temperature range, and excellent breaking strength.
• the organic filler functions as an impact mitigating agent with stress relaxation properties.
• the epoxy resin composition of the present embodiment can further improve adhesion to various connecting members and also tends to suppress the occurrence and progression of fillet cracks.
• organic filler examples include, but are not limited to, acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), silicone modified resin, and organic fine particles of copolymers containing these as components.
• organic fine particles include alkyl (meth)acrylate-butadiene-styrene copolymers, alkyl (meth)acrylate-silicone copolymers, silicone-(meth)acrylic copolymers, complexes of silicone and (meth)acrylic acid, complexes of alkyl (meth)acrylate-butadiene-styrene and silicone, and complexes of alkyl (meth)acrylate and silicone.
• organic fine particles having a core-shell structure in which the composition of the core layer is different from that of the shell layer
• the core-shell type organic fine particles include particles having a silicone-acrylic rubber core to which an acrylic resin is grafted, and particles having an acrylic resin grafted to an acrylic copolymer, but are not particularly limited thereto.
• the inclusion of the core-shell type organic fine particles reduces the elastic modulus, which tends to reduce the stress generated in the fillet portion and suppress the occurrence of fillet cracks.
• the contained core-shell type organic fine particles act as a stress relaxation agent and tend to suppress the progression of the fillet cracks.
• the core layer is preferably made of a material having excellent flexibility, and examples of the material that can be used for the core layer include, but are not limited to, silicone elastomers, butadiene elastomers, styrene elastomers, acrylic elastomers, polyolefin elastomers, and silicone/acrylic composite elastomers.
• the material constituting the shell layer is preferably a material having excellent affinity to other components of the semiconductor resin encapsulant, particularly to epoxy resin. Examples of the material constituting the shell layer include, but are not limited to, acrylic resin and epoxy resin. Among these, acrylic resin is particularly preferred from the viewpoint of affinity to other components of the encapsulant, particularly to epoxy resin.
• the content of the organic filler in the epoxy resin composition of the present embodiment can be appropriately set depending on the desired performance and is not particularly limited, but is preferably 1 to 20 mass %, more preferably 2 to 18 mass %, and even more preferably 3 to 16 mass %, relative to the total amount of the epoxy resin composition.
• the content of the organic filler is 1% by mass or more, stress relaxation works, and there is a tendency that the effect of improving adhesive strength can be obtained.
• the content of the organic filler By setting the content of the organic filler to 20% by mass or less, the effect of heat reflow resistance tends to be obtained.
• the epoxy resin composition of the present embodiment may further contain the above-mentioned component (B): a curing agent other than the compounds of general formulas (1) and (2) (hereinafter, may be referred to as curing agent (D) or component (D)).
• component (D) a wide variety of conventionally known curing agents used for epoxy resins can be used, and there is no particular limitation thereon.
• the curing agent examples include amine-based curing agents, amide-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, imidazole-based curing agents (excluding component (B)), active ester-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, benzoxazine-based curing agents, phosphorus-based curing agents, thiol-based curing agents, catalyst-type curing agents, and modified products thereof. These may be used alone or in combination of two or more.
• amine-based curing agent examples include, but are not limited to, aliphatic amines, aromatic amines, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, and the like.
• aliphatic amines include, but are not limited to, triethylamine, tributylamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, and 1,2-diaminocyclohexane.
• aromatic amines include, but are not limited to, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane, trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate, aminobenzylamine, jER Cure WA (trade name) manufactured by Mitsubishi Chemical Corporation, and KAYAHARD (trade name) manufactured by Nippon Kay
• AA trade names of which are Ethacure 100, Ethacure 100 Plus, Ethacure 300, and Ethacure 420, manufactured by Mitsui Fine Chemicals, Inc., are given.
• an aromatic amine from the viewpoint of improving the glass transition temperature, it is preferable to contain an aromatic amine, and from the viewpoint of excellent handling properties, filling properties, and adhesion in a liquid state, it is more preferable to contain diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, or 3,5,3',5'-tetramethyl-4,4'-diaminodiphenylmethane.
• Amide-based hardeners include, but are not limited to, dicyandiamide and its derivatives, such as guanidine compounds, or amine-based hardeners to which acid anhydrides are added, as well as hydrazide-based compounds. From the standpoint of high adhesion and availability, it is preferable to use dicyandiamide or hydrazide-based compounds.
• Hydrazide-based hardeners made of hydrazide-based compounds include, but are not limited to, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, maleic acid dihydrazide, etc.
• Guanidine-based hardeners made of guanidine compounds include, but are not limited to, dicyandiamide derivatives such as dicyandiamide, dicyandiamide-aniline adduct, dicyandiamide-methylaniline adduct, dicyandiamide-diaminodiphenylmethane adduct, and dicyandiamide-diaminodiphenyl ether adduct; guanidine salts such as guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate, and aminoguanidine bicarbonate; methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, cyclohexylguanidine, phenylguanidine, diphenylguanidine,
• phenol-based curing agents include, but are not limited to, phenol novolac resin, bisphenol A novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, allyl acrylic phenol resin, dicyclopentadiene skeleton-containing phenol resin, biphenyl skeleton-containing phenol resin, naphthalene skeleton-containing phenol resin, and triazine skeleton-containing phenol resin.
• the triazine skeleton-containing phenol resin functions as a curing agent for epoxy resins and has both a triazine skeleton and a structure derived from a phenol-based compound in one molecule, and is generally produced by condensation of a phenol-based compound with a compound having a triazine ring such as melamine or benzoguanamine and formaldehyde.
• a phenol-based curing agent having a bisphenol A type structure, a bisphenol F type structure, a bisphenol AF type structure, a naphthalene structure, a phenol novolac structure, a cyclohexane structure, a cyclohexane dimethanol structure, a butadiene structure, a biphenyl type structure, a bixylenol structure, a cresol novolac structure, a dicyclopentadiene structure, a trisphenol structure, a naphthol structure, a naphthylene ether structure, an anthracene structure, a tetraphenylethane structure, a bisphenol acetophenone structure, a fluorene structure, or a triazine structure.
• phenolic hardeners are not particularly limited, but examples include DIC products under the trade names TD2090 (phenol novolac resin), EXB-9500 (naphthalene skeleton-containing phenolic resin), LA3018, LA3018-50P, LA7052, LA7054, and LA1356 (triazine skeleton-containing phenolic resin), and UBE products under the trade name HF-1M (phenol novolac resin). ), MEH-7700, MEH-7810, MEH-7851 (phenolic resins containing a biphenyl skeleton), Nippon Kayaku Co., Ltd.
• acid anhydride curing agents include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.
• Imidazole-based curing agents other than component (C) are not limited to the following, but examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl
• the active ester curing agent functions as a curing agent for epoxy resins and has an active ester in the molecule.
• the epoxy resin composition of the present embodiment contains an active ester-based curing agent as component (D)
• the dielectric loss tangent tends to be low because hydroxyl groups, which are a factor in increasing the dielectric loss tangent, are not generated in the epoxy resin composition due to the reaction between the active ester and the epoxy group.
• the active ester curing agent is not particularly limited, but from the viewpoint of ensuring crosslink density, a compound having two or more active ester groups in one molecule is preferred.
• an active ester compound obtained by reacting a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is more preferred, and an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from a phenolic compound, a naphthol compound, and a thiol compound is even more preferred.
• an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferred.
• an aromatic compound obtained by reacting a compound having at least two or more carboxylic acids in one molecule with an aromatic compound having a phenolic hydroxyl group, and an aromatic compound having two or more active ester groups in one molecule of the aromatic compound is even more preferred.
• the active ester curing agent may be linear or multi-branched. If the compound having at least two or more carboxylic acids in one molecule is a compound containing an aliphatic chain, it can increase the compatibility with the epoxy resin, and if it is a compound having an aromatic ring, it tends to have a high glass transition temperature and an effect of suppressing the decrease in elastic modulus in a high temperature range.
• carboxylic acid compound examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc.
• succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred.
• the thiocarboxylic acid compound examples include, but are not limited to, thioacetic acid and thiobenzoic acid.
• phenol compound or naphthol compound examples include, but are not limited to, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyl diphenol, and phenol novolak.
• bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadienyldiphenol, and phenol novolak are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone,
• the active ester compound that is the active ester-based curing agent is not particularly limited, but may be, for example, the active ester compounds disclosed in JP-A-2004-277460 and JP-A-2013-40270, or may be commercially available active ester compounds.
• Cyanate ester-based curing agents function as curing agents for epoxy resins and have cyanato groups in the molecule.
• the epoxy resin composition of this embodiment contains a cyanate ester-based curing agent as component (D)
• it reacts with the epoxy groups to produce oxazoline rings or oxazolidinone rings, imparting flexibility to the epoxy resin composition, and also causes the trimerization of the cyanato groups to form a triazine skeleton, which tends to reduce warpage while achieving a particularly high glass transition temperature.
• a cyanate ester-based curing agent as component (D)
• cyanate ester resins include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl)thioether, and bis(4-cyanate phenyl)ether; polyfunctional cyanate resins derived from phenol novolac, cresol novolac, and dicyclopentadiene structure-containing phenolic resins;
• cyanate ester resins are not particularly limited, but examples thereof include CYTESTER (registered trademark) TA (bisphenol A-type cyanate ester resin) manufactured by Mitsubishi Gas Chemical Company, Inc.
• Carbodiimide-based curing agents include, but are not limited to, products manufactured by Nisshinbo Chemical Co., Ltd. under the trade names Carbodilite V-02B, V-03, V-04K, V-07, and V-09, and products manufactured by Rhein Chemie under the trade names Stavaxol P, P400, and Hi-Kasil 510. Modified carbodiimide compounds such as those disclosed in Patent No. 7226954 may also be used.
• benzoxazine-based curing agents include, but are not limited to, Showa Polymer Co., Ltd. (product name: HFB2006M), Shikoku Kasei Holdings Co., Ltd. (product names: P-d, F-a, ALP-d, etc.)
• Phosphorus-based curing agents include, but are not limited to, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc.
• a thiol-based curing agent may be any agent containing two or more thiol groups in one molecule, and is not limited to the following, for example, 3,3'-dithiodipropionic acid, trimethylolpropane tris(thioglycolate), pentaerythritol tetrakis(thioglycolate), ethylene glycol dithioglycolate, 1,4-bis(3-mercaptobutyryloxy)butane, tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,
• the mercaptothiol include 3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionat
• catalyst type curing agents include, but are not limited to, cationic thermosetting catalysts, BF 3 -amine complexes, and the like.
• Curing agents that are modified products include, but are not limited to, polyamine compounds, amine-epoxy adducts, amine-urea adducts, imidazole-epoxy adducts, amine imide compounds, microcapsule-type curing agents coated with these, and curing agents adsorbed on porous bodies.
• Specific examples include, but are not limited to, products manufactured by Asahi Kasei Corporation under the trade names Novacure HX-3722, HX-3742, HX-3088, HX-3613, HXA3932HP, HXA9322HP, HXA9382HP, and HXA9192HP; products manufactured by Ajinomoto Fine-Techno Co., Ltd. under the trade names Amicure PN-23J, PN-40J, and MY-24; and products manufactured by Fuji Chemical Industry Co., Ltd. under the trade names Fujicure FXR-1020 and FXR-1030.
• the content of component (D) in the epoxy resin composition of this embodiment can be set appropriately depending on the reactivity with the above-mentioned components (A) and (B) and the desired performance, and is not particularly limited. From the viewpoint of obtaining good reactivity, the content is preferably 0.01 mass% or more of all non-volatile components excluding the solvent, more preferably 0.1 mass% or more, and even more preferably 1.0 mass% or more. Also, from the viewpoint of obtaining good storage stability, the content is preferably 50 mass% or less, more preferably 40 mass% or less, and even more preferably 30 mass% or less.
• thermoplastic resin (E) Thermoplastic resin
• the epoxy resin composition of the present embodiment may further contain a thermoplastic resin (hereinafter, may be referred to as thermoplastic resin (E) or component (E)).
• thermoplastic resin (E) thermoplastic resin
• component (E) thermoplastic resin
• thermoplastic resin (E) when the epoxy resin composition of the present embodiment is formed into a film by casting or applying to a certain thickness and drying, it is possible to prevent cracks and breaks and maintain the film shape.
• thermoplastic resin (E) examples include, but are not limited to, phenoxy resin, polyvinyl acetal resin, acid anhydride group-containing vinyl resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamide-imide resin, styrene-based elastomer resin, polyethersulfone resin, polyphenylene ether resin, polysulfone resin, and acrylic resin.
• the thermoplastic resin (E) may be used alone or in combination of two or more kinds.
• the weight average molecular weight of the thermoplastic resin (E) is preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, even more preferably 25,000 or more or 30,000 or more.
• the upper limit of the weight average molecular weight of the thermoplastic resin (E) is preferably 200,000 or less, more preferably 180,000 or less, even more preferably 160,000 or less, even more preferably 150,000 or less.
• the weight average molecular weight of the thermoplastic resin (E) can be measured, for example, by gel permeation chromatography (GPC) method.
• the weight average molecular weight (polystyrene equivalent) of the thermoplastic resin can be measured at a column temperature of 40°C using a Tosoh HLC-8320GPC measuring device, a Resonaq ShodeX KF-804/KF-803/KF-802/KF-802 column, and tetrahydrofuran or the like as the mobile phase, and calculated using the calibration curve of standard polystyrene.
• the thermoplastic resin (E) has a functional group containing one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms, or a carbon-carbon double bond.
• Such functional groups include one or more selected from the group consisting of hydroxyl groups, carboxy groups, acid anhydride groups, epoxy groups, amino groups, thiol groups, enol groups, enamine groups, urea groups, cyanate groups, isocyanate groups, thioisocyanate groups, diimide groups, alkenyl groups, allene groups, and ketene groups.
• the acid anhydride group a carboxylic acid anhydride group is preferable.
• alkenyl groups include vinyl groups, allyl groups, and styryl groups.
• the functional group equivalent of the thermoplastic resin (G) is preferably 100,000 or less, more preferably 90,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 40,000 or less, 30,000 or less, 20,000 or less, 10,000 or less, 8,000 or less, 6,000 or less, or 5,000 or less.
• the lower limit of the functional group equivalent is not particularly limited, but can usually be 50 or more, 100 or more, etc.
• thermoplastic resins (E) are described in more detail, but thermoplastic resins in which the above-mentioned functional groups have been further added to the thermoplastic resins shown below according to known procedures can also be suitably used as component (E).
• a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a phenol novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton can be suitably used, and the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
• phenoxy resin examples include, but are not limited to, Mitsubishi Chemical Corporation's product names: 1256, 4250 (phenoxy resin containing a bisphenol A skeleton), YX8100 (phenoxy resin containing a bisphenol S skeleton), YX6954, YX6954BH30 (phenoxy resin containing a bisphenol acetophenone skeleton), YX7553, YX7553BH30 (phenoxy resin containing a biscresol fluorenone skeleton), YL6794 (phenoxy resin containing a terpene skeleton), YL7213, YL7290 (phenoxy resin containing a trimethylcyclohexane skeleton), YL7500BH30, YL7769BH30, YL7482, and Nippon Steel Chemical & Material Co., Ltd.'s product names: FX280, FX293 (phenoxy resin containing a bisphenol fluorenone skeleton).
• polyvinyl acetal resins include, but are not limited to, Denki Kagaku Kogyo Co., Ltd. product names: Denka Butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd. product names: S-LEC BH series, BX series, KS series (e.g. KS-1), BL series, BM series, etc.
• the acid anhydride group-containing vinyl resin is not particularly limited, but can be obtained, for example, by copolymerizing an acid anhydride group-containing monomer (d1) with another monomer (d2).
• the acid anhydride group-containing monomer (d1) is not particularly limited, but examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride.
• the other monomer (d2) is not particularly limited as long as it can be copolymerized with the acid anhydride group-containing monomer (d1), and for example, an ethylenically unsaturated monomer such as (meth)acrylic acid, (meth)acrylic acid ester, or styrene may be used.
• Specific examples of the acid anhydride group-containing vinyl resin are not particularly limited, but examples thereof include Cray Valley's product names: EF-30, EF-40, EF-60, and EF-80.
• polyimide resins include, but are not limited to, Rikacoat SN-20 and PN-20 manufactured by New Japan Chemical Co., Ltd., and Unidic V-8000 manufactured by DIC Corporation.
• polyimide resins also include linear polyimides obtained by reacting bifunctional hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (JP Patent Publication No. 2006-37083), and modified polyimides such as polysiloxane skeleton-containing polyimides (JP Patent Publication No. 2002-12667, JP Patent Publication No. 2000-319386, WO2010/53186, etc.).
• polyamide-imide resins include, but are not limited to, Toyobo's Viromax HR11NN and HR16NN products, and Resonaq's HPC-5020, HPC-6000, HPC-7200, and HPC-9000 products.
• the styrene-based elastomer resin is not particularly limited, but examples thereof include block copolymers containing a block of styrene or an analog thereof as at least one terminal block and an elastomer block of a conjugated diene or its hydrogenated product as at least one intermediate block.
• styrene-butadiene diblock copolymer examples include styrene-butadiene diblock copolymer, styrene-butadiene triblock copolymer, styrene-isoprene diblock copolymer, styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene triblock copolymer, hydrogenated styrene-isoprene diblock copolymer, hydrogenated styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene random copolymer, etc.
• styrene-based elastomer resin examples include Asahi Kasei's product names: Asaprene, Tufprene, Asaflex, and Kuraray's product names: Hybler and Septon.
• polyethersulfone resins include, but are not limited to, PES5003P, a product manufactured by Sumitomo Chemical Co., Ltd.
• polysulfone resins include, but are not limited to, Polysulfone P1700 and P3500, both of which are manufactured by Solvay Advanced Polymers.
• polybutadiene resins include, but are not limited to, Nippon Soda Co., Ltd. (trade names: G-1000, G-3000, GI-1000, GI-3000), Idemitsu Petrochemical Co., Ltd. (trade name: R-45EPI), Daicel Corporation (trade name: Epofriend AT501), and Cray Valley Corporation (trade names: Ricon 130, Ricon 142, Ricon 150, Ricon 657, Ricon 130MA).
• acrylic resins include, but are not limited to, Nagase ChemteX Corporation product names: SG-P3, SG-600LB, SG-280, SG-790, SG-K2, and Negami Chemical Industries Co., Ltd. product names: SN-50, AS-3000E, ME-2000, etc.
• the thermoplastic resin (E) contains one or more resins selected from the group consisting of phenoxy resins, polyvinyl acetal resins, acid anhydride group-containing vinyl resins, polyimide resins, polyamide-imide resins, styrene-based elastomer resins, and acrylic resins.
• thermoplastic resin (E) can reduce the elasticity of the cured layer of the epoxy resin composition, thereby preventing breakage and peeling.
• the thermoplastic resin (E) is not limited to the following, but for example, if it contains a resin having one or more structures selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, and a polycarbonate structure in the molecule, it is preferable because it is easy to obtain the effect of low elasticity.
• a thermoplastic resin whose glass transition temperature is 25°C or less or which is liquid at 25°C, it can also be used preferably from the viewpoint of obtaining the effect of low elasticity.
• thermoplastic resin (E) in the epoxy resin composition of this embodiment can be set appropriately depending on the type and content of components (A) to (D) used and the desired performance, and is not particularly limited. From the viewpoint of ensuring the adhesion and flexibility of the epoxy resin composition of this embodiment, the content is preferably 0.5 mass% or more of all non-volatile components excluding the solvent, more preferably 1 mass% or more, even more preferably 1.2 mass% or more, and even more preferably 1.5 mass% or more.
• the content is preferably 50 mass% or less, more preferably 40 mass% or less, even more preferably 30 mass% or less, and even more preferably 20 mass% or less.
• the epoxy resin composition of the present embodiment may further contain a solvent (hereinafter, may be referred to as solvent (F) or component (F)).
• solvent (F) may be referred to as solvent (F) or component (F)).
• the inclusion of the solvent (F) tends to facilitate uniform dissolution of the compound of component (B) in the epoxy resin composition, which improves the curing uniformity of the cured layer made of the epoxy resin composition of the present embodiment, and makes it easier to design a composition that can further demonstrate the effects of the present invention by selecting component (B) having various structures according to the desired reaction temperature range and reaction rate.
• the solvent (F) is not particularly limited, and any known solvent can be used.
• the solvent (F) include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and solvent naphtha; ketones such as acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and acetophenone; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether acetate, and ⁇ -butyrolactone; alcohols such as methanol, ethanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, 2-phenoxyethanol, and 1-methoxy-2-propanol; and amide solvents such as dimethylformamide, di
• the content of the solvent (F) in the epoxy resin composition of the present embodiment is not particularly limited, but from the viewpoints of uniformly dissolving various components and controlling the viscosity within an appropriate range to improve handleability, when the epoxy resin composition is used in the form of a varnish or paste by blending the solvent, the content of the solvent (F) is preferably 5 to 80 mass %, more preferably 10 to 75 mass %, even more preferably 15 to 70 mass %, even more preferably 20 to 65 mass %, and even more preferably 25 to 60 mass %, based on the total mass of the epoxy resin composition.
• component (D) contains a solvent
• the above content is a preferred range of the solvent ratio in the entire epoxy resin composition, including those solvents.
• the content of the solvent (F) is not particularly limited, but from the viewpoint of suppressing the generation of bubbles, it is preferably 10 mass% or less, more preferably 8 mass% or less, and even more preferably 6 mass% or less, based on the entire epoxy resin composition.
• the viewpoint of preventing a decrease in the adhesion and flexibility of the resin film due to excessive reduction in the solvent it is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and even more preferably 0.1 mass% or more, based on the entire epoxy resin composition.
• the epoxy resin composition of the present embodiment may further contain a silane coupling agent (hereinafter, may be referred to as silane coupling agent (G) or component (G)).
• a silane coupling agent (G) is preferred because it can improve the affinity between the resin component and the filler, or between the resin component and the substrate, and tends to improve the uniform dispersion of the filler component and the adhesiveness of the epoxy resin composition.
• containing the silane coupling agent (G) means that in the step of obtaining the epoxy resin composition of the present embodiment, the silane coupling agent is incorporated into the composition of the epoxy resin composition by any one of the following methods (i) to (iii).
• any of the above methods (i) to (iii) may be used, with (i) being preferred from the viewpoints that alcohol, which is a by-product of the silane coupling reaction, is less likely to remain in the system and that the filler is more dispersible, and (ii) and (iii) are preferred from the viewpoints that they can act not only between the resin and the filler but also between the resin and the substrate to be adhered, thereby improving the adhesiveness and adhesion.
• the silane coupling agent (G) is a compound in which at least one hydrolyzable group such as an alkoxy group or an aryloxy group is bonded to a silicon atom, and in addition, an alkyl group, an alkenyl group, or an aryl group may be bonded to the silicon atom.
• the alkyl group may be substituted with an amino group, an alkoxy group, an epoxy group, or a (meth)acryloyloxy group.
• the silane coupling agent (G) is not limited to the following, but from the viewpoint of improving the uniform dispersion of the filler component and improving the adhesiveness and adhesion of the resin composition, it is preferable to include one or more silane coupling agents selected from, for example, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, styrylsilane-based coupling agents, acrylate silane-based coupling agents, isocyanate silane-based coupling agents, sulfide silane-based coupling agents, vinyl silane-based coupling agents, silane-based coupling agents, organosilazane compounds, and titanate-based coupling agents.
• silane coupling agents selected from, for example, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, styrylsilane-based coupling agents, acrylate silane-based coupling agents
• silane coupling agent (G) examples include, but are not limited to, aminosilane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, N-phenyl-3-aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-2(-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane; epoxysilane coupling agents such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyl(dimethoxy)methylsilane,
• aminosilane-based coupling agents aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, and organosilazane compounds are preferred, and from the viewpoint of filler fluidity when used in combination with component (B), aminosilane-based coupling agents are more preferred.
• Examples of commercially available products include, but are not limited to, trade names of KBM403 (3-glycidoxypropyltrimethoxysilane), KBM803 (3-mercaptopropyltrimethoxysilane), KBE903 (3-aminopropyltriethoxysilane), KBM573 (N-phenyl-3-aminopropyltrimethoxysilane), and SZ-31 (hexamethyldisilazane), all of which are manufactured by Shin-Etsu Chemical Co., Ltd.
• the content of the silane coupling agent (G) in the epoxy resin composition of this embodiment is not particularly limited, but from the viewpoint of improving the dispersibility of the filler (C) and the adhesiveness and adhesion of the epoxy resin composition of this embodiment while suppressing excessive side reactions, it is preferably 0.1 to 2.0 parts by mass per 100 parts by mass of the filler (C).
• the epoxy resin composition of the present embodiment may further contain a compound having a polyalkylene oxide structure and a non-epoxy group at its terminal (a non-epoxy group-terminated compound having a polyalkylene oxide structure, hereinafter sometimes referred to as component (H)), excluding the above-mentioned components (A) to (G).
• component (H) a non-epoxy group-terminated compound having a polyalkylene oxide structure
• the component (H) is a compound having a terminal hydroxyl group.
• Component (H) may be, but is not limited to, linear polyalkylene oxide glycols (linear polyalkylene glycols) such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, polyoxyethylene trimethylolpropane ether, polyoxypropylene trimethylolpropane ether, polyoxyethylene polyoxypropylene trimethylolpropane ether, polyoxyethylene diglyceryl ether, polyoxypropylene diglyceryl ether, polyoxyethylene polyoxypropylene diglyceryl ether, polyoxyethylene pentaerythritol ether, polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene sorbitol, polyoxypropylene diglyceryl
• polyalkylene oxide glycols such as polyoxyethylene polyoxypropylene sorbitol and polyoxyethylene polyoxypropylene sorbitol
• polyalkylene oxide alkyl ethers such as polyoxyethylene monoalkyl ethers, polyoxyethylene dialkyl ethers, polyoxypropylene monoalkyl ethers, polyoxyethylene polyoxypropylene monoalkyl ethers and polyoxyethylene polyoxypropylene dialkyl ethers
• polyalkylene oxide esters such as polyoxyethylene monoesters, polyoxyethylene diesters, polypropylene glycol monoesters, polypropylene glycol diesters, polyoxyethylene polyoxypropylene monoesters and polyoxyethylene polyoxypropylene diesters (including acetates, propionates, butyrates, (meth)acrylates, etc.) polyoxyethylene monoesters, polyoxyethylene diesters, polyoxypropylene monoesters, polyoxypropylene diesters, polyoxyethylene polyoxypropylene diesters
• component (H) include, but are not limited to, "Pronon #102", “Pronon #104", “Pronon #201", “Pronon #202B”, “Pronon #204", “Pronon #208", “Unilube 70DP-600B”, and “Unilube 70DP-950B” (polyoxyethylene polyoxypropylene glycol) manufactured by NOF Corporation; “Pluronic L-23”, “Pluronic L-31”, and “Pluronic L-22” manufactured by ADEKA Corporation; “Pluronic L-44”, “Pluronic L-61”, “ADEKA Pluronic L-62”, “Pluronic L-64", “Pluronic L-71”, “Pluronic L-72", “Pluronic L-101", “Pluronic L-121", “Pluronic P-84”, “Pluronic P-85”, “Pluronic P-103", “Pluronic F-68", “Pluronic F-88”, “Pl
• the component (H) may contain a compound represented by the following formula (3).
• R 3 and R 4 are each independently an alkyl group having 1 to 12 carbon atoms, and R 3 and R 4 may be the same or different.
• p and q are each independently an integer of 1 or more.
• R 5 and R 6 are each independently one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 6 to 20 carbon atoms which may have a substituent, and an aryl group having 6 to 20 carbon atoms which may have a substituent.
• R 5 and R 6 may be the same or different.
• p and q are not particularly limited, but for example, from the viewpoint of the balance between the strength and toughness of the cured product, the total value p+q of the number of repetitions thereof is preferably 2 or more and 12 or less, more preferably 3 or more and 10 or less, even more preferably 4 or more and 8 or less, and even more preferably 5 or more and 8 or less.
• the compound represented by the above formula (3) is preferred because it has excellent compatibility with component (A) and can provide heat resistance and strength due to the aromatic ring portion in the structure, and low stress and low warpage due to the polyalkylene oxide chain portion.
• the compounds represented by the above formula (3) are not limited to the following, but examples include products manufactured by Sanyo Chemical Industries, Ltd. under the trade names: Newpol BPE-20, BPE-40, BPE-60, BPE-100, BPE-180, BP-2P, BP-3P, BP-5P, etc. These may be used alone or in combination of two or more types.
• Component (H) may be added independently, may be mixed with components other than component (H), or may be generated in the system by using a constituent material containing component (H) during the production of component (A) or during the production of an epoxy resin composition containing component (A).
• the content of component (H) in the epoxy resin composition of this embodiment can be set appropriately depending on the desired performance, and is not particularly limited, but is preferably 1% by mass to 50% by mass, more preferably 1.5% by mass to 40% by mass, and even more preferably 2% by mass to 30% by mass, of all non-volatile components excluding the solvent. By setting the content of component (H) within the above range, it tends to be possible to achieve both heat resistance and strength, as well as low stress and low warpage.
• the epoxy resin composition of the present embodiment may further contain, as necessary, additives such as a diluent, a reactive diluent, a pigment, a dye, a flow control agent, a thickener, a reinforcing agent, a release agent, a wetting agent, a flame retardant, a surfactant, a stabilizer, and an adhesion aid, in addition to the above-mentioned components (A) to (H).
• additives such as a diluent, a reactive diluent, a pigment, a dye, a flow control agent, a thickener, a reinforcing agent, a release agent, a wetting agent, a flame retardant, a surfactant, a stabilizer, and an adhesion aid, in addition to the above-mentioned components (A) to (H).
• Diluents include, but are not limited to, dioctyl phthalate, dibutyl phthalate, benzyl alcohol, etc.
• the reactive diluent is a compound having a reactive functional group that can be incorporated into a cured structure such as an epoxy group or an acrylic group, and is a compound that has the effect of reducing the viscosity of the epoxy resin composition by adding it to the epoxy resin composition of the present embodiment.
• reactive diluents include, but are not limited to, acrylate compounds and epoxy compounds that can reduce the viscosity without impairing the reactivity.
• acrylate compounds that are reactive diluents include, but are not limited to, compounds having (meth)acryloyl groups at both ends of a polyalkylene oxide, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, trimethylolpropane type multifunctional (meth)acrylate, pentaerythritol type multifunctional (meth)acrylate, dipentaerythritol type multifunctional (meth)acrylate, etc.
• Epoxy compounds that are reactive diluents include, but are not limited to, n-butyl glycidyl ether, tert-butyl glycidyl ether, diglycidyl aniline, N,N'-glycidyl-o-toluidine, phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether.
• the reactive diluent various monoepoxy compounds and glycidyl ether compounds of polyhydric alcohols can also be used, but since there is only one functional group (epoxy group, glycidyl group) that contributes to the reaction with component (B) and component (D) in one molecule, and although it does not volatilize and cause voids, it is difficult to form three-dimensional crosslinks during curing, and therefore the glass transition temperature and toughness of the epoxy resin composition tend not to be sufficient. Therefore, as the reactive diluent, a compound containing two or more glycidyl groups in one molecule is preferable from the viewpoint of being able to form three-dimensional crosslinks during curing.
• the reactive diluents may be used alone or in combination of two or more.
• the amount of reactive diluent can be set appropriately according to the desired performance, and is not particularly limited, but is preferably 1.0 part by mass or more and 30 parts by mass or less per 100 parts by mass of epoxy resin (A). By setting the amount to 1.0 part by mass or more, sufficient low-viscosity curing can be obtained, and the resin paste tends to fill gaps well and the resin film tends to adhere well. On the other hand, by setting the amount of reactive diluent to 30 parts by mass or less per 100 parts by mass of epoxy resin (A), creeping of the resin paste and leakage to unintended places due to excessively low viscosity can be prevented, the dimensional stability of the resin film can be improved, and peeling during moisture absorption reflow testing tends to be suppressed. It is also preferable to further include a reactive diluent in order to suppress the increase in viscosity that occurs when the filler (C) is highly filled.
• Pigments include, but are not limited to, kaolin, chalk powder, gypsum, antimony trioxide, pentone, aerosol, lithopone, baryte, titanium dioxide, etc.
• Dyes include, but are not limited to, natural dyes such as dyes derived from plants, such as madder and indigo, dyes derived from minerals, such as yellow ocher and red clay, synthetic dyes, such as alizarin and indigo, and fluorescent dyes.
• Flow control agents include, but are not limited to, organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxybis(acetylacetonate); organic zirconium compounds such as zirconium tetra-normal-butoxide and zirconium tetraacetylacetonate; and the like.
• Thickeners include, but are not limited to, animal-based thickeners such as gelatin; vegetable-based thickeners such as polysaccharides and cellulose; and chemically synthesized thickeners such as polyacrylics, modified polyacrylics, polyethers, urethane-modified polyethers, and carboxymethylcellulose.
• the reinforcing agent may be, but is not limited to, polyethylene sulfone powder such as "Sumika Excel PES” manufactured by Sumitomo Chemical Co., Ltd.; nano-sized functional group-modified core-shell rubber particles such as "Kane Ace MX” manufactured by Kaneka Corporation; silicone-based reinforcing agents such as polyorganosiloxane; etc.
• Releasing agents include, but are not limited to, fluorine-based releasing agents, silicone-based releasing agents, and acrylic-based releasing agents made of a copolymer of glycidyl (meth)acrylate and linear alkyl (meth)acrylate ester having 16 to 22 carbon atoms.
• Wetting agents include, but are not limited to, unsaturated polyester copolymer wetting agents having acidic groups, such as acrylic polyphosphate esters.
• Examples of the flame retardant include, but are not limited to, bromine-based flame retardants, phosphorus-based flame retardants, and inorganic flame retardants.
• Examples of brominated flame retardants include, but are not limited to, tetrabromophenol.
• Examples of phosphorus-based flame retardants include, but are not limited to, 9,10-dihydro-9-oxa-10-phosphananthrene-10-oxide and its epoxy derivatives, triphenylphosphine and its derivatives, phosphate esters, condensed phosphate esters, and phosphazene compounds.
• nitrogen-based flame retardant examples include, but are not limited to, melamine polyphosphate, isocyanuric acid, guanidine-based flame retardants, and triazine-based flame retardants.
• inorganic flame retardant compounds include, but are not limited to, magnesium hydroxide and aluminum hydroxide.
• the flame retardants may be used alone or in combination of two or more.
• the content of the flame retardant is not particularly limited, but is preferably 5.0 parts by mass or more and 200 parts by mass or less, and more preferably 10 parts by mass or more and 100 parts by mass or less, relative to the mass (100 parts by mass) of the epoxy resin (A).
• Surfactants include, but are not limited to, anionic surfactants such as alkylbenzenesulfonates and alkylpolyoxyethylenesulfates, cationic surfactants such as alkyldimethylammonium salts, amphoteric surfactants such as alkyldimethylamine oxides and alkylcarboxybetaines, and nonionic surfactants such as linear alcohols and fatty acid esters having 25 or more carbon atoms.
• anionic surfactants such as alkylbenzenesulfonates and alkylpolyoxyethylenesulfates
• cationic surfactants such as alkyldimethylammonium salts
• amphoteric surfactants such as alkyldimethylamine oxides and alkylcarboxybetaines
• nonionic surfactants such as linear alcohols and fatty acid esters having 25 or more carbon atoms.
• the stabilizer which improves the storage stability of the epoxy resin composition
• boric acid for example, boric acid, a cyclic borate ester compound, isocyanuric acid, barbituric acid, an aluminum chelating agent, etc.
• a cyclic borate ester compound is one in which boron is contained in a cyclic structure.
• the cyclic borate ester compound is preferably 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane).
• the stabilizer may be used alone or in combination of two or more kinds.
• adhesion aids can be used as long as they are components that are added for the purpose of forming coordinate bonds with metals or substrate materials or improving affinity, but thiazole-based compounds and triazole-based compounds are preferred from the viewpoint of forming a good film on the adherend surface and further improving adhesion.
• additives described above can be added in functionally equivalent amounts, for example, pigments and/or dyes can be added in amounts that can impart the desired color to the epoxy resin composition of this embodiment.
• a person skilled in the art can set appropriate amounts to be added depending on the formulation and the desired performance.
• the epoxy resin composition of the present embodiment and the resin paste using the same contain the above-mentioned component (A) and component (B), and can be obtained by adding, as necessary, components (C) to (G) and the above-mentioned additives and mixing them. That is, the resin paste of the present embodiment contains the epoxy resin composition of the present embodiment.
• the mixing method is not particularly limited, and any method known to those skilled in the art can be used.
• the mixture can be sufficiently mixed until it becomes homogeneous using a mixing roll such as a three-roll mixer, a dissolver, a planetary mixer, a rotary mixer, a kneader, an extruder, or the like, but is not limited thereto.
• the epoxy resin composition of the present embodiment is completely uniform and has sufficient filling property, and even when a polyfunctional epoxy resin is blended therein, in addition to having a high glass transition temperature, it is possible to suppress a decrease in elastic modulus at high temperatures. Therefore, the epoxy resin composition can be suitably used as a resin paste for use in sealing materials for electric and electronic components, such as underfill materials and relay sealing materials, paste materials such as various insulating liquid adhesives, die attach pastes, conductive pastes, and thermally conductive pastes, ink materials such as solder resist inks and hole-filling inks, matrix resins for fiber-reinforced plastics, and impregnating and fixing materials for motor coils.
• sealing materials for electric and electronic components such as underfill materials and relay sealing materials
• paste materials such as various insulating liquid adhesives, die attach pastes, conductive pastes, and thermally conductive pastes
• ink materials such as solder resist inks and hole-filling inks
• the epoxy resin composition of the present embodiment for example, in an underfill material, is completely uniform and has sufficient filling properties, so that permeability can be ensured when the composition is heated and permeated into the gap between the semiconductor chip and the substrate.
• the composition can fill large-area semiconductor chips and narrow gaps.
• the composition exhibits a high glass transition temperature and is capable of suppressing a decrease in elastic modulus at high temperatures. This makes the composition more suitable for providing an underfill material and a semiconductor device that are highly durable against heat generation and long-term use of electronic components and have excellent long-term connection reliability.
• the epoxy resin composition of this embodiment which is completely uniform, does not leave any granular residue when the paste or ink is applied or filled, and a cured product with high curing uniformity is obtained, which is excellent in strength and long-term durability and is more suitable.
• the filler (C) used in this embodiment according to the application and blending one or more types of silica, conductive filler, or thermally conductive filler, it is possible to impart the desired die attachment properties, electrical conductivity, and thermal conductivity while obtaining the effects of the present invention.
• the epoxy resin composition of the present embodiment can be made into a resin film.
• the resin film of the present embodiment has a support and a resin layer containing the above-mentioned epoxy resin composition on the support.
• the resin film of the present embodiment has, for example, a predetermined support and a resin layer formed on the support from the above-mentioned epoxy resin composition, and may have a protective layer as necessary.
• the resin film may have a protective layer on the surface of the resin layer opposite to the support.
• the support constituting the resin film is preferably made of a material that can withstand the temperature during solvent drying.
• supports include, but are not limited to, polyethylene terephthalate films, polyvinyl alcohol films, polyvinyl chloride films, vinyl chloride copolymer films, polyvinylidene chloride films, vinylidene chloride copolymer films, polymethyl methacrylate copolymer films, polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. These films may be stretched as necessary.
• the protective layer is preferably made of a material capable of sufficiently maintaining the smoothness of the surface of the resin layer constituting the resin film.
• a protective layer is preferably made of, but not limited to, a polyethylene film, a polypropylene film, a polyethylene terephthalate film treated for easy peeling, an oriented polypropylene film, or the like.
• the resin film of the present embodiment can be produced by sequentially laminating a support, a resin layer, and, if necessary, a protective layer.
• the support, the resin layer and the protective layer may be laminated by any known method.
• the epoxy resin composition of the present embodiment to which the solvent (F) is added is prepared, and the composition is first applied to a support using a known method such as an applicator, a bar coater, a lip coater, a die coater, a roll coater, or a doctor blade coater, and then dried to form a resin layer on the support.
• the drying method is not particularly limited, and examples thereof include an oven and hot air blowing.
• drying temperature and time there are also no particular limitations on the drying temperature and time, but from the viewpoint of sufficiently removing the solvent while suppressing deformation of the support due to excessive heating and excessive reaction of the resin layer during drying, it is preferable to dry at a temperature range of 50°C to 160°C and within a drying time of 1 minute to 30 minutes, and more preferably at 80°C to 150°C and for 3 minutes to 25 minutes.
• the drying temperature may be a constant temperature or may be a temperature gradient.
• a protective layer may be laminated on the formed resin layer to produce a resin film.
• the resin film of the present embodiment can be used, for example, as an interlayer insulating film, a film-type solder resist, a sealing sheet, a die attach film, a conductive film, an anisotropic conductive film, a non-conductive film, a thermally conductive film, and the like, although not limited thereto.
• the resin film using the epoxy resin composition of this embodiment not only do they have various stabilities required in the production of resin films, such as varnish storage stability until coating and drying, stability at drying temperature, and film storage stability, but they also have sufficient filling properties, low warpage of the cured layer, a high glass transition temperature, and a function to suppress the decrease in elastic modulus in the high temperature range, so they are particularly effective in materials such as resin films in which reliability must be ensured in the thin cured layer portion.
• component (B) dissolves uniformly in the epoxy resin composition or solvent, the resin film has excellent surface smoothness and can be adhered to the substrate without gaps.
• the cured product of the present embodiment is obtained by curing the above-mentioned epoxy resin composition.
• the semiconductor device of the present embodiment includes a semiconductor element sealed or bonded with the above-mentioned resin paste, or includes a semiconductor element sealed or bonded with the above-mentioned resin film, and therefore has a cured layer of the above-mentioned epoxy resin composition.
• the epoxy resin composition of the present embodiment uniform sealing or adhesion can be achieved, and the cured layer has a high glass transition temperature and is inhibited from decreasing in elastic modulus in a high temperature range, so that a semiconductor device with excellent reliability capable of withstanding heat generation and long-term use can be preferably produced.
• Semiconductor devices are not particularly limited as long as they are devices that function with semiconductor components built in, but examples include various semiconductor devices used in electrical appliances such as personal computers, smartphones, game consoles, digital cameras and televisions, vehicles such as motorcycles, automobiles, trains, ships and aircraft, and high-speed communication antennas and servers.
• the semiconductor device of this embodiment can be manufactured, for example but not limited to, by mounting various semiconductor chips at the locations of the wiring board where the circuit connections are made, thereby establishing electrical continuity.
• the method of mounting the semiconductor chip when manufacturing the semiconductor device is not particularly limited, but specific examples include a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless build-up layer (BBUL), a mounting method using an anisotropic conductive film, a mounting method using a non-conductive film, etc., and in mounting, the epoxy resin composition of this embodiment, and a resin paste and a resin film using the same can be used to seal and bond the semiconductor chip.
• BBUL bumpless build-up layer
• the epoxy resin composition contained the solvent (F)
• the solvent was evaporated by heating the epoxy resin composition at 130°C or 150°C for 3 minutes, respectively, and the above measurement was performed.
• 1/T was plotted on the horizontal axis and Lnt on the vertical axis, and the values of Lnt versus 1/T obtained as described above were plotted.
• An approximation line was created for the plotted data points by the least squares method, and ⁇ was calculated as the slope of the line.
• the viscosity did not reach 10,000 Pa ⁇ s even after 30 minutes at 130° C., the epoxy resin composition was judged to have insufficient reaction sensitivity within a practical temperature range, and was recorded as "ineligible for evaluation" in the table.
• the measurement device used was a HAAKE MARS manufactured by Thermo Scientific.
• the resin composition contained the solvent (F)
• the resin composition was heated at 130°C for 3 minutes to volatilize the solvent, and the measurement was performed on the resin composition.
• an epoxy resin composition layer was applied to the center of an aluminum foil having a length of 15 cm, width of 8 cm, and thickness of 1.7 mm, so as to have a length of 12 cm, width of 5 cm, and dry film thickness of 150 ⁇ m, and then the layer was dried by heating for 5 minutes in an oven preheated to 120°C to form a film, which was then cured by heating for 1 hour in an oven preheated to 150°C.
• the epoxy resin composition was cured by the method described above in (Evaluation of heat resistance) to obtain a cured product, and then DMA measurement (RSA-G2, manufactured by TA Instruments, Inc.) was performed at a temperature increase rate of 4°C/min from 25°C to 250°C to measure the storage modulus at 25°C (room temperature elastic modulus) and the minimum value of the storage modulus in the temperature range equal to or higher than the glass transition temperature measured in (Evaluation of heat resistance) above (high temperature storage modulus).
• the elastic modulus retention rate around the glass transition temperature was calculated using the following mathematical formula (1).
• Elastic modulus retention rate (%) high-temperature storage elastic modulus/room-temperature elastic modulus ⁇ 100 Formula (1) If the elastic modulus retention rate was more than 10%, it was evaluated as good and indicated by ⁇ in the table, and if it was 10% or less, it was evaluated as poor and indicated by ⁇ in the table. However, if the cured product was brittle and a test specimen could not be prepared, it was indicated as "evaluation not possible" in the table.
• Component (B) Compounds represented by general formula (1) and general formula (2)
• B-1 2-(2-hydroxyphenyl)imidazole (manufactured by Ambeed, Inc.)
• B-2 2-(2-hydroxyphenyl)benzimidazole (Tokyo Chemical Industry Co., Ltd.)
• R-1 2MZ-A (2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, manufactured by Shikoku Kasei Holdings Co., Ltd.)
• R-2 2MA-OK (2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine with isocyanuric acid, manufactured by Shikoku Kasei Holdings Co., Ltd.)
• R-3 2P4MZ (2-phenyl-4-methylimidazole, manufactured by Shikoku Kasei Holdings Co., Ltd.)
• R-4 1B2PZ (1-benzyl-2-phenylimidazole, manufactured by Shikoku Kasei Holdings Co., Ltd.)
• R-5 2P4MHZ (2-phenyl-4-methyl-5-hydroxymethylimidazole, manufactured by Shikoku
• D-1 MEH-8000H (liquid phenol novolac resin curing agent, OH equivalent 140 g/eq, manufactured by UBE)
• D-2 HF-1M (solid phenol novolac resin hardener, OH equivalent 106 g/eq, manufactured by UBE)
• E-1 PKHB (phenoxy resin, weight average molecular weight 32,000, manufactured by Gabriel Phenoxies)
• F-1 Methyl ethyl ketone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• F-2 Cyclohexanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• H-1 BPE-100 (bisphenol A ethylene oxide 10 mol adduct, liquid at 25°C, hydroxyl group structure at both ends, manufactured by Sanyo Chemical Industries, Ltd.)
• Examples 1 to 14 [Comparative Examples 1 to 12] The components were mixed in the ratios (parts by mass) shown in Tables 1 and 2, and epoxy resin compositions were prepared by the method described above. The properties of the prepared epoxy resin compositions were measured and evaluated by the methods described above. The results are shown in Tables 1 and 2.
• the examples which used component (B) in combination with a trifunctional or higher polyfunctional epoxy resin and had a parameter ⁇ that satisfied the condition 690 ⁇ 1000, all had sufficient uniformity and filling properties, and the glass transition temperature exceeded 150° C., and in the cases of Examples 1 to 8, exceeded 200° C. Furthermore, it was found that the examples also had sufficient elastic modulus retention.
• Comparative Examples 1 to 4 and 10 to 12 which used a compound not corresponding to component (B), the glass transition temperature was lowered to a maximum of about 60° C. compared with the Examples using component (B), and the elastic modulus retention rate was also insufficient, despite the use of a multifunctional epoxy resin.
• Comparative Examples 8 and 9 the glass transition temperature was sufficient, but both the uniformity and filling property were insufficient.
• Comparative Example 5 In Comparative Example 5, in which component (B) was used but no multifunctional epoxy resin was used, neither the filling property nor the elastic modulus retention rate was satisfied. In Comparative Example 6, in which component (B) was used but no multifunctional epoxy resin was used, neither the glass transition temperature nor the elastic modulus retention rate was satisfied. In Comparative Example 7, in which component (B) and a multifunctional epoxy resin were used but the parameter ⁇ did not satisfy 690 ⁇ 1000, the filling property was found to be insufficient.
• the epoxy resin composition of the present invention is completely uniform and has sufficient filling property, and when a polyfunctional epoxy resin is blended therewith, in addition to having a significantly high glass transition temperature exceeding the curing temperature, it is also possible to suppress a decrease in elastic modulus at high temperatures, and therefore has high heat resistance and excellent reliability capable of withstanding long-term use.
• the epoxy resin composition has industrial applicability in the fields of sealing materials for electric and electronic components such as underfill materials and relay sealing materials, paste materials such as various insulating liquid adhesives, die attach pastes, conductive pastes, and thermally conductive pastes, ink materials such as solder resist inks and hole-filling inks, matrix resins for fiber-reinforced plastics, resin paste materials such as impregnating adhesives for motor coils, and film materials such as interlayer insulating films, film-type solder resists, sealing sheets for semiconductor packages, die attach films, conductive films, anisotropic conductive films, non-conductive films, and thermally conductive films.
• paste materials such as various insulating liquid adhesives, die attach pastes, conductive pastes, and thermally conductive pastes
• ink materials such as solder resist inks and hole-filling inks
• matrix resins for fiber-reinforced plastics resin paste materials such as impregnating adhesives for motor coils
• film materials such as interlayer insul

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• 2024
  • 2024-10-25 JP JP2025506049A patent/JPWO2025121026A1/ja active Pending
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