WO2024150765A1 - 接着剤組成物、回路接続用接着剤フィルム、接続構造体及び接続構造体の製造方法 - Google Patents
接着剤組成物、回路接続用接着剤フィルム、接続構造体及び接続構造体の製造方法 Download PDFInfo
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- WO2024150765A1 WO2024150765A1 PCT/JP2024/000306 JP2024000306W WO2024150765A1 WO 2024150765 A1 WO2024150765 A1 WO 2024150765A1 JP 2024000306 W JP2024000306 W JP 2024000306W WO 2024150765 A1 WO2024150765 A1 WO 2024150765A1
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- 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
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- 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
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
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- 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
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- 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
- 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
- C09J7/35—Heat-activated
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- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Definitions
- the present disclosure relates to an adhesive composition, an adhesive film for circuit connection, a connection structure, and a method for manufacturing the connection structure.
- adhesive films with conductive particles dispersed in the adhesive have been used as adhesive materials for connecting a liquid crystal display and an integrated circuit for driving the liquid crystal, connecting a liquid crystal display and a tape carrier package (TCP), connecting a flexible printed circuit board (FPC) and a TCP, or connecting an FPC and a printed wiring board (see, for example, Patent Document 1).
- an adhesive film is desirable for an adhesive film to be usable for mounting over a wide range of temperatures, from low to high.
- one aspect of the present disclosure aims to provide an adhesive composition that can be mounted at low temperatures (e.g., 120°C) to high temperatures (e.g., 150°C), and that has excellent appearance even after HAST testing and produces little air bubbles in both low-temperature and high-temperature mounting.
- Another aspect of the present disclosure aims to provide an adhesive composition, an adhesive film for circuit connection, a connection structure, and a method for manufacturing a connection structure that use the adhesive composition.
- a composition comprising a cationically polymerizable compound and a curing agent, the cationically polymerizable compound contains an epoxy compound which is tri- or higher functional and has an epoxy equivalent of more than 100 g/eq and not more than 250 g/eq, the curing agent contains a pyridinium salt;
- the pyridinium salt has a benzyl group at the 1-position and an electron-withdrawing group at the 2-position;
- the adhesive composition wherein the benzyl group has an electron donating group.
- the adhesive composition according to [1], wherein the epoxy compound has an aromatic ring.
- the cationically polymerizable compound comprises at least one selected from the group consisting of an epoxy compound having a trisphenolmethane structure, an epoxy compound having a bisphenol structure and having a glycidyl group and a glycidyloxy group, an epoxy compound having a tetravalent organic group and an aromatic ring bonded to the organic group, wherein the aromatic ring has a substituent containing an epoxy group, and an epoxy compound having a naphthalene structure.
- the number of the electron-donating groups in the benzyl group is 3, The adhesive composition according to any one of [1] to [6], wherein the electron donating group is an alkyl group.
- the pyridinium salt comprises a pyridinium cation and an anion, The adhesive composition according to any one of [1] to [7], wherein the anion is B(C 6 F 5 ) 4 -- .
- An adhesive film for circuit connection comprising an adhesive layer formed from the adhesive composition according to any one of [1] to [9].
- a method for producing a connection structure comprising the steps of: interposing an adhesive film for circuit connection according to [10] or [11] between a first circuit member having a first electrode and a second circuit member having a second electrode; and thermocompressing the first circuit member and the second circuit member to electrically connect the first electrode and the second electrode to each other.
- an adhesive composition that can be mounted at low temperatures (e.g., 120°C) to high temperatures (e.g., 150°C) and that can achieve an excellent appearance even after HAST testing in both low-temperature and high-temperature mounting.
- an adhesive composition an adhesive film for circuit connection, a connection structure, and a method for manufacturing a connection structure that use the adhesive composition.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of an adhesive film for circuit connection.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of an adhesive film for circuit connection.
- FIG. 1 is a schematic cross-sectional view showing one embodiment of a connection structure.
- 4A to 4C are schematic cross-sectional views showing a method for manufacturing the connection structure of FIG. 3.
- the upper or lower limit of the numerical range may be replaced with the values shown in the examples.
- the lower and upper limits of the numerical ranges may be arbitrarily combined with the lower or upper limit of other numerical ranges.
- the numerical values A and B at both ends are included as the lower and upper limits of the numerical range, respectively.
- the description "10 or more” means 10 and a numerical value exceeding 10, and this also applies when the numerical values are different.
- the description "10 or less” means a numerical value less than 10 and a numerical value less than 10, and this also applies when the numerical values are different.
- each component and material exemplified in this specification may be used alone or in combination of two or more types, unless otherwise specified.
- the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component are present in the composition.
- (meth)acrylate means at least one of an acrylate and the corresponding methacrylate.
- epoxy group includes substituents that contain an epoxy group in the structure, such as a glycidyl group and a glycidyloxy group.
- One embodiment of the present disclosure is an adhesive composition containing a cationically polymerizable compound and a curing agent.
- the cationically polymerizable compound contains at least an epoxy compound that is trifunctional or higher and has an epoxy equivalent of more than 100 g/eq and 250 g/eq or less.
- the curing agent contains at least a pyridinium salt, the pyridinium salt having a benzyl group at the 1-position and an electron-withdrawing group at the 2-position, and the benzyl group has an electron-donating group.
- the cationic polymerizable compound may be, for example, a compound that reacts with a curing agent by heating to crosslink, and includes at least an epoxy compound that is trifunctional or more and has an epoxy equivalent of more than 100 g/eq and 250 g/eq or less (such an epoxy compound is also referred to as "epoxy compound X").
- An epoxy compound that is trifunctional or more means an epoxy compound having three or more epoxy groups.
- the epoxy equivalent means a value measured in accordance with JIS K7236.
- the reason why the cationic polymerizable compound contains epoxy compound X and the adhesive composition has excellent appearance and generates less air bubbles is presumed to be as follows. That is, when the number of epoxy groups in the epoxy compound is 3 or more and the epoxy equivalent is 250 g/eq or less, the crosslinking density of the adhesive composition is high, the adhesion to the substrate is improved, and the appearance is excellent even after the HAST test. In addition, when the adhesive composition is made into a film, tack of the film can be suppressed and air bubbles that get between the substrate and the film when the film is attached can be easily removed, thereby suppressing the generation of air bubbles.
- the number of epoxy groups in the epoxy compound X may be 4 or more, or 15 or less, 12 or less, 10 or less, 8 or less, 6 or less, or 4 or less.
- the epoxy equivalent of the epoxy compound X may be 105 g/eq or more, 110 g/eq or more, 120 g/eq or more, 130 g/eq or more, 140 g/eq or more, or 150 g/eq or more, and may be 240 g/eq or less, 230 g/eq or less, 220 g/eq or less, 210 g/eq or less, or 200 g/eq or less.
- Epoxy compound X may have an aromatic ring.
- the epoxy compound has a rigid skeleton, so that an adhesive composition can be obtained that has a better appearance even after the HAST test and generates less air bubbles.
- Epoxy compound X may be a solid at room temperature (25°C). When epoxy compound X is a solid at room temperature and has an epoxy equivalent within a specific range, it is easier to achieve an excellent appearance even after the HAST test and to reduce the generation of bubbles, compared to epoxy compounds that are liquid at room temperature.
- the molecular weight of the epoxy compound X may be 200 or more, 250 or more, or 300 or more, and may be 1500 or less, 1000 or less, 900 or less, 800 or less, 700 or less, or 650 or less.
- epoxy compound X examples include epoxy compounds having a trisphenolmethane structure (hereinafter, such epoxy compounds are also referred to as "compound A”), epoxy compounds having a bisphenol structure and having a glycidyl group and a glycidyloxy group (hereinafter, such epoxy compounds are also referred to as “compound B”), epoxy compounds having a tetravalent organic group and an aromatic ring bonded to the organic group, the aromatic ring having a substituent containing an epoxy group (hereinafter, such epoxy compounds are also referred to as “compound C”), and epoxy compounds having a naphthalene structure (hereinafter, such epoxy compounds are also referred to as "compound D”).
- compound A epoxy compounds having a trisphenolmethane structure
- compound B epoxy compounds having a bisphenol structure and having a glycidyl group and a glycidyloxy group
- compound C epoxy compounds having a substituent containing an epoxy group
- compound D epoxy compounds having a
- Compound A may be a compound represented by the following general formula (1A), from the viewpoint of more easily achieving an excellent appearance even after the HAST test and from the viewpoint of less generation of bubbles.
- R 11 , R 12 , and R 13 each independently represent a hydrogen atom or an organic group, at least one of R 11 , R 12 , and R 13 represents an organic group having an epoxy group, R 14 represents a hydrogen atom or an alkyl group, and R 15 represents a hydrogen atom or an organic group.
- Examples of the organic group represented by R 11 , R 12 , and R 13 include an alkyl group, an alkyl ether group, and an alkenyl group. These organic groups may have a substituent. The number of carbon atoms of the organic group may be, for example, 2 or more, or 3 or more, and may be 8 or less, 6 or less, or 4 or less. At least one of R 11 , R 12 , and R 13 may be an organic group having a glycidyl group, or may be an organic group having a glycidyloxy group. R 11 , R 12 , and R 13 may be the same or different.
- R 11 , R 12 , and R 13 may be an organic group having a glycidyl group, or may be an organic group having a glycidyloxy group, from the viewpoint of more easily achieving an excellent appearance even after the HAST test and less generation of bubbles.
- R 14 is an alkyl group
- the alkyl group may be, for example, a methyl group, an ethyl group, or a propyl group.
- the alkyl group may have a substituent.
- R 14 may be a hydrogen atom from the viewpoint of more easily achieving an excellent appearance even after the HAST test and from the viewpoint of less generation of bubbles.
- the organic group represented by R 15 may be, for example, an alkyl group, an alkyl ether group, or an alkenyl group.
- the organic group may have a substituent.
- R 15 may be an alkyl group, an alkyl group having a substituent, or an alkyl group having a phenyl group, from the viewpoint of more easily realizing an excellent appearance even after the HAST test and less occurrence of bubbles.
- the phenyl group may have a substituent, for example, an epoxy group, a glycidyl group, or a glycidyloxy group.
- R 15 may be an alkyl group having a phenyl group having a glycidyloxy group, from the viewpoint of more easily realizing an excellent appearance even after the HAST test and less occurrence of bubbles.
- the number of epoxy groups contained in compound A may be 15 or less, 12 or less, or 10 or less.
- compound A may be a compound represented by the following formula (2A).
- formula (2A) k represents an integer of 1 to 3.
- Compound B may be a compound represented by the following general formula (1B), from the viewpoint of more easily achieving an excellent appearance even after the HAST test and from the viewpoint of less generation of bubbles.
- R 21 , R 22 , R 23 , and R 24 each independently represent a hydrogen atom, an organic group, an organic group having a glycidyl group, or an organic group having a glycidyloxy group, at least one of R 21 , R 22 , R 23 , and R 24 represents an organic group having a glycidyl group, at least one of R 21 , R 22 , R 23 , and R 24 represents an organic group having a glycidyloxy group, and R 25 and R 26 each independently represent a hydrogen atom or an organic group.
- Examples of the organic group represented by R21 , R22 , R23 , and R24 include an alkyl group, an alkyl ether group, and an alkenyl group. These organic groups may have a substituent.
- the number of carbon atoms of the organic group may be, for example, 2 or more, or 3 or more, and may be 8 or less, 6 or less, or 4 or less.
- R 21 , R 22 , R 23 , and R 24 may be the same or different. From the viewpoint of more easily realizing an excellent appearance even after the HAST test and less generation of bubbles, R 21 and R 22 may be different from each other, and one of R 21 and R 22 may be an organic group having a glycidyl group, and the other may be an organic group having a glycidyloxy group. From the viewpoint of more easily realizing an excellent appearance even after the HAST test and less generation of bubbles, R 23 and R 24 may be different from each other, and one of R 23 and R 24 may be an organic group having a glycidyl group, and the other may be an organic group having a glycidyloxy group.
- R 25 and/or R 26 are organic groups
- examples of the organic groups include alkyl groups, aryl groups, alkyl ether groups, and alkenyl groups. These organic groups may have a substituent.
- the alkyl group may be, for example, a methyl group, an ethyl group, or a propyl group.
- the alkyl group may have a substituent.
- R 25 and R 26 may be a hydrogen atom, an alkyl group, or a methyl group from the viewpoint of more easily achieving an excellent appearance even after the HAST test and less generation of bubbles.
- the number of epoxy groups contained in compound B may be 4 or more, or 10 or less, 8 or less, 6 or less, or 4 or less.
- Compound B may be a compound having multiple glycidyl groups and multiple glycidyloxy groups, from the viewpoint of more easily achieving an excellent appearance even after the HAST test and from the viewpoint of less generation of bubbles.
- compound B may be a compound represented by the following formula (2B).
- Compound C may have four aromatic rings bonded to a tetravalent organic group, and each of the four aromatic rings may have an epoxy group, from the viewpoint of more easily achieving an excellent appearance even after the HAST test and less generating bubbles.
- the four aromatic rings may be different from each other, or may be the same from the viewpoint of more easily achieving an excellent appearance even after the HAST test and less generating bubbles.
- Compound C may be, for example, a compound represented by the following general formula (1C).
- R 31 represents a tetravalent organic group
- R 32 represents an organic group having an epoxy group.
- Examples of the organic group represented by R 31 include an alkyl group, an alkyl ether group, and an alkenyl group. These organic groups may have a substituent.
- the number of carbon atoms of the organic group may be, for example, 2 or more, or 3 or more, and may be 8 or less, 6 or less, 4 or less, or 3 or less.
- R 31 may be an alkyl group or an ethyl group from the viewpoint of more easily achieving an excellent appearance even after the HAST test and less generation of bubbles.
- R 32 may be an organic group having a glycidyl group or an organic group having a glycidyloxy group. From the viewpoint of more easily realizing an excellent appearance even after the HAST test and from the viewpoint of less generation of bubbles, R 32 may be an organic group having a glycidyloxy group.
- the number of epoxy groups possessed by compound C may be 4 or more, or 10 or less, 8 or less, 6 or less, or 4 or less.
- compound C may be a compound represented by the following formula (2C).
- Compound D may be a compound represented by the following general formula (1D), from the viewpoint of more easily achieving an excellent appearance even after the HAST test and from the viewpoint of less generation of bubbles.
- X 41 represents an oxygen atom, a sulfur atom, or an alkylene group having 1 to 10 carbon atoms
- R 42 and R 43 each independently represent a glycidyl group or a glycidyloxy group
- m and n each independently represent an integer of 1 to 7, and m+n is 3 or greater.
- X 41 may have a substituent.
- the number of carbon atoms of the alkylene group may be 8 or less, 6 or less, 4 or less, 3 or less, or 2 or less, from the viewpoint of more easily realizing an excellent appearance even after the HAST test and from the viewpoint of less occurrence of bubbles.
- X 41 may be an ethylene group, from the viewpoint of more easily realizing an excellent connection resistance even after the HAST test and from the viewpoint of less occurrence of bubbles.
- Compound C may be a compound represented by the following formula (2D), from the viewpoint of more easily realizing an excellent appearance even after the HAST test and less generation of bubbles.
- R 44 , R 45 , R 46 and R 47 each independently represent a hydrogen atom, a glycidyl group, or a glycidyloxy group, and three or more of R 44 , R 45 , R 46 and R 47 are a glycidyl group or a glycidyloxy group.
- R 44 , R 45 , R 46 and R 47 may be a glycidyl group or a glycidyloxy group.
- the cationic polymerizable compound may contain any one of compounds A to D alone, or may contain two or more of compounds A to D.
- the cationic polymerizable compound may contain at least one selected from the group consisting of an epoxy compound having a trisphenolmethane structure, an epoxy compound having a bisphenol structure and a glycidyl group and a glycidyloxy group, an epoxy compound having a tetravalent organic group and an aromatic ring bonded to the organic group, the aromatic ring having a substituent containing an epoxy group, and an epoxy compound having a naphthalene structure.
- the cationic polymerizable compound may contain, in addition to compounds A to D, cationic polymerizable compounds other than compounds A to D.
- cationic polymerizable compounds other than compounds A to D include epoxy compounds (excluding compounds A to D), vinyl ether compounds, and oxetane compounds.
- epoxy compounds examples include bisphenol A type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, tetramethyl bisphenol A type epoxy resins, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (bi-7-oxabicyclo[4,1,0]heptane), 3,4-epoxycyclohexylmethyl (meth)acrylate, (3,3',4,4'-diepoxy)bicyclohexyl, dicyclopentadiene dimethanol diglycidyl ether, xylene novolac type glycidyl ether, biphenyl type epoxy resins, etc.
- the epoxy compound may contain at least one selected from the group consisting of bisphenol A type epoxy resin, tetramethyl bisphenol A type epoxy resin, dicyclopentadiene dimethanol diglycidyl ether, xylene-novolac type glycidyl ether, and alicyclic epoxy resin.
- the epoxy compound may contain a glycidyl ether compound. From the viewpoint of further improving low-temperature curing properties, the epoxy compound may contain an alicyclic epoxy resin. Furthermore, from the viewpoint of easily achieving both low-temperature curing properties and good storage stability, the epoxy compound does not need to contain an alicyclic epoxy resin.
- the cationic polymerizable compound may contain an epoxy compound having two or less functionalities (hereinafter, such an epoxy compound is also referred to as "epoxy compound Y") together with the epoxy compound X.
- epoxy compound Y an epoxy compound having two or less functionalities
- the epoxy equivalent of epoxy compound Y may be 100 g/eq or more, more than 100 g/eq, 110 g/eq or more, 120 g/eq or more, 140 g/eq or more, or 160 g/eq or more, and may be 300 g/eq or less, 250 g/eq or less, 220 g/eq or less, or 200 g/eq or less.
- the ratio of the content of epoxy compound Y to the content of epoxy compound X may be 0.1 or more, 0.2 or more, 0.5 or more, or 0.8 or more, and may be 10 or less, 8 or less, 6 or less, 4 or less, 2 or less, or 1.5 or less.
- the oxetane compound any compound having one or more oxetane ring structures in the molecule can be used without any particular restrictions.
- the cationic polymerizable compound may contain an oxetane compound.
- the cationic polymerizable compound may not contain an oxetane compound.
- the cationic polymerizable compound may contain an epoxy compound (excluding compound X) and an oxetane compound together with compound X.
- the cationic polymerizable compound may contain only one of an epoxy compound (excluding compound X) and an oxetane compound.
- the case where only one of an epoxy compound (excluding compound X) and an oxetane compound is contained includes the case where, as the cationic polymerizable compound, a single type selected from an epoxy compound other than compound X and an oxetane compound is used together with compound X, and the case where a cationic polymerizable compound such as a vinyl ether compound is used in combination with a type selected from an epoxy compound other than compound X and an oxetane compound is used together with compound X.
- oxetane compounds include xylylene bisoxetane, 2-ethylhexyl oxetane, 3-hydroxymethyl-3-methyl oxetane, 3-hydroxymethyl-3-ethyl oxetane, 3-hydroxymethyl-3-propyl oxetane, 3-hydroxymethyl-3-n-butyl oxetane, 3-hydroxymethyl-3-phenyl oxetane, 3-hydroxymethyl-3-benzyl oxetane, 3-hydroxyethyl-3-methyl oxetane, 3-hydroxyethyl-3-ethyl oxetane, and 3-hydroxyethyl 3-propyloxetane, 3-hydroxyethyl-3-phenyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxypropyl-3-ethyloxetane, 3-hydroxypropyl-3-methyloxetane, 3-hydroxyprop
- the content of the cationic polymerizable compound may be 10 mass% or more, 20 mass% or more, 30 mass% or more, or 35 mass% or more based on the total mass of the adhesive composition, from the viewpoint of ensuring sufficient curability of the adhesive composition.
- the content of the cationic polymerizable compound may be 70 mass% or less, 60 mass% or less, 50 mass% or less, or 45 mass% or less based on the total mass of the adhesive composition, from the viewpoint of ensuring formability of the adhesive composition.
- the content of the epoxy compound (including compounds A to D) in the cationic polymerizable compound may be 50% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more based on the total mass of the cationic polymerizable compound, from the viewpoint of more easily achieving an excellent appearance even after the HAST test and from the viewpoint of less generation of air bubbles.
- the content of the epoxy compound (including compounds A to D) in the cationic polymerizable compound may be substantially 100% by mass (an embodiment in which the cationic polymerizable compound is composed of the epoxy compound (including compounds A to D)).
- the total content of epoxy compound X in the cationic polymerizable compound may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more based on the total mass of the cationic polymerizable compound, from the viewpoint of more easily achieving an excellent appearance even after the HAST test and from the viewpoint of less generation of bubbles.
- the total content of epoxy compound X in the cationic polymerizable compound may be 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less based on the total mass of the cationic polymerizable compound.
- the total content of compounds A to D in the cationic polymerizable compound may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more based on the total mass of the cationic polymerizable compound, from the viewpoint of more easily achieving an excellent appearance even after the HAST test and from the viewpoint of less generation of bubbles.
- the total content of compounds A to D in the cationic polymerizable compound may be 90% by mass or less, 80% by mass or less, 70% by mass or less, or 60% by mass or less based on the total mass of the cationic polymerizable compound.
- the curing agent contains a pyridinium salt having a benzyl group at position 1 and an electron-withdrawing group at position 2, with the benzyl group having an electron-donating group (hereinafter, such a pyridinium salt is also referred to as "pyridinium salt A").
- a pyridinium salt having an electron-donating group
- an adhesive composition can be obtained that is mountable from low temperatures (e.g., 120°C) to high temperatures (e.g., 150°C), and that has excellent appearance even after HAST testing and generates little air bubbles in both low-temperature and high-temperature mounting.
- the pyridinium salt A may be, for example, a compound represented by the following general formula (3):
- R 1 represents an electron-withdrawing group
- R 2 represents an electron-donating group
- X ⁇ represents an anion.
- the electron-withdrawing group that pyridinium salt A has at the 2-position may be a cyano group, a halogeno group, a nitro group, a carbonyl group, a carboxy group, a sulfo group, etc.
- the halogeno group may be a fluoro group, a chloro group, a bromo group, an iodo group, etc.
- the electron-withdrawing group may be a cyano group or a halogeno group, or may be a cyano group or a chloro group.
- Pyridinium salt A may contain an electron-withdrawing group other than the potential-withdrawing group located at the 2-position.
- the number of electron-withdrawing groups that pyridinium salt A has may be 3 or less, 2 or less, or 1.
- the electron donating group of the benzyl group arranged at the 1-position of the pyridinium salt A may be an alkyl group, an alkoxy group, a hydroxyl group, an amino group, or an alkylamino group.
- the alkyl group include a methyl group, an ethyl group, a normal propyl group, and an isopropyl group.
- the alkoxy group include a methoxy group and an ethoxy group.
- the electron withdrawing group may be an alkyl group or an alkoxy group, or a methyl group or a methoxy group.
- the benzene ring may contain multiple electron donating groups, and the number of electron donating groups of the benzyl group arranged at the 1-position of the pyridinium salt A may be 1 or more, 2 or more, or 3 or more, or may be 3.
- the benzyl group arranged at the 1-position of the pyridinium salt A may have at least one electron donating group at the 4-position (the 4-position when the bonding position of the benzyl group to the pyridine ring is the 1-position. The para-position to the bonding position of the benzyl group to the pyridine ring).
- the pyridinium salt A When the number of electron donating groups possessed by the benzyl group arranged at the 1st position of the pyridinium salt A is 3, all of the three electron donating groups may be alkyl groups or may be methyl groups. When the bonding position of the benzyl group to the pyridine ring is the 1st position, the pyridinium salt A may have an alkyl group as an electron donating group at each of the 2nd, 4th, and 6th positions of the benzyl group.
- an adhesive film using such a curing agent By containing a pyridinium salt in which the number of electron donating groups possessed by the benzyl group arranged at the 1st position of the pyridinium salt A is 3 and all of the electron donating groups are alkyl groups (or methyl groups), an adhesive film using such a curing agent has excellent physical properties (e.g., elastic modulus). Therefore, an adhesive film using such a curing agent can achieve, for example, excellent adhesion to circuit members and excellent peelability of the substrate from the adhesive film.
- an adhesive film using such a curing agent has, for example, excellent storage stability, and even when the adhesive film is stored for a certain period of time (for example, 15 hours at 40°C), it is easy to maintain excellent adhesion to circuit members and excellent peelability of the substrate from the adhesive film.
- a certain period of time for example, 15 hours at 40°C
- the benzyl group located at position 1 of pyridinium salt A has three electron-donating groups, which results in a well-balanced structure that maintains low-temperature curing properties while preventing deterioration during storage for a certain period of time (e.g., 15 hours at 40°C) (excellent storage stability).
- Examples of the pyridinium cation of pyridinium salt A include 2-cyano-1-(4-methoxybenzyl)pyridinium cation, 2-chloro-1-(4-methoxybenzyl)pyridinium cation, 2-bromo-1-(4-methoxybenzyl)pyridinium cation, 2-cyano-1-(4-methylbenzyl)pyridinium cation, 2-chloro-1-(4-methylbenzyl)pyridinium cation, 2-bromo-1-(4-methylbenzyl)pyridinium cation, 2-cyano-1-(2,4,6-trimethylbenzyl)pyridinium cation, 2-chloro-1-(2,4,6-trimethylbenzyl)pyridinium cation, and 2-bromo-1-(2,4,6-trimethylbenzyl)pyridinium cation.
- the pyridinium cation of the pyridinium salt A may be at least one selected from the group consisting of 2-cyano-1-(4-methoxybenzyl)pyridinium cation, 2-chloro-1-(4-methoxybenzyl)pyridinium cation, 2-cyano-1-(2,4,6-trimethylbenzyl)pyridinium cation, and 2-chloro-1-(2,4,6-trimethylbenzyl)pyridinium cation.
- Examples of the anion of pyridinium salt A include SbF 6 - , PF 6 - , PF X (CF 3 ) 6-X - (wherein X is an integer of 1 to 5), BF 4 - , B(C 6 F 5 ) 4 - , RSO 3 - (wherein R is an alkyl group having 1 to 3 carbon atoms, or a substituted or unsubstituted aryl group), C(SO 2 CF 3 ) 3 - , N(SO 2 CF 3 ) 2 - , O(SO 2 CF 3 ) - , and B(C 6 H 3 (CF 3 ) 2 ) 4 - (wherein the CF 3 group is substituted at the 3- and 5-positions of the phenyl group).
- the anion of the pyridinium salt A may be B(C 6 F 5 ) 4 — , from the viewpoint of excellent connection resistance even after a high temperature and high humidity test (eg, 85° C
- the pyridinium salt A may be a compound that combines the pyridinium cation and the anion. That is, the pyridinium salt A may contain at least any of the pyridinium cations and any of the anions. From the viewpoint of being able to cure the adhesive composition in a shorter time, the pyridinium salt A may be at least one selected from the group consisting of 2-cyano-1-(4-methoxybenzyl)pyridinium tetrakis(pentafluorophenyl)borate, 2-chloro-1-(4-methoxybenzyl)pyridinium tetrakis(pentafluorophenyl)borate, 2-cyano-1-(2,4,6-trimethylbenzyl)pyridinium tetrakis(pentafluorophenyl)borate, and 2-chloro-1-(2,4,6-trimethylbenzyl)pyridinium tetrakis(pentafluor
- the content of pyridinium salt A in the curing agent may be 80% by mass or more, 90% by mass or more, or 95% by mass or more, based on the total mass of the curing agent, and may be 100% by mass (an embodiment in which the curing agent is essentially composed of pyridinium salt A).
- the curing agent may contain a pyridinium salt other than pyridinium salt A.
- the content of pyridinium salt other than pyridinium salt A in the curing agent may be 20 mass% or less, 10 mass% or less, or 5 mass% or less based on the total mass of the curing agent, or may be 0 mass% (an embodiment in which the curing agent is essentially composed of pyridinium salt A).
- a curing agent containing pyridinium salt A can be obtained by a manufacturing method including the steps of reacting at least one of a pyridine compound having an electron-withdrawing group at the 2-position, a benzyl chloride compound having an electron-donating group, or a benzyl bromide compound having an electron-donating group with an alkali metal iodide salt (e.g., sodium iodide) in a solvent (e.g., acetonitrile) to obtain pyridinium iodide having a pyridine ring and a benzene ring, and reacting the obtained pyridinium iodide with an anion salt in a solvent (e.g., dichloromethane) to obtain pyridinium salt A.
- an alkali metal iodide salt e.g., sodium iodide
- a solvent e.g., acetonitrile
- the pyridine compound having an electron-withdrawing group at the 2-position may be a pyridine compound having the above-mentioned electron-withdrawing group at the 2-position, and may be, for example, 2-cyanopyridine or 2-chloropyridine.
- the benzyl chloride compound having an electron donating group may be a benzyl chloride compound having the above electron donating group, for example, 4-methoxybenzyl chloride, 2,4,6-trimethylbenzyl chloride.
- the benzyl bromide compound having an electron donating group may be a benzyl bromide compound having the above electron donating group, for example, 4-methoxybenzyl bromide, 2,4,6-trimethylbenzyl bromide.
- the anion salt may be any compound capable of introducing the anion possessed by pyridinium salt A, and may be, for example, a lithium salt, sodium salt, potassium salt, or cesium salt of the anion of pyridinium salt A.
- the reaction may be carried out, for example, at room temperature (20 to 30°C).
- the reaction time may be, for example, 10 to 50 hours, or 20 to 30 hours.
- the obtained pyridinium iodide may be washed with acetone, distilled water, etc., and vacuum dried to remove the solvent used.
- the yield of pyridinium iodide may be 40% or more, 55% or more, 70% or more, or 80% or more.
- the yield of pyridinium iodide is defined as the ratio of the amount of pyridinium iodide actually obtained to the maximum amount of pyridinium iodide that can be obtained from the raw materials used in the synthesis of pyridinium iodide.
- the reaction may be carried out, for example, at room temperature (20 to 30°C).
- the reaction time may be, for example, 1 to 15 hours or 1 to 5 hours.
- the obtained pyridinium salt A may be washed with acetone, distilled water, etc., and vacuum dried to remove the solvent used.
- the yield of pyridinium salt A may be 70% or more, 80% or more, or 85% or more.
- the yield of pyridinium salt A is the ratio of the amount of pyridinium salt A actually obtained to the maximum amount of pyridinium salt A that can be obtained from the pyridinium iodide used in the synthesis of pyridinium salt A.
- pyridinium salt A has been obtained can be confirmed by measuring the obtained compound by nuclear magnetic resonance spectroscopy ( 1 H-NMR). Specifically, it can be confirmed by the method described in the Examples below.
- the content of the curing agent in the adhesive composition may be 1 mass% or more, 2 mass% or more, 3 mass% or more, 4 mass% or more, or 5 mass% or more, based on the total mass of the adhesive composition, from the viewpoint of sufficiently promoting the curing reaction.
- the content of the curing agent in the adhesive composition may be 20 mass% or less, 15 mass% or less, 10 mass% or less, 8 mass% or less, or 6 mass% or less, based on the total mass of the adhesive composition, from the viewpoint of improving the physical properties of the cured product. From these viewpoints, the content of the curing agent in the adhesive composition may be 1 to 20 mass%, based on the total mass of the adhesive composition.
- the content of the curing agent in the adhesive composition may be 1 mass% or more, 3 mass% or more, 5 mass% or more, or 7 mass% or more, based on the total mass of the adhesive composition excluding the conductive particles, from the viewpoint of sufficiently promoting the curing reaction.
- the content of the curing agent in the adhesive composition may be 30 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less, based on the total mass of the adhesive composition excluding the conductive particles, from the viewpoint of improving the physical properties of the cured product. From these viewpoints, the content of the curing agent in the adhesive composition may be 1 to 30 mass%, based on the total mass of the adhesive composition excluding the conductive particles.
- the content of the curing agent in the adhesive composition may be 1 mass% or more, 3 mass% or more, 5 mass% or more, or 7 mass% or more, based on the total mass of the adhesive composition excluding the conductive particles and filler, from the viewpoint of sufficiently promoting the curing reaction.
- the content of the curing agent in the adhesive composition may be 30 mass% or less, 25 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less, based on the total mass of the adhesive composition excluding the conductive particles and filler, from the viewpoint of improving the physical properties of the cured product. From these viewpoints, the content of the curing agent in the adhesive composition may be 1 to 30 mass%, based on the total mass of the adhesive composition excluding the conductive particles and filler.
- the content of the curing agent in the adhesive composition may be 1 part by mass or more, 5 parts by mass or more, 8 parts by mass or more, 10 parts by mass or more, or 12 parts by mass or more, based on 100 parts by mass of the cationically polymerizable compound, from the viewpoint of sufficiently promoting the curing reaction.
- the content of the curing agent in the adhesive composition may be 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, 18 parts by mass or less, or 16 parts by mass or less, based on 100 parts by mass of the cationically polymerizable compound, from the viewpoint of improving the physical properties of the cured product. From these viewpoints, the content of the curing agent in the adhesive composition may be 1 to 40 parts by mass, based on 100 parts by mass of the cationically polymerizable compound.
- the adhesive composition may contain conductive particles.
- the conductive particles are not particularly limited as long as they are conductive particles, and examples thereof include metal particles made of metals such as gold, silver, palladium, nickel, copper, and solder; conductive carbon particles made of conductive carbon; and coated conductive particles having a core containing non-conductive glass, ceramic, plastic (polystyrene, etc.), and a coating layer containing the above metal or conductive carbon and coating the core.
- the conductive particles may be coated conductive particles, which are easily deformed by heating and/or pressure, and can increase the contact area between the electrodes and the conductive particles when electrically connecting the electrodes, thereby further improving the conductivity between the electrodes.
- the average particle diameter of the conductive particles may be 1 ⁇ m or more, 2 ⁇ m or more, or 2.5 ⁇ m or more, from the viewpoint of excellent dispersibility and conductivity.
- the average particle diameter of the conductive particles may be 20 ⁇ m or less, 15 ⁇ m or less, 10 ⁇ m or less, 8 ⁇ m or less, 6 ⁇ m or less, 5.5 ⁇ m or less, or 5 ⁇ m or less, from the viewpoint of ensuring insulation between adjacent electrodes. From these viewpoints, the average particle diameter of the conductive particles may be 1 to 20 ⁇ m, 1 to 15 ⁇ m, 1 to 10 ⁇ m, 1 to 8 ⁇ m, or 1 to 6 ⁇ m.
- the average particle diameter of the conductive particles is determined by observing 300 conductive particles contained in the adhesive composition using a scanning electron microscope (SEM) to measure the particle diameter of each conductive particle, and averaging the particle diameters of the 300 conductive particles. Note that if the conductive particles are not spherical, the particle diameter of the conductive particles is the diameter of a circle circumscribing the conductive particles in the image observed using the SEM.
- SEM scanning electron microscope
- the particle density of the conductive particles in the adhesive composition may be 100 particles/mm 2 or more, 1000 particles/mm 2 or more, or 3000 particles/mm 2 or more, from the viewpoint of obtaining a stable connection resistance.
- the particle density of the conductive particles in the adhesive composition may be 100,000 particles/mm 2 or less, 50,000 particles/mm 2 or less, or 30,000 particles/mm 2 or less, from the viewpoint of ensuring insulation between adjacent electrodes. From these viewpoints, the particle density of the conductive particles in the adhesive composition may be 100 to 100,000 particles/mm 2 , 1000 to 50,000 particles/mm 2 , or 3000 to 30,000 particles/mm 2 .
- the conductive particle content may be 10% by mass or more, 20% by mass or more, or 25% by mass or more, based on the total mass of the adhesive composition.
- the conductive particle content may be 50% by mass or less, 40% by mass or less, or 35% by mass or less, based on the total mass of the adhesive composition.
- the content of the conductive particles may be 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, or 70 parts by mass or more based on 100 parts by mass of the cationic polymerizable compound.
- the content of the conductive particles may be 200 parts by mass or less, 150 parts by mass or less, 120 parts by mass or less, or 100 parts by mass or less based on 100 parts by mass of the cationic polymerizable compound.
- the adhesive composition may further contain other components in addition to the above components.
- the other components may include a thermoplastic resin, a coupling agent, a filler, a stabilizer, a colorant, an antioxidant, a curing agent other than the curing agent containing pyridinium salt A, and the like.
- the adhesive composition may further contain a radically polymerizable compound and a radical polymerization initiator.
- the adhesive composition may further contain a thermoplastic resin.
- the adhesive composition is easily formed into a film by containing a thermoplastic resin.
- the thermoplastic resin include phenoxy resin, epoxy resin, polyester resin, polyamide resin, polyurethane resin, polyester urethane resin, acrylic rubber, etc. These may be used alone or in combination of two or more. If the epoxy equivalent of the epoxy resin is 400 g/eq or more, it is treated as a thermoplastic resin.
- the weight average molecular weight (Mw) of the thermoplastic resin may be, for example, 5,000 or more, 10,000 or more, 20,000 or more, or 40,000 or more, and may be 200,000 or less, 100,000 or less, 80,000 or less, or 60,000 or less.
- the weight average molecular weight of the thermoplastic resin is measured by gel permeation chromatography (GPC) and converted using a calibration curve based on standard polystyrene.
- the content of the thermoplastic resin may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, based on the total mass of the adhesive composition.
- the content of the thermoplastic resin may be 60% by mass or less, 50% by mass or less, or 40% by mass or less, based on the total mass of the adhesive composition.
- the content of the thermoplastic resin may be 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, or 60 parts by mass or more based on 100 parts by mass of the cationic polymerizable compound.
- the content of the thermoplastic resin may be 150 parts by mass or less, 120 parts by mass or less, 100 parts by mass or less, 80 parts by mass or less, 60 parts by mass or less, 40 parts by mass or less, or 20 parts by mass or less based on 100 parts by mass of the cationic polymerizable compound.
- the adhesive composition may further contain a coupling agent.
- the coupling agent may be a silane coupling agent, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysi
- the content of the coupling agent may be 0.5% by mass or more, 1% by mass or more, or 2% by mass or more, based on the total mass of the adhesive composition.
- the content of the coupling agent may be 15% by mass or less, 10% by mass or less, or 5% by mass or less, based on the total mass of the adhesive composition.
- the content of the coupling agent may be 1 part by mass or more, 3 parts by mass or more, or 5 parts by mass or more based on 100 parts by mass of the cationic polymerizable compound.
- the content of the coupling agent may be 30 parts by mass or less, 20 parts by mass or less, 10 parts by mass or less, or 8 parts by mass or less based on 100 parts by mass of the cationic polymerizable compound.
- the adhesive composition may further contain a filler. By containing the filler, the adhesive composition can further improve the connection reliability.
- the filler may be a non-conductive filler (e.g., non-conductive particles).
- the filler may be either an inorganic filler or an organic filler.
- inorganic fillers include metal oxide particles such as silica particles, alumina particles, silica-alumina particles, titania particles, and zirconia particles; metal nitride particles, etc. These may be used alone or in combination of two or more types.
- organic fillers examples include silicone particles, methacrylate-butadiene-styrene particles, acrylic-silicone particles, polyamide particles, and polyimide particles. These may be used alone or in combination of two or more.
- the filler may be an inorganic filler or silica particles from the viewpoint of improving the film formability and the reliability of the connection structure.
- the silica particles may be crystalline silica particles or non-crystalline silica particles, and these silica particles may be synthetic products.
- the silica may be synthesized by a dry method or a wet method.
- the silica particles may include at least one type selected from the group consisting of fumed silica particles and sol-gel silica particles.
- the silica particles may be surface-treated silica particles from the viewpoint of excellent dispersibility in the adhesive component.
- the surface-treated silica particles are, for example, silica particles whose surface hydroxyl groups have been hydrophobized with a silane compound or a silane coupling agent.
- the surface-treated silica particles may be, for example, silica particles surface-treated with a silane compound such as an alkoxysilane compound, a disilazane compound, or a siloxane compound, or may be silica particles surface-treated with a silane coupling agent.
- Alkoxysilane compounds include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dimethoxydiphenylsilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and 3,3,3-trifluoropropyltrimethoxysilane.
- disilazane compounds examples include 1,1,1,3,3,3-hexamethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-bis(3,3,3-trifluoropropyl)-1,1,3,3-tetramethyldisilazane, and 1,3-divinyl-1,1,3,3-tetramethyldisilazane.
- Siloxane compounds include tetradecamethylcycloheptasiloxane, decamethylcyclopentasiloxane, hexaphenylcyclosiloxane, octadecamethylcyclononasiloxane, hexadecamethylcyclooctasiloxane, dodecamethylcyclohexasiloxane, octaphenylcyclotetrasiloxane, hexamethylcyclotrisiloxane, heptaphenyldisiloxane, tetradecamethylhexasiloxane, dodecamethylpentasiloxane, hexa Methyldisiloxane, decamethyltetrasiloxane, hexamethoxydisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, 1,3-vinylte
- Silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(amino ethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-
- Silica particles that have been surface-treated with a silane compound or a silane coupling agent may be surface-treated with a silane compound such as 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, or trimethoxyphenylsilane to further hydrophobize the hydroxyl group residues on the surface of the silica particles.
- a silane compound such as 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, or trimethoxyphenylsilane to further hydrophobize the hydroxyl group residues on the surface of the silica particles.
- the surface-treated silica particles may contain at least one selected from the group consisting of a reaction product (hydrolysis product) of silica and trimethoxyoctylsilane, a reaction product of silica and dimethylsiloxane, a reaction product of silicon dioxide or silica and dichloro(dimethyl)silane, a reaction product (hydrolysis product) of silica and bis(trimethylsilyl)amine, and a reaction product of silica and hexamethyldisilazane, or may contain at least one selected from the group consisting of a reaction product of silica and trimethoxyoctylsilane, and a reaction product of silica and bis(trimethylsilyl)amine, from the viewpoint of easily controlling the fluidity when the adhesive film for circuit connection is compressed when the adhesive composition is used as an adhesive film for circuit connection, and from the viewpoint of improving the mechanical properties and water resistance of the connection structure after compression.
- the filler content may be 1 mass% or more, 3 mass% or more, or 5 mass% or more, based on the total mass of the adhesive composition.
- the filler content may be 50 mass% or less, 40 mass% or less, or 35 mass% or less, based on the total mass of the adhesive composition.
- the amount of the filler may be 1 part by mass or more, 5 parts by mass or more, or 10 parts by mass or more based on 100 parts by mass of the cationic polymerizable compound.
- the amount of the filler may be 200 parts by mass or less, 150 parts by mass or less, or 100 parts by mass or less based on 100 parts by mass of the cationic polymerizable compound.
- the radical polymerizable compound may be an acrylic compound.
- the acrylic compound include (meth)acrylic acid compounds, (meth)acrylate compounds, and imide compounds thereof. These may be used in either a monomer or oligomer state, or a combination of a monomer and an oligomer.
- the radical polymerizable compound may be used alone or in combination of two or more types.
- Acrylic compounds include, for example, alkyl (meth)acrylate compounds such as methyl acrylate, ethyl acrylate, isopropyl acrylate, and isobutyl acrylate; polyol poly(meth)acrylate compounds such as ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, and tetramethylolmethane tetraacrylate; aryloxy-hydroxyalkyl (meth)acrylate compounds such as 2-hydroxy-1,3-diacryloxypropane, 2,2-bis[4-(acryloxymethoxy)phenyl]propane, and 2,2-bis[4-(acryloxypolyethoxy)phenyl]propane; dicyclopentenyl acrylate, tricyclodecanyl acrylate, and tris(acryloyloxyethyl)isocyanurate.
- alkyl (meth)acrylate compounds such as methyl acrylate, ethyl
- the radical polymerization initiator may be one that generates free radicals by light or heat.
- examples of the radical polymerization initiator include organic peroxides and azo compounds.
- examples of the organic peroxides include peroxy esters, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyketals, hydroperoxides, and silyl peroxides.
- the radical polymerization initiator may be used alone or in combination of two or more types.
- Peroxy esters include cumyl peroxy neodecanoate, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxy 2-ethylhexanoate, L-hexyl peroxy 2-ethylhexanoate, L- Examples include butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane
- dialkyl peroxides examples include ⁇ , ⁇ '-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, etc.
- hydroperoxides examples include diisopropylbenzene hydroperoxide and cumene hydroperoxide, etc.
- Diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoylperoxytoluene, and benzoyl peroxide.
- peroxydicarbonates examples include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxy peroxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutylperoxy)dicarbonate.
- peroxyketals include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-(t-butylperoxy)cyclododecane, and 2,2-bis(t-butylperoxy)decane.
- silyl peroxides include t-butyltrimethylsilyl peroxide, bis(t-butyl)dimethylsilyl peroxide, t-butyltrivinylsilyl peroxide, bis(t-butyl)divinylsilyl peroxide, tris(t-butyl)vinylsilyl peroxide, t-butyltriallylsilyl peroxide, bis(t-butyl)diallylsilyl peroxide, and tris(t-butyl)allylsilyl peroxide.
- the adhesive composition may be in the form of a film. That is, another embodiment of the present disclosure is an adhesive film for circuit connection, which contains a cationic polymerizable compound containing an epoxy compound X and a curing agent containing a pyridinium salt A.
- the adhesive film for circuit connection may contain conductive particles.
- the particle density of the conductive particles in the adhesive film for circuit connection may be 100 particles/ mm2 or more, 1000 particles/ mm2 or more, or 3000 particles/ mm2 or more, from the viewpoint of obtaining a stable connection resistance.
- the particle density of the conductive particles in the adhesive film for circuit connection may be 100,000 particles/ mm2 or less, 50,000 particles/ mm2 or less, or 30,000 particles/mm2 or less , from the viewpoint of ensuring insulation between adjacent electrodes. From these viewpoints, the particle density of the conductive particles in the adhesive film for circuit connection may be 100 to 100,000 particles/ mm2 , 1000 to 50,000 particles/ mm2 , or 3000 to 30,000 particles/ mm2 .
- the conductive particle content may be 10% by mass or more, 20% by mass or more, or 25% by mass or more, based on the total mass of the circuit connection adhesive film.
- the conductive particle content may be 50% by mass or less, 40% by mass or less, or 35% by mass or less, based on the total mass of the circuit connection adhesive film.
- the content of the conductive particles may be 10 parts by mass or more, 30 parts by mass or more, 50 parts by mass or more, or 70 parts by mass or more based on 100 parts by mass of the cationic polymerizable compound.
- the content of the conductive particles may be 200 parts by mass or less, 150 parts by mass or less, 120 parts by mass or less, or 100 parts by mass or less based on 100 parts by mass of the cationic polymerizable compound.
- the content of the cationic polymerizable compound in the circuit connection adhesive film may be 10% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more, based on the total mass of the circuit connection adhesive film, from the viewpoint of ensuring sufficient curability of the circuit connection adhesive film.
- the content of the cationic polymerizable compound in the circuit connection adhesive film may be 60% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less, based on the total mass of the circuit connection adhesive film, from the viewpoint of ensuring formability of the circuit connection adhesive film. From these viewpoints, the content of the cationic polymerizable compound in the circuit connection adhesive film may be 10 to 60% by mass, based on the total mass of the circuit connection adhesive film.
- the content of epoxy compound X in the circuit connection adhesive film may be 5 mass% or more, 10 mass% or more, 12 mass% or more, or 15 mass% or more, based on the total mass of the circuit connection adhesive film, from the viewpoint of ensuring sufficient curing properties of the circuit connection adhesive film.
- the content of epoxy compound X in the circuit connection adhesive film may be 50 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less, based on the total mass of the circuit connection adhesive film, from the viewpoint of ensuring formability of the circuit connection adhesive film. From these viewpoints, the content of epoxy compound X in the circuit connection adhesive film may be 10 to 50 mass%, based on the total mass of the circuit connection adhesive film.
- the total content of compounds A to D in the circuit connection adhesive film may be 5 mass% or more, 10 mass% or more, 12 mass% or more, or 15 mass% or more, based on the total mass of the circuit connection adhesive film, from the viewpoint of ensuring sufficient curability of the circuit connection adhesive film.
- the total content of compounds A to D in the circuit connection adhesive film may be 50 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less, based on the total mass of the circuit connection adhesive film, from the viewpoint of ensuring formability of the circuit connection adhesive film. From these viewpoints, the total content of compounds A to D in the circuit connection adhesive film may be 5 to 50 mass% or 10 to 50 mass%, based on the total mass of the circuit connection adhesive film.
- the content of the curing agent in the circuit connection adhesive film may be 1 mass % or more, 2 mass % or more, 3 mass % or more, 4 mass % or more, or 5 mass % or more, based on the total mass of the circuit connection adhesive film, from the viewpoint of sufficiently promoting the curing reaction.
- the content of the curing agent in the circuit connection adhesive film may be 20 mass % or less, 15 mass % or less, 10 mass % or less, 8 mass % or less, or 6 mass % or less, based on the total mass of the circuit connection adhesive film, from the viewpoint of improving the physical properties of the cured product. From these viewpoints, the content of the curing agent in the circuit connection adhesive film may be 1 to 20 mass %, based on the total mass of the circuit connection adhesive film.
- the content of the curing agent in the circuit connection adhesive film may be 1 mass % or more, 3 mass % or more, 5 mass % or more, or 7 mass % or more, based on the total mass of the circuit connection adhesive film excluding the conductive particles, from the viewpoint of sufficiently promoting the curing reaction.
- the content of the curing agent in the circuit connection adhesive film may be 30 mass % or less, 25 mass % or less, 20 mass % or less, 15 mass % or less, or 10 mass % or less, based on the total mass of the circuit connection adhesive film excluding the conductive particles, from the viewpoint of improving the physical properties of the cured product. From these viewpoints, the content of the curing agent in the circuit connection adhesive film may be 1 to 30 mass %, based on the total mass of the circuit connection adhesive film excluding the conductive particles.
- the content of the curing agent in the circuit connection adhesive film may be 1 mass % or more, 3 mass % or more, 5 mass % or more, or 7 mass % or more, based on the total mass of the circuit connection adhesive film excluding the conductive particles and filler, from the viewpoint of sufficiently promoting the curing reaction.
- the content of the curing agent in the circuit connection adhesive film may be 30 mass % or less, 25 mass % or less, 20 mass % or less, 15 mass % or less, or 10 mass % or less, based on the total mass of the circuit connection adhesive film excluding the conductive particles and filler, from the viewpoint of improving the physical properties of the cured product. From these viewpoints, the content of the curing agent in the circuit connection adhesive film may be 1 to 30 mass %, based on the total mass of the circuit connection adhesive film excluding the conductive particles and filler.
- the thermoplastic resin content in the circuit connection adhesive film may be 5 mass% or more, 10 mass% or more, or 15 mass% or more, based on the total mass of the circuit connection adhesive film.
- the thermoplastic resin content in the circuit connection adhesive film may be 40 mass% or less, 30 mass% or less, or 20 mass% or less, based on the total mass of the circuit connection adhesive film.
- the content of the coupling agent in the circuit connection adhesive film may be 0.5 mass% or more, 1 mass% or more, or 1.5 mass% or more, based on the total mass of the circuit connection adhesive film.
- the content of the coupling agent in the circuit connection adhesive film may be 10 mass% or less, 5 mass% or less, or 3 mass% or less, based on the total mass of the circuit connection adhesive film.
- the filler content in the circuit connection adhesive film may be 1 mass % or more, 3 mass % or more, or 5 mass % or more, based on the total mass of the circuit connection adhesive film.
- the filler content in the circuit connection adhesive film may be 50 mass % or less, 40 mass % or less, or 35 mass % or less, based on the total mass of the circuit connection adhesive film.
- the content of each component of the circuit-connecting adhesive film based on 100 parts by mass of the cationic polymerizable compound may be within the same range as the content of each component of the above-mentioned adhesive composition based on 100 parts by mass of the cationic polymerizable compound.
- the circuit connection adhesive film may be a single layer, or may have a multilayer structure in which multiple layers are laminated.
- the circuit connection adhesive film may have, for example, a first adhesive layer containing a cationic polymerizable compound containing an epoxy compound X and a curing agent containing a pyridinium salt A, and a second adhesive layer other than the first adhesive layer. That is, the circuit connection adhesive film may have a first adhesive layer and a second adhesive layer laminated on the first adhesive layer. At least one of the first adhesive layer and the second adhesive layer may contain a cationic polymerizable compound containing an epoxy compound X, a curing agent containing a pyridinium salt A, and conductive particles.
- the content of each of the above components in each layer may be within the above content range based on the total mass of each layer.
- the circuit connection adhesive film may have multiple regions with different types and contents of components.
- the circuit connection adhesive film may have, for example, a first region and a second region disposed on the first region, and the first region may be a region containing a cationic polymerizable compound containing an epoxy compound X and a curing agent containing a pyridinium salt A. That is, the circuit connection adhesive film may have a first region that is a region formed from a first adhesive composition containing a cationic polymerizable compound containing an epoxy compound X and a curing agent containing a pyridinium salt A, and a second region that is a region formed from a second adhesive composition disposed on the first region.
- the content of each of the above components in each region may be within the above content range based on the total mass of each region.
- the circuit connection adhesive film may be provided on a substrate (e.g., a PET film) or the like.
- the circuit connection adhesive film with a substrate can be produced, for example, by applying an adhesive composition containing conductive particles onto a substrate using a knife coater, roll coater, applicator, comma coater, die coater, or the like.
- FIG. 1 is a schematic cross-sectional view showing an adhesive film for circuit connection according to one embodiment.
- the adhesive film for circuit connection 1 is composed of a single layer consisting of an adhesive component 2 and conductive particles 3 dispersed in the adhesive component 2.
- the adhesive component 2 contains at least a cationic polymerizable compound containing an epoxy compound X and a curing agent containing a pyridinium salt A.
- the adhesive film for circuit connection 1 may be in an uncured state or in a partially cured state.
- the thickness of the circuit connection adhesive film 1 may be, for example, 3 ⁇ m or more or 5 ⁇ m or more, and 30 ⁇ m or less or 20 ⁇ m or less.
- the adhesive film for circuit connection may have a multilayer structure having two or more layers.
- the adhesive film for circuit connection 1 may have a two-layer structure including a layer containing conductive particles 3A (a first adhesive layer consisting of adhesive component 2A and conductive particles 3A dispersed in adhesive component 2A) 1A and a layer not containing conductive particles (a second adhesive layer consisting of adhesive component 2B) 1B.
- the first adhesive layer 1A may be a layer consisting of an adhesive composition (first adhesive composition) containing a cationic polymerizable compound containing epoxy compound X, a curing agent containing pyridinium salt A, and conductive particles.
- the second adhesive layer 1B may be a layer consisting of an adhesive composition (second adhesive composition) containing a cationic polymerizable compound containing epoxy compound X and a curing agent containing pyridinium salt A.
- the type, content, etc. of each component contained in the second adhesive layer 1B may be the same as or different from that of the first adhesive layer 1A.
- the first adhesive layer 1A and the second adhesive layer 1B of the circuit connection adhesive film 1 may each be in an uncured state or in a partially cured state.
- the thickness of the first adhesive layer 1A may be, for example, 1 ⁇ m or more or 3 ⁇ m or more, and 15 ⁇ m or less or 10 ⁇ m or less.
- the thickness of the second adhesive layer 1B may be, for example, 1 ⁇ m or more or 3 ⁇ m or more, and 20 ⁇ m or less or 15 ⁇ m or less.
- the thickness of the first adhesive layer 1A may be the same as or different from the thickness of the second adhesive layer 1B.
- the ratio of the thickness of the first adhesive layer 1A to the thickness of the second adhesive layer 1B may be 0.1 or more or 0.3 or more, and 1.5 or less or 0.5 or less.
- the above-mentioned circuit connection adhesive film may be an anisotropic conductive adhesive film (anisotropic conductive film), or it may be a conductive adhesive film that does not have anisotropic conductivity.
- connection structure comprising a first circuit member having a first electrode, a second circuit member having a second electrode, and a connection portion disposed between the first circuit member and the second circuit member and electrically connecting the first electrode and the second electrode to each other, wherein the connection portion comprises a cured product of the above-mentioned adhesive film for circuit connection.
- Figure 3 is a schematic cross-sectional view showing one embodiment of a connection structure.
- the structure 10 includes a first circuit member 4 and a second circuit member 5 that face each other, and a connection portion 6 that connects the first circuit member 4 and the second circuit member 5 between the first circuit member 4 and the second circuit member 5.
- the first circuit member 4 includes a first circuit board 41 and a first electrode 42 formed on the main surface 41a of the first circuit board 41.
- the second circuit member 5 includes a second circuit board 51 and a second electrode 52 formed on the main surface 51a of the second circuit board 51.
- the first circuit member 4 and the second circuit member 5 are not particularly limited as long as they are members on which electrodes that require electrical connection are formed.
- members on which electrodes are formed include inorganic substrates such as semiconductors, glass, and ceramics; polyimide substrates such as TCP, FPC, and COF; substrates on which electrodes are formed on films such as polycarbonate, polyester, and polyethersulfone; printed wiring boards, and the like; and a combination of two or more of these may be used.
- the connection portion 6 includes a cured product of the circuit connection adhesive film 1, and contains an insulating material 7, which is a cured product of the adhesive component 2, and conductive particles 3.
- the conductive particles 3 may be disposed not only between the opposing first electrode 42 and second electrode 52, but also between the main surface 41a of the first circuit board 41 and the main surface 51a of the second circuit board 51.
- the first electrode 42 and the second electrode 52 are electrically connected via the conductive particles 3. That is, the conductive particles 3 are in contact with both the first electrode 42 and the second electrode 52.
- the opposing first electrode 42 and second electrode 52 are electrically connected via the conductive particles 3. This sufficiently reduces the connection resistance between the first electrode 42 and the second electrode 52. This allows the current to flow smoothly between the first electrode 42 and the second electrode 52, allowing the functions of the first circuit member 4 and the second circuit member 5 to be fully exerted.
- Another embodiment of the present disclosure is a method for producing a connection structure, comprising the steps of interposing the above-mentioned adhesive film for circuit connection between a first circuit member having a first electrode and a second circuit member having a second electrode, and thermocompressing the first circuit member and the second circuit member to electrically connect the first electrode and the second electrode to each other.
- FIG. 4 is a schematic cross-sectional view showing one embodiment of a method for manufacturing a connection structure.
- a first circuit member 4 and a circuit connection adhesive film 1 are prepared.
- the circuit connection adhesive film 1 is placed on the main surface 41a of the first circuit member 4.
- the circuit connection adhesive film 1 is laminated on a substrate (not shown)
- the laminate is placed on the first circuit member 4 so that the circuit connection adhesive film 1 side of the substrate faces the first circuit member 4.
- the circuit connection adhesive film 1 has a first adhesive layer 1A and a second adhesive layer 1B as shown in FIG. 2, it is preferable to place the adhesive layer (first adhesive layer 1A) containing conductive particles in contact with the main surface 41a of the first circuit member 4 from the viewpoint of increasing the number of conductive particles captured between the opposing electrodes.
- circuit connection adhesive film 1 is pressed in the directions of arrows A and B in FIG. 4(a) to temporarily connect the circuit connection adhesive film 1 to the first circuit member 4 (see FIG. 4(b)). At this time, heating may be performed in addition to the pressing.
- the second circuit member 5 is further placed on the circuit connection adhesive film 1 placed on the first circuit member 4 with the second electrode 52 facing the first circuit member 4 (i.e., the first electrode 42 and the second electrode 52 are placed opposite each other, and the circuit connection adhesive film 1 is interposed between the first circuit member 4 and the second circuit member 5). If the circuit connection adhesive film 1 is laminated on a substrate (not shown), the substrate is peeled off and then the second circuit member 5 is placed on the circuit connection adhesive film 1.
- circuit connection adhesive film 1 is thermocompressed in the directions of arrows A and B in FIG. 4(c). This hardens the circuit connection adhesive film 1, and completes the electrical connection between the first electrode 42 and the second electrode 52. As a result, a structure 10 as shown in FIG. 3 is obtained.
- the adhesive component 2 hardens and becomes an insulating material 7 while the distance between the first electrode 42 and the second electrode 52 is kept sufficiently small, and the first circuit member 4 and the second circuit member 5 are firmly connected via the connection portion 6. Furthermore, in the structure 10, the adhesive strength remains sufficiently high for a long period of time. Therefore, in the structure 10, the change over time in the distance between the first electrode 42 and the second electrode 52 is sufficiently suppressed, and the long-term reliability of the electrical properties between the first electrode 42 and the second electrode 52 is excellent.
- the resulting compound was measured by nuclear magnetic resonance spectroscopy ( 1 H-NMR, JNM-ECX400II, manufactured by JEOL Ltd.), and the following spectral data was obtained. From the 1 H-NMR measurement, it was confirmed that the resulting compound was 2-cyano-1-(2,4,6-trimethylbenzyl)pyridinium tetrakis(pentafluorophenyl)borate having the following structure.
- a high performance liquid chromatograph GP8020 manufactured by Tosoh Corporation, column: Gelpack GL-A150S and GLA160S manufactured by Showa Denko Materials K.K., eluent: tetrahydrofuran, flow rate: 1.0 mL/min
- a layer of nickel was formed on the surface of the crosslinked polystyrene particles to a thickness of 0.15 ⁇ m, to obtain conductive particles having an average particle size of 3.0 ⁇ m.
- a first adhesive composition for forming a first adhesive layer and a second adhesive composition for forming a second adhesive layer were prepared by mixing the components in the amounts (unit: parts by mass) shown in Table 1.
- the details of each component in Table 1 are as follows, and the amount of each component in the table represents the amount of non-volatile content.
- Cationic polymerizable compound A1 bisphenol A type epoxy resin (bifunctional epoxy resin, manufactured by Mitsubishi Chemical Corporation, product name: YL980, epoxy equivalent: 180 to 190 g/eq)
- A2 Naphthalene-type epoxy resin (tetrafunctional epoxy resin, manufactured by DIC Corporation, product name: HP4700, epoxy equivalent: 165 g/eq, solid at room temperature)
- A3 Trisphenolmethane type epoxy resin (multifunctional epoxy resin, manufactured by Mitsubishi Chemical Corporation, product name: jER1032H60, epoxy equivalent: 163 to 175 g/eq, solid at room temperature)
- A4 Tetrakisphenolmethane type epoxy resin (tetrafunctional epoxy resin, manufactured by Mitsubishi Chemical Corporation, product name: jER1031S, epoxy equivalent: 180 to 220 g/eq, solid at room temperature)
- A5 Bisphenol A type epoxy resin (tetrafunctional epoxy resin, epoxy resin having two glycidyl groups and two glycidyloxy groups, manufactured by
- the second adhesive composition was applied onto the substrate (PET film) to form a second adhesive layer on the substrate. Furthermore, the first adhesive composition was applied onto the second adhesive layer to form a first adhesive layer, producing an adhesive film for circuit connection in which the first adhesive layer, the second adhesive layer, and the substrate were laminated in this order.
- the thickness of the first adhesive layer of the adhesive film for circuit connection was 7 ⁇ m
- the thickness of the second adhesive layer was 7 ⁇ m.
- an alkali-free glass substrate (OA-11, manufactured by Nippon Electric Glass Co., Ltd., outer dimensions: 38 mm x 28 mm, thickness: 0.3 mm) was prepared on the surface of which was formed a wiring pattern of AlNd (100 nm)/Mo (50 nm)/ITO (100 nm) (pattern width: 19 ⁇ m, space between electrodes: 5 ⁇ m).
- an IC chip (outer dimensions: 0.9 mm x 20.3 mm, thickness: 0.3 mm, bump electrode size: 70 ⁇ m x 12 ⁇ m, space between bump electrodes: 12 ⁇ m, bump electrode thickness: 8 ⁇ m) was prepared in which bump electrodes were arranged in two rows in a staggered pattern.
- a connection structure was prepared using each circuit connection adhesive film of each Example and Comparative Example.
- the first adhesive layer of the circuit connection adhesive film was placed on the first circuit member.
- a thermocompression bonding device manufactured by Ohashi Manufacturing Co., Ltd.
- the circuit connection adhesive film was attached to the first circuit member by heating and pressing for 1 second under conditions of 60 ° C. and 0.98 MPa (10 kgf / cm 2 ).
- the substrate on the opposite side of the circuit connection adhesive film from the first circuit member was peeled off, and the bump electrodes of the first circuit member and the circuit electrodes of the second circuit member were aligned.
- the second adhesive layer of the circuit connection adhesive film was attached to the second circuit member by heating and pressing at 60 MPa for 5 seconds at the mounting temperature shown in Table 2 on a pedestal heated to 90 ° C. via a PTFE sheet having a thickness of 50 ⁇ m as a buffer material, to prepare a connection structure.
- the mounting temperature was the highest temperature actually measured of the adhesive film for circuit connection, and the pressure was a value calculated with respect to the total area of the surface of the bump electrodes of the second circuit member facing the first circuit member.
- ⁇ Appearance evaluation> The appearance after the HAST test was evaluated.
- the HAST test was performed by setting the device in an accelerated life tester (manufactured by Hirayama Manufacturing Co., Ltd., product name: PC-242HSR2, conditions: 110°C/85% RH/150 hours).
- the appearance was evaluated as follows: a peeled area of the circuit connection adhesive film was less than 1% of the area of the adhesive surface, 1% or more and less than 10%, 10% or more and less than 50%, and 50% or more.
- the evaluation results are shown in Table 2.
- the adhesive composition contains an epoxy compound that is trifunctional or higher and has an epoxy equivalent of more than 100 g/eq and 250 g/eq or less as a cationic polymerizable compound, and a pyridinium salt that has a benzyl group at the 1st position and an electron-withdrawing group at the 2nd position, in which the benzyl group has an electron-donating group, as a curing agent.
- This allows mounting at low temperatures (e.g., 120°C) to high temperatures (e.g., 150°C), and it has been confirmed that the adhesive composition has excellent appearance and little generation of bubbles even after HAST testing in both low-temperature and high-temperature mounting.
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Abstract
Description
[1]カチオン重合性化合物と、硬化剤と、を含有し、
前記カチオン重合性化合物が、3官能以上であり、且つ、エポキシ当量が100g/eq超250g/eq以下であるエポキシ化合物を含み、
前記硬化剤が、ピリジニウム塩を含有し、
前記ピリジニウム塩が、1位にベンジル基を有し、且つ、2位に電子求引基を有し、
前記ベンジル基が電子供与基を有する、接着剤組成物。
[2]前記エポキシ化合物が芳香環を有する、[1]に記載の接着剤組成物。
[3]前記エポキシ化合物が室温で固体である、[1]又は[2]に記載の接着剤組成物。
[4]前記カチオン重合性化合物が、トリスフェノールメタン構造を有するエポキシ化合物、ビスフェノール構造を有し、且つ、グリシジル基とグリシジルオキシ基と、を有するエポキシ化合物、4価の有機基と、前記有機基に結合した芳香族環と、を有し、前記芳香族環がエポキシ基を含む置換基を有するエポキシ化合物、及び、ナフタレン構造を有するエポキシ化合物からなる群より選ばれる少なくとも一種を含む、[1]~[3]のいずれか一つに記載の接着剤組成物。
[5]前記電子求引基が、シアノ基又はハロゲノ基である、[1]~[4]のいずれか一つに記載の接着剤組成物。
[6]前記電子供与基が、アルキル基又はアルコキシ基である、[1]~[5]のいずれか一つに記載の接着剤組成物。
[7]前記ベンジル基が有する前記電子供与基の数が3であり、
前記電子供与基がアルキル基である、[1]~[6]のいずれか一つに記載の接着剤組成物。
[8]前記ピリジニウム塩が、ピリジニウムカチオンと、アニオンと、を含み、
前記アニオンがB(C6F5)4 -である、[1]~[7]のいずれか一つに記載の接着剤組成物。
[9]導電粒子を更に含有する、[1]~[8]のいずれか一つに記載の接着剤組成物。
[10][1]~[9]のいずれか一つに記載の接着剤組成物により形成された接着剤層を備える、回路接続用接着剤フィルム。
[11]第一の接着剤層と、前記第一の接着剤層上に積層された第二の接着剤層と、を備え、
前記第一の接着剤層及び前記第二の接着剤層の少なくとも一方が、[1]~[9]のいずれか一つに記載の接着剤組成物により形成された層である、回路接続用接着剤フィルム。
[12]第一の電極を有する第一の回路部材と、
第二の電極を有する第二の回路部材と、
前記第一の回路部材及び前記第二の回路部材の間に配置され、前記第一の電極及び前記第二の電極を互いに電気的に接続する接続部と、
を備え、
前記接続部が、[10]又は[11]に記載の回路接続用接着剤フィルムの硬化物を含む、接続構造体。
[13]第一の電極を有する第一の回路部材と、第二の電極を有する第二の回路部材との間に、[10]又は[11]に記載の回路接続用接着剤フィルムを介在させ、前記第一の回路部材及び前記第二の回路部材を熱圧着して、前記第一の電極及び前記第二の電極を互いに電気的に接続する工程を備える、接続構造体の製造方法。
本開示の一実施形態は、カチオン重合性化合物と、硬化剤と、を含有する接着剤組成物である。カチオン重合性化合物は、3官能以上であり、且つ、エポキシ当量が100g/eq超250g/eq以下であるエポキシ化合物を少なくとも含む。硬化剤は、ピリジニウム塩を少なくとも含有し、当該ピリジニウム塩は、1位にベンジル基を有し、且つ、2位に電子求引基を有し、ベンジル基が電子供与基を有する。
カチオン重合性化合物は、例えば、加熱することによって硬化剤と反応して、架橋する化合物であってよく、3官能以上であり、且つ、エポキシ当量が100g/eq超250g/eq以下であるエポキシ化合物(このようなエポキシ化合物を「エポキシ化合物X」ともいう)を少なくとも含む。3官能以上のエポキシ化合物とは、エポキシ基の数が3以上のエポキシ化合物を意味する。エポキシ当量は、JIS K7236に準拠して測定される値を意味する。
硬化剤は、1位にベンジル基を有し、且つ、2位に電子求引基を有し、ベンジル基が電子供与基を有するピリジニウム塩(以下、このようなピリジニウム塩を「ピリジニウム塩A」ともいう)を含む。接着剤組成物が、カチオン重合性化合物としてエポキシ化合物Xを含み、硬化剤として、ピリジニウム塩Aを含有することにより、低温(例えば、120℃)から高温(例えば、150℃)にかけて実装可能であり、且つ、低温実装時及び高温実装時のいずれの場合においても、HAST試験後であっても外観が優れ、気泡の発生が少ない接着剤組成物を得ることができる。
接着剤組成物は、導電粒子を含有していてもよい。導電粒子としては、導電性を有する粒子であれば特に制限されず、金、銀、パラジウム、ニッケル、銅、はんだ等の金属で構成された金属粒子;導電性カーボンで構成された導電性カーボン粒子;非導電性のガラス、セラミック、プラスチック(ポリスチレン等)などを含む核と、上記の金属又は導電性カーボンを含み、核を被覆する被覆層と、を備える被覆導電粒子などが挙げられる。導電粒子は、加熱及び/又は加圧することにより変形させることが容易であり、電極同士を電気的に接続する際に、電極と導電粒子との接触面積を増加させて、電極間の導電性をより向上させることができる観点から、被覆導電粒子であってよい。
接着剤組成物は、熱可塑性樹脂を更に含有してよい。接着剤組成物は、熱可塑性樹脂を含有することで、フィルム状に形成しやすくなる。熱可塑性樹脂としては、フェノキシ樹脂、エポキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリエステルウレタン樹脂、アクリルゴム等が挙げられる。これらは、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。エポキシ樹脂のエポキシ当量が400g/eq以上であれば、熱可塑性樹脂として扱うものとする。
接着剤組成物は、カップリング剤を更に含有してよい。接着剤組成物は、カップリング剤を含有することで、接着性をより向上させることができる。カップリング剤は、シランカップリング剤であってよく、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-(メタ)アクリロキシプロピルメチルジメトキシシラン、3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルメチルジエトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、及び、これらの縮合物であってもよい。これらは、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
接着剤組成物は、充填材を更に含有してよい。接着剤組成物は、充填材を含有することで、接続信頼性をより向上させることができる。充填材としては、非導電性のフィラー(例えば、非導電粒子)が挙げられる。充填材は、無機フィラー及び有機フィラーのいずれであってもよい。
接着剤組成物は、フィルム状であってよい。すなわち、本開示の他の一実施形態は、エポキシ化合物Xを含むカチオン重合性化合物と、ピリジニウム塩Aを含有する硬化剤と、を含有する、回路接続用接着剤フィルムである。回路接続用接着剤フィルムは、導電粒子を含有していてもよい。
本開示の他の実施形態は、第一の電極を有する第一の回路部材と、第二の電極を有する第二の回路部材と、第一の回路部材及び第二の回路部材の間に配置され、第一の電極及び第二の電極を互いに電気的に接続する接続部と、を備え、接続部が、上記の回路接続用接着剤フィルムの硬化物を含む、接続構造体である。
本開示の他の実施形態は、第一の電極を有する第一の回路部材と、第二の電極を有する第二の回路部材との間に、上記の回路接続用接着剤フィルムを介在させ、第一の回路部材及び第二の回路部材を熱圧着して、第一の電極及び第二の電極を互いに電気的に接続する工程を備える、接続構造体の製造方法である。
[硬化剤B1の合成、分析]
アセトニトリル100mLと、スターラーチップと、を300mL三角フラスコに入れ、マグネチックスターラー上に設置した。2-シアノピリジン12.5g(120mmol、東京化成工業株式会社製)、2,4,6-トリメチルベンジルクロリド16.8g(100mmol、東京化成工業株式会社製)、及びヨウ化ナトリウム17.8g(119mmol、東京化成工業株式会社製)を300mL三角フラスコ中のアセトニトリルに加え、室温(25℃)で24時間反応させて結晶を得た。得られた結晶をガラスフィルターでろ過し、ガラスフィルター上の結晶をアセトン及び蒸留水により洗浄後、真空乾燥することで、29.1gの2-シアノ-1-(2,4,6-トリメチルベンジル)ピリジニウム・ヨーダイド(収率80%)を得た。
1H-NMR(400MHz,CD3OD),δ:2.26(s,6H),2.32(s,3H),6.10(s,2H),7.08(s,2H),8.25(td,1H,J=3.2,6.4Hz)8.43(d,1H,J=6.4Hz)8.77-8.82(m,2H)
ジムロート冷却管と、塩化カルシウム管と、攪拌モーターに接続されたテフロン(登録商標)攪拌棒と、を装着した3000mLの3つ口フラスコ中で、4,4’-(9-フルオレニリデン)-ジフェノール45g(シグマアルドリッチジャパン株式会社製)及び3,3’,5,5’-テトラメチルビフェノールジグリシジルエーテル50g(商品名:YX-4000H、三菱ケミカル株式会社製)をN-メチルピロリドン1000mLに溶解して反応液とした。この反応液に炭酸カリウム21gを加え、マントルヒーターで110℃に加熱しながら3時間攪拌した。攪拌後の反応液を1000mLのメタノールが入ったビーカーに滴下し、吸引ろ過することによって生成した沈殿物をろ取した。ろ取した沈殿物をさらに300mLのメタノールで3回洗浄して、フェノキシ樹脂aを75g得た。得られたフェノキシ樹脂aの分子量を高速液体クロマトグラフ(東ソー株式会社製、GP8020、カラム:昭和電工マテリアルズ株式会社製Gelpack GL-A150S及びGLA160S、溶離液:テトラヒドロフラン、流速:1.0mL/分)を用いて測定したところ、ポリスチレン換算でMn=15769、Mw=38045、Mw/Mn=2.413であった。
架橋ポリスチレン粒子の表面上に、層の厚さが0.15μmとなるようにニッケルからなる層を形成して、平均粒子径3.0μmの導電粒子を得た。
表1に示す配合量(単位:質量部)で各成分を混合し、第一の接着剤層を形成する第一の接着剤組成物、及び第二の接着剤層を形成する第二の接着剤組成物を調製した。なお、表1中の各成分の詳細は以下のとおりであり、表中の各成分の配合量は不揮発分の配合量を表す。
・カチオン重合性化合物
A1:ビスフェノールA型エポキシ樹脂(2官能エポキシ樹脂、三菱ケミカル株式会社製、商品名:YL980、エポキシ当量:180~190g/eq)
A2:ナフタレン型エポキシ樹脂(4官能エポキシ樹脂、DIC株式会社製、商品名:HP4700、エポキシ当量:165g/eq、室温で固体)
A3:トリスフェノールメタン型エポキシ樹脂(多官能エポキシ樹脂、三菱ケミカル株式会社製、商品名:jER1032H60、エポキシ当量:163~175g/eq、室温で固体)
A4:テトラキスフェノールメタン型エポキシ樹脂(4官能エポキシ樹脂、三菱ケミカル株式会社製、商品名:jER1031S、エポキシ当量:180~220g/eq、室温で固体)
A5:ビスフェノールA型エポキシ樹脂(4官能エポキシ樹脂、2つのグリシジル基と2つのグリシジルオキシ基を有するエポキシ樹脂、昭和電工株式会社製、商品名:BATG、エポキシ当量:120~128g/eq、室温で液体)
A6:ビスフェノールF型エポキシ樹脂(2官能エポキシ樹脂、三菱ケミカル株式会社製、商品名:YL983U、エポキシ当量:165~175g/eq)
A7:アラルキル骨格を有するノボラック型エポキシ樹脂(3官能エポキシ樹脂、三菱ケミカル株式会社製、商品名:YX7700、エポキシ当量:260~285g/eq、室温で固体)
A8:脂肪族エポキシ樹脂(4官能エポキシ樹脂、昭和電工株式会社製、商品名:PETG、エポキシ当量:90~100g/eq)
・硬化剤
B1:上記で合成した硬化剤
B2:スルホニウム塩(三新化学株式会社製、商品名:SI60)
・熱可塑性樹脂
C1:上記で合成したフェノキシ樹脂a
C2:エポキシ樹脂(三菱ケミカル株式会社製、商品名:jER1010、エポキシ当量:3000~5000g/eq)
・充填材
D1:表面処理されたシリカ粒子(シリカとビス(トリメチルシリル)アミンとの加水分解生成物)
D2:表面処理されたシリカ粒子(トリメトキシオクチルシランとシリカの加水分解生成物、Evonik Industries AG社製、商品名:アエロジルR805、有機溶媒で不揮発分の含有量を10質量%に希釈したものを使用)
・カップリング剤
E1:シランカップリング剤(3-グリシドキシプロピルトリメトキシシラン、商品名:KBM-403、信越化学工業株式会社製)
・導電粒子
F1:上記で作製した導電粒子
第一の回路部材として、無アルカリガラス基板(OA-11、日本電気硝子株式会社製、外形:38mm×28mm、厚さ:0.3mm)の表面に、AlNd(100nm)/Mo(50nm)/ITO(100nm)の配線パターン(パターン幅:19μm、電極間スペース:5μm)を形成したものを準備した。第二の回路部材として、バンプ電極を2列で千鳥状に配列したICチップ(外形:0.9mm×20.3mm、厚さ:0.3mm、バンプ電極の大きさ:70μm×12μm、バンプ電極間スペース:12μm、バンプ電極厚さ:8μm)を準備した。
HAST試験後の外観を評価した。HAST試験は、加速寿命試験装置(株式会社平山製作所製、商品名:PC-242HSR2、条件:110℃/85%RH/150時間)に設置し、HAST試験を実施した。外観の評価は、回路接続用接着剤フィルムの剥離面積が接着面の面積に対して1%未満であるものを評価A、1%以上10%未満であるものを評価B、10%以上50%未満であるものを評価C、50%以上であるものを評価Dとして、評価した。評価結果を表2に示す。
HAST試験後の気泡の有無を評価した。HAST試験は、加速寿命試験装置(株式会社平山製作所製、商品名:PC-242HSR2、条件:110℃/85%RH/150時間)に設置し、HAST試験を実施した。気泡の評価は、回路接続用接着剤フィルムの接着面の面積に対して、気泡が発生した箇所の面積が10%未満であるものを評価A、10%以上であるものを評価Bとして、評価した。評価結果を表2に示す。
Claims (13)
- カチオン重合性化合物と、硬化剤と、を含有し、
前記カチオン重合性化合物が、3官能以上であり、且つ、エポキシ当量が100g/eq超250g/eq以下であるエポキシ化合物を含み、
前記硬化剤が、ピリジニウム塩を含有し、
前記ピリジニウム塩が、1位にベンジル基を有し、且つ、2位に電子求引基を有し、
前記ベンジル基が電子供与基を有する、接着剤組成物。 - 前記エポキシ化合物が芳香環を有する、請求項1に記載の接着剤組成物。
- 前記エポキシ化合物が室温で固体である、請求項1に記載の接着剤組成物。
- 前記カチオン重合性化合物が、トリスフェノールメタン構造を有するエポキシ化合物、ビスフェノール構造を有し、且つ、グリシジル基とグリシジルオキシ基と、を有するエポキシ化合物、4価の有機基と、前記有機基に結合した芳香族環と、を有し、前記芳香族環がエポキシ基を含む置換基を有するエポキシ化合物、及びナフタレン構造を有するエポキシ化合物からなる群より選ばれる少なくとも一種を含む、請求項1に記載の接着剤組成物。
- 前記電子求引基が、シアノ基又はハロゲノ基である、請求項1に記載の接着剤組成物。
- 前記電子供与基が、アルキル基又はアルコキシ基である、請求項1に記載の接着剤組成物。
- 前記ベンジル基が有する前記電子供与基の数が3であり、
前記電子供与基がアルキル基である、請求項1に記載の接着剤組成物。 - 前記ピリジニウム塩が、ピリジニウムカチオンと、アニオンと、を含み、
前記アニオンがB(C6F5)4 -である、請求項1に記載の接着剤組成物。 - 導電粒子を更に含有する、請求項1に記載の接着剤組成物。
- 請求項1~9のいずれか一項に記載の接着剤組成物により形成された接着剤層を備える、回路接続用接着剤フィルム。
- 第一の接着剤層と、前記第一の接着剤層上に積層された第二の接着剤層と、を備え、
前記第一の接着剤層及び前記第二の接着剤層の少なくとも一方が、請求項1~9のいずれか一項に記載の接着剤組成物により形成された層である、回路接続用接着剤フィルム。 - 第一の電極を有する第一の回路部材と、
第二の電極を有する第二の回路部材と、
前記第一の回路部材及び前記第二の回路部材の間に配置され、前記第一の電極及び前記第二の電極を互いに電気的に接続する接続部と、
を備え、
前記接続部が、請求項10に記載の回路接続用接着剤フィルムの硬化物を含む、接続構造体。 - 第一の電極を有する第一の回路部材と、第二の電極を有する第二の回路部材との間に、請求項10に記載の回路接続用接着剤フィルムを介在させ、前記第一の回路部材及び前記第二の回路部材を熱圧着して、前記第一の電極及び前記第二の電極を互いに電気的に接続する工程を備える、接続構造体の製造方法。
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| JPH10251610A (ja) * | 1997-03-07 | 1998-09-22 | Hitachi Chem Co Ltd | 回路部材接続用接着剤 |
| JP2021185256A (ja) * | 2016-05-31 | 2021-12-09 | 昭和電工マテリアルズ株式会社 | 接着剤組成物及びフィルム状接着剤組成物 |
| JP7133746B1 (ja) * | 2021-04-16 | 2022-09-08 | 昭和電工マテリアルズ株式会社 | 硬化剤、接着剤組成物、回路接続用接着剤フィルム、接続構造体及び接続構造体の製造方法 |
| WO2023136273A1 (ja) * | 2022-01-12 | 2023-07-20 | 株式会社レゾナック | 接着剤組成物、回路接続用接着剤フィルム、及び、接続構造体の製造方法 |
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| JP2014084400A (ja) | 2012-10-23 | 2014-05-12 | Asahi Kasei E-Materials Corp | 接着フィルム |
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| JPH0243202A (ja) * | 1988-04-15 | 1990-02-13 | Koei Chem Co Ltd | 重合触媒およびそれを含有する硬化性組成物 |
| JPH10251610A (ja) * | 1997-03-07 | 1998-09-22 | Hitachi Chem Co Ltd | 回路部材接続用接着剤 |
| JP2021185256A (ja) * | 2016-05-31 | 2021-12-09 | 昭和電工マテリアルズ株式会社 | 接着剤組成物及びフィルム状接着剤組成物 |
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| WO2023136273A1 (ja) * | 2022-01-12 | 2023-07-20 | 株式会社レゾナック | 接着剤組成物、回路接続用接着剤フィルム、及び、接続構造体の製造方法 |
| WO2023136272A1 (ja) * | 2022-01-12 | 2023-07-20 | 株式会社レゾナック | 接着剤組成物、回路接続用接着剤フィルム、及び、接続構造体の製造方法 |
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